w</sub> (Da) | M<sub>n</sub> (Da) | PDI |\n| BF<sub>3</sub>.EtO<sub>2</sub> | 0.02 | 97 | 282000 | 44100 | 6.39 |\n| FeCl<sub>3</sub> | 0.1 | 90 | 45200 | 17400 | 2.60 |\n| SnCl<sub>4</sub> | 0.1 | 93 | 111000 | 25200 | 4.40 |\n| AlCl<sub>3</sub> | 0.1 | 0 | - | - | - |\n| TiCl<sub>4</sub> | 0.1 | 0 | - | - | - |\n| HBF<sub>4</sub> | 0.02 | 95 | 85000 | 22500 | 3.78 |\n| CF<sub>3</sub>SO<sub>3</sub>H | 0.1 | 92 | 165000 | 35700 | 4.62 |\n| ClSO<sub>3</sub>H | 0.1 | 0 | - | - | - |\n| CF<sub>3</sub>CO<sub>2</sub>H | 0.1 | 0 | - | - | - |\n| H<sub>2</sub>SO<sub>4</sub> | 0.1 | 0 | - | - | - |\n\nM<sub>w</sub> = weight average molecular weight, M<sub>n</sub> = number average molecular weight, PDI = polydispersity index\n\nThe analysis of the copolymers produced from reactions was conducted with gel permeation chromatography (GPC) and was calibrated with polymethacrylate polymers. The GPC analysis of the monomer (2.17) indicated a number average molecular weight (M<sub>n</sub>) of about 1500 Da.\n\nOut of the five evaluated Lewis acids, only three of the Lewis acids (BF<sub>3</sub>.EtO<sub>2</sub>, FeCl<sub>3</sub> and SnCl<sub>4</sub>) yielded the desired copolymers when (2.17) was used. On the other hand, two out of the three superacids (HBF<sub>4</sub>, CF<sub>3</sub>SO<sub>3</sub>H) were able to catalyze the copolymerization of (2.17) with THF. Meanwhile, the relatively weak acids (CF<sub>3</sub>CO<sub>2</sub>H and H<sub>2</sub>SO<sub>4</sub>) were not able to catalyze the reaction.\n\nFor all the acids that were able to catalyze the copolymerization reaction (BF$_3$.EtO$_2$, FeCl$_3$, SnCl$_4$, HBF$_4$ and CF$_3$SO$_3$H), a control reactions for each acid was conducted, where the copolymerization reaction in Figure 4.8 was conducted using the same protocols but without (2.17) (Figure 4.9). The experimental results show that ring opening polymerization of THF catalyzed by these acids do not happen without (2.17) as they failed to get any oligomeric or polymer material and end up with the starting material. This indicates that the (2.17) was needed for the ring opening polymerization of THF under reaction condition in Figure 4.8.\n\n\n\nFigure 4.9 Control reactions of ring opening polymerization of THF with acid catalysts\n\nReferring to Table 4.1, two boron based compounds (BF$_3$.EtO$_2$ and HBF$_4$) were used at lower amounts (0.02 mol equivalent per mol of epoxide group) compared to other acids (0.1 mol equivalent) because when both boron based compounds were used at higher amounts (0.1 mol equivalent), the resultant copolymers were cross-linked (gelled) polymers, which were difficult to characterize. Based on the results in Table 4.1, both boron based acids were found to be better catalysts for the copolymerization of (2.17) with THF because lower catalyst loading was possible. Furthermore, BF$_3$.Et$_2$O was chosen as the catalyst for the copolymerization of epoxidized plant oils with THF for further studies because it can produce copolymers with higher molecular weight.\n\n4.2 COPOLYMERS OF EPOXIDIZED METHYL OLEATE AND TETRAHYDROFURAN\n\nThe epoxidized methyl oleate (EMO, 2.3) was copolymerized with THF and boron trifluoride etherate as the catalyst at room temperature to yield copolymers (EMO-THF, 4.4) (Figure 4.10). The following are the properties of the copolymers (4.4) tabulated in Table 4.2.\n\n\\[\n\\begin{align*}\n\\text{n} \\quad & \\text{R}_1 \\quad \\text{O} \\\\\n& \\text{R}_2 \\quad \\text{O} \\\\\n\\text{m} \\quad & \\text{O} \\\\\n\\text{BF}_3 \\cdot \\text{Et}_2 \\text{O} \\quad & \\text{20 °C, 24 h} \\\\\n\\end{align*}\n\\]\n\n(2.3) \\quad (4.4)\n\n\\[ R_1 = \\quad \\text{R}_2 = \\quad \\text{O} \\]\n\nFigure 4.10 Copolymerization of (2.3) with THF\n\nTable 4.2 Properties of (4.4)\n\n| Entry | Mol equivalent of BF₃.Et₂O | Yield (%) | Gel permeation chromatography |\n|-------|---------------------------|-----------|------------------------------|\n| | | | M_w (Da) | M_n (Da) | PDI |\n| 1 | 0.01 | 0 | - | - | - |\n| 2 | 0.025 | 75 | 17700 | 8500 | 2.08|\n| 3 | 0.05 | 97 | 54200 | 26100 | 2.07|\n\nM_w = weight average molecular weight, M_n = number average molecular weight, PDI = polydispersity index\n\nGPC analysis was conducted on the produced copolymers with (2.3) as a standard, which indicated a M_n = 500 Da. Referring to Table 4.2, the optimum amount of catalyst needed to give good yield of copolymers (4.4) was 0.05 mol equivalent of\n\nBF₃·Et₂O per mol epoxide of (2.3) (Entry 3), which gave 97% copolymers (4.4) that have a number average molecular weight \\((M_n)\\) of 26100 Da. Lower yield of copolymers was obtained with lower catalyst loading and when the reaction was conducted with 0.01 mol equivalent of catalyst only starting material was recovered. MALDI-TOF-MS analysis confirmed that (4.4) (Figure 4.11) was a copolymer with a molecular weight up to 3000 Da. The peak at 664 Da corresponds to (4.5), a sodium adduct of (2.3) dimer (Figure 4.12) and the peak at 1817 Da corresponds to (4.6), a sodium adduct of (4.5) with 17 repeating units of ring opened THF (Figure 4.13).\n\n\n\n**Figure 4.11** MALDI-TOF-MS spectrum of (4.4) by using DHB as the matrix in the analysis\n\n\n\n**Figure 4.12** Dimer of (2.3)\n\nFigure 4.13 Dimer of (2.3) with 17 repeating units of ring opened THF\n\nFigure 4.14 shows the stacked 400 MHz $^1$H NMR spectrum of (2.3) and (4.4). Referring to the $^1$H NMR spectrum, the epoxide group of (2.3) at 2.80-3.15 ppm was ring opened to copolymerize with THF yielding ether and hydroxyl functionalities (3.51-3.60 ppm) and peaks corresponding to ring opened THF [1.56-1.66 ppm (peak b) and 3.35-3.45 ppm (peak a)].\n\nFigure 4.14 Stacked 400MHz $^1$H NMR spectrum of (2.3) and (4.4) in CDCl$_3$.\n\n4.3 COPOLYMERS OF EPOXIDIZED COCOA BUTTER AND TETRAHYDROFURAN\n\nThe copolymerization of epoxidized cocoa butter (ECB, 2.16) and THF was conducted using the same method as for (2.3) (Figure 4.15). The properties of the copolymers (ECB-THF, 4.7) are tabulated in Table 4.3.\n\n\n\n**Figure 4.15 Copolymerization of (2.16) with THF**\n\n| Entry | Mol equivalent of BF₃.Et₂O | Yield (%) | Gel permeation chromatography |\n|-------|---------------------------|-----------|-------------------------------|\n| | | | Mₜ (Da) | Mₙ (Da) | PDI |\n| 1 | 0.02 | 0 | - | - | - |\n| 2 | 0.05 | 82 | 37100 | 16500 | 2.25 |\n| 3 | 0.1 | 93 | 83200 | 29600 | 2.81 |\n\nMₜ = weight average molecular weight, Mₙ = number average molecular weight, PDI = polydispersity index\n\nThe optimum catalyst loading for copolymerization of (2.16) with THF was 0.1 mol equivalent of BF₃.Et₂O, which yielded 93% (Entry 3) of copolymers (4.7). Lower\n\namount of catalyst gave lower yields of copolymers and lower $M_n$. Catalyst loading at 0.02 mol equivalent of BF$_3$.Et$_2$O was not sufficient to catalyze the reaction.\n\nMALDI-TOF-MS analysis of (4.7) (Figure 4.16) confirmed the copolymerization of (2.16) with THF, in which the peak at 1116 Da corresponds to the sodium adduct of (2.16) plus 3 units of THF (4.8) (Figure 4.17). Furthermore, the peak at 1920 Da corresponds to dimer of (2.16) plus 2 units of THF (4.9) (Figure 4.17).\n\n\n\n**Figure 4.16** MALDI-TOF-MS spectrum of (4.7) by using DHB as the matrix in the analysis\n\n\n\n**Figure 4.17** Copolymers of (2.16) with THF\n\nThe stacked 400 MHz $^1$H NMR spectrum of (2.16) and (4.7) (Figure 4.18) shows that the epoxide group of (2.16) at 2.78-3.05 ppm was ring opened to copolymerize with THF similar to (2.3).\n\n\n\n**Figure 4.18** Stacked 400 MHz $^1$H NMR spectrum of (2.16) and (4.7) in CDCl$_3$.\n\n### 4.4 COPOLYMERS OF EPOXIDIZED PALM OIL AND TETRAHYDROFURAN\n\nThe copolymerization of epoxidized palm oil (2.17) and THF was conducted in the same way as epoxidized cocoa butter (2.17) (Figure 4.19) and the products (4.10) were analyzed by GPC, MALDI-TOF-MS and $^1$H NMR as before. The properties of the copolymers (EPO-THF, 4.10) are tabulated in Table 4.4.\n\nFigure 4.19 Copolymerization of (2.17) with THF\n\nTable 4.4 Properties of (4.10)\n\n| Entry | Mol equivalent of BF$_3$.Et$_2$O | Yield (%) | Gel permeation chromatography |\n|-------|---------------------------------|-----------|-------------------------------|\n| | | | M$_w$ (Da) | M$_n$ (Da) | PDI |\n| 1 | 0.005 | 0 | - | - | - |\n| 2 | 0.01 | 80 | 147000 | 44800 | 3.28|\n| 3 | 0.02 | 97 | 366000 | 55800 | 6.56|\n| 4 | 0.03 | Gelled | - | - | - |\n\nM$_w$ = weight average molecular weight, M$_n$ = number average molecular weight, PDI = polydispersity index\n\nReferring to Table 4.4, the optimum catalyst loading was 0.02 mol equivalent of BF$_3$.Et$_2$O, in which we were able to achieve about 95% yield of copolymers that have a number average molecular weight of about 56,000 Da. Catalyst loading at 0.005 mol equivalent was not sufficient to catalyze the reaction, while catalyst loading at 0.03 mol equivalent yielded cross-linked polymers, which indicates that higher amounts of catalyst generated more active polymer chains that promoted cross-linking during polymerization. This prompted the study on the effect of other\n\nreaction parameters (monomer ratio, temperature and duration) on the properties of copolymers\n\n4.5 EFFECT OF MONOMER RATIO ON THE PROPERTIES OF COPOLYMERS\n\n\\[\n\\begin{align*}\n&\\text{Figure 4.20 Copolymerization of (2.17) with THF on different monomer ratio} \\\\\n&\\text{For this study, epoxidized palm oil (2.17) was used as the renewable epoxidized plant oil to copolymerize with THF (Figure 4.20). The ratio between (2.17) and THF was varied in order to observe changes in the properties of the copolymers (4.10). The following Table 4.5 displays the properties of the copolymer from this study.}\n\\end{align*}\n\\]\n\nTable 4.5 Properties of (4.10) from different monomer ratio\n\n| Entry | Monomer ratio THF : (2.17) (ml : g) | Yield (%) | Gel permeation chromatography |\n|-------|-----------------------------------|-----------|------------------------------|\n| | | | M\\textsubscript{w} (Da) | M\\textsubscript{n} (Da) | PDI |\n| 1 | 4 : 1 | Gelled | - | - | - |\n| 2 | 8 : 1 | Gelled | - | - | - |\n| 3 | 12 : 1 | Gelled | - | - | - |\n| 4 | 16 : 1 | 79 | 147000 | 44800 | 3.28|\n| 5 | 20 : 1 | 81 | 173000 | 56000 | 3.09|\n| 6 | 24 : 1 | 83 | 169000 | 56100 | 3.01|\n\nM\\textsubscript{w} = weight average molecular weight, M\\textsubscript{n} = number average molecular weight, PDI = polydispersity index\n\nThe results in Table 4.5 shows that the minimum ratio between THF and (2.17) must be equal to or above the 16 : 1 ratio (Entry 4) in order to get non-cross-linked (liquid) product. Below the specific ratio, we achieved cross-linked copolymers (Entry 1 to 3). Higher ratios of THF to (2.17) (Entry 5 and 6) yielded copolymers with higher number average molecular weight as compared to copolymer from Entry 4.\n\nIt is proposed that the cross-linking of copolymers (Entry 1 to 3) was due to the higher amount of (2.17) presence in the monomers mixture. Results from section 2.5, (page 71) show that (2.17) will form cross-linked polymers if it was ring opened with BF\\textsubscript{3}.Et\\textsubscript{2}O without solvent. However, it will form liquid oligomeric polyols if it was ring opened in solvent. In other word, it needs solvent to prevent the formation of cross-linked products. In this copolymerization reaction system, THF acts as a monomer as well as a solvent for the reaction system. Therefore, at lower THF : (2.17) ratios (Entry 1 to 3), the amount of THF was not sufficient to prevent the\n\ncross-linking of (2.17). At higher THF ratios (Entry 4 to 6), the amount of THF as solvent was sufficient to prevent/retard cross-linking of the copolymers.\n\nHigher amounts of THF in the reaction mixture also yielded copolymers with higher molecular weights. This suggests that reaction RN4 (Figure 4.6) is now dominating the reaction pathway. Furthermore, the presence of THF in the reaction system activated the epoxy ring opening reaction because the amount of catalyst needed \\((\\text{BF}_3.\\text{Et}_2\\text{O})\\) (0.01 mol equivalent) for getting high yields of polymer was comparatively lower than similar epoxy ring opening reaction conducted without THF in n-hexane (0.035 mol equivalent). In other words, it takes less amount of catalyst to cause gelation in reaction conducted in THF than a reaction conducted in n-hexane.\n\n### 4.6 EFFECT OF REACTION TEMPERATURE ON THE PROPERTIES OF THE COPOLYMERS\n\nThe copolymerization of (2.17) with THF was repeated at different temperature to evaluate the effect of temperature on the properties of the copolymers (4.10). The following Table 4.6 tabulates the result of this study.\n\nTable 4.6 Properties of (4.10) from copolymerization at different temperature\n\n| Entry | Temperature (°C) | Mol equivalent of BF₃.Et₂O | Yield (%) | Gel permeation chromatography |\n|-------|-----------------|----------------------------|-----------|------------------------------|\n| | | | | Mₜ (Da) | Mₙ (Da) | PDI |\n| 1 | 60 | 0.025 | 80 | 62900 | 16500 | 3.81 |\n| 2 | 20 | 0.025 | Gelled | - | - | - |\n\nMₜ = weight average molecular weight, Mₙ = number average molecular weight, PDI = polydispersity index\n\nWhen the reaction was conducted at 60 °C with 0.025 mol equivalent of BF₃.Et₂O (Entry 1), the product was liquid copolymers (80% yield) with an average molecular weight (Mₙ) of 16500. However, by lowering the reaction temperature to 20 °C (Entry 2), the product was a cross-linked (gelled) copolymer.\n\nResults from Chapter 2 show that gelation occurs during homopolymerization of (2.17) catalyzed by BF₃.Et₂O (page 71) and this occurred through cross-linking of epoxide. The same cross-linking of epoxide caused the gelation in the copolymerization of (2.17) and THF at 20 °C. This is due to the lower activation energy for epoxide ring opening (20 kcal/mol)¹⁰⁴ as compared to THF ring opening (51.3 kcal/mol).¹¹⁶ Therefore, when the copolymerization was conducted at low temperature (20 °C), the epoxide ring opening reaction predominates thus causing gelation but when the reaction was conducted at higher temperature (60 °C), the THF ring opening reaction predominates yielding liquid copolymers.\n\n4.7 THE EXTENT OF COPOLYMERIZATION REACTION AGAINST TIME\n\nA study was conducted to evaluate the extent of copolymerization reaction of (2.17) with THF catalyzed by $\\text{BF}_3\\cdot\\text{Et}_2\\text{O}$ against time (Figure 4.21). A small aliquot was removed from the reaction mixture after 5 minutes and 30 minutes of reaction and then at every hour of reaction. The small sample was washed with water to quench the reaction before analyzing it with GPC. The following Table 4.7 and Figure 4.22 show the result of this study.\n\nTable 4.7 The extent of copolymerization of (2.17) with THF catalyzed by BF$_3$.Et$_2$O against time\n\n| Reaction time (minutes) | Polymer content (%) | Gel permeation chromatography |\n|------------------------|---------------------|-------------------------------|\n| | | $M_w$ (Da) | $M_n$ (Da) | PDI |\n| 5 | 2 | 27900 | 26500 | 1.05 |\n| 30 | 22 | 50800 | 32300 | 1.57 |\n| 60 | 37 | 64000 | 36100 | 1.77 |\n| 120 | 54 | 87800 | 40800 | 2.15 |\n| 240 | 65 | 112000 | 46300 | 2.41 |\n| 480 | 73 | 150000 | 48600 | 3.09 |\n| 720 | 78 | 181000 | 53800 | 3.36 |\n| 1440 | 82 | 234000 | 58700 | 3.99 |\n\n$M_w =$ weight average molecular weight, $M_n =$ number average molecular weight, PDI = polydispersity index\n\nFigure 4.22 Graph to show the copolymerization of (2.17) with THF against time\n\nReferring to Table 4.7, after 5 minutes into the reaction, the amount of (4.10) was low (2%) but the $M_n$ of (4.10) was significantly high (26500 Da). The copolymers content increased progressively with reaction time, in which it reached 82% in 24 hours and at the same time the PDI of the copolymers also broadens indicating more\n\npolymer chains were cross-linking with the longer reaction time. Referring to Figure 4.20, the polymer content starts to level out (plateau), indicating that the polymer content will not increase significantly with a longer reaction time.\n\nThe number average molecular weight ($M_n$) of (4.10) analyzed by GPC was about 58700 Da. MALDI-TOF-MS analysis of (4.10) (Figure 4.23) shows peak at 1086 Da, which correspond to sodium adduct of epoxide ring opened (2.17) plus 2 units of THF (4.11) (Figure 4.24). The other peaks in the spectrum were (4.11) plus additional units of THF (72 Da). The peak 1158 Da to 1246 Da is an additional 89 Da which is a unit of THF (72 Da) plus one hydroxyl group (-OH, 17 Da).\n\nFigure 4.23 MALDI-TOF-MS spectrum of (4.10) by using DHB as the matrix in the analysis\n\nFigure 4.24 Copolymers of (4.11)\n\nThe reaction was also followed by $^1$H NMR and the following Figure 4.25 shows the stacked 400 MHz $^1$H NMR plot of copolymers (4.10) at 30 minute, 6 hours, 12 hours and 24 hours of reaction time. $^1$H NMR analysis shows that the epoxide group of (2.17) (2.80-3.10 ppm) diminishes with time as expected.\n\nFigure 4.25 Stacked 400 MHz $^1$H NMR spectrum of (2.17) and reaction mixture in CDCl$_3$ at certain reaction time during copolymerization.\n\n4.8 COPOLYMERS OF EPOXIDIZED RAPSEED OIL AND TETRAHYDROFURAN\n\n\\[\n\\begin{align*}\n&\\text{Figure 4.26 Copolymerization of (2.13) with THF} \\\\\n&\\text{The copolymerization of epoxidized rapeseed oil (2.13) and THF was conducted in the same way as epoxidized cocoa butter (2.16) (Figure 4.26) in order to evaluate the effect of higher epoxide functionality on the properties of the copolymers. The products (4.12) were analyzed by GPC, MALDI-TOF-MS and } ^1\\text{H NMR as before and the properties of the copolymers (ERO-THF, 4.12) are tabulated in Table 4.8.}\n\\end{align*}\n\\]\n\nTable 4.8 Properties of (4.12)\n\n| Entry | Monomer ratio THF : (2.13) (g : ml) | Mol equivalent of BF$_3$.Et$_2$O | Yield (%) | Gel permeation chromatography |\n|-------|-----------------------------------|-------------------------------|-----------|-----------------------------|\n| | | | | M$_w$ (Da) | M$_n$ (Da) | PDI |\n| 1 | 50 : 1 | 0.02 | Gelled | - | - | - |\n| 2 | 80 : 1 | 0.02 | 95 | 229000 | 53900 | 4.25|\n| 3 | 100 : 1 | 0.02 | 97 | 276000 | 74300 | 3.71|\n\nM$_w$ = weight average molecular weight, M$_n$ = number average molecular weight, PDI = polydispersity index\n\nIn comparison to (2.17), the copolymerization of (2.13) needed more THF as solvent to prevent gelation of the reaction mixture, in which the ratio between THF and (ERO,X) must be at least 80 : 1 (THF : 2.13) to yield liquid copolymers. When the ratio was 100 : 1 (THF : 2.13), the yield of the copolymers was about 97% and the $M_n = 74300$ Da.\n\nMALDI-TOF-MS analysis of (4.12) (Figure 4.27) shows a peak at 1170 Da which corresponds to a ring opened (2.13) plus 3 units of THF (4.13), while peak at 1262 Da correspond to (4.14) (Figure 4.28). Subsequent peaks are (4.14) plus additional units of THF (72 Da) as shown in Figure 4.27.\n\n\n\n**Figure 4.27** MALDI-TOF-MS spectrum of (4.12) by using DHB as the matrix in the analysis\n\nFigure 4.28 Copolymers of (2.13) and THF, (4.13) and (4.14)\n\nThe stacked 400 MHz $^1$H NMR spectrum of (2.13) and (4.12) (Figure 4.29) shows that the epoxide group of (2.13) at 2.84-3.22 ppm was ring opened to copolymerize with THF. The larger incorporation of THF to the copolymer can also be seen.\n\nFigure 4.29 400 MHz $^1$H NMR spectrum of (2.13) and (4.12) in CDCl$_3$\n\n4.9 COPOLYMERS OF EPOXIDIZED SOYBEAN OIL AND TETRAHYDROFURAN\n\nThe copolymerization of epoxidized soybean oil (2.6) with THF was conducted in similar method as epoxidized rapeseed oil (2.13) (Figure 4.30).\n\nTable 4.9 Properties of (4.15)\n\n| Entry | Monomer ratio THF : (2.6) (g : ml) | Mol equivalent of BF₃.Et₂O | Yield (%) | Gel permeation chromatography |\n|-------|----------------------------------|---------------------------|-----------|------------------------------|\n| | | | | Mₜ (Da) | Mₙ (Da) | PDI |\n| 1 | 50 : 1 | 0.02 | Gelled | - | - | - |\n| 2 | 80 : 1 | 0.02 | 96 | 233000 | 57800 | 4.03|\n| 3 | 100 : 1 | 0.02 | 98 | 364000 | 115000 | 3.17|\n\nMₜ = weight average molecular weight, Mₙ = number average molecular weight, PDI = polydispersity index\n\nSimilar to (2.13), the copolymerization of (2.6) needed more THF as solvent to prevent gelation of the reaction mixture, in which the ratio between THF and (2.6) must be at least 80 : 1 (THF : 2.6) to yield liquid copolymers. When the ratio was 100 : 1 (THF : 2.6), the yield of the copolymers was about 97% and the number\n\naverage molecular weight was about 115000 Da, which is higher than (4.12) because of the additional epoxide group of (2.6).\n\nMALDI-TOF-MS analysis of (4.15) (Figure 4.31) shows a peak at 1033 Da which corresponds to a ring opened (2.6) (4.16), while peak at 1103 Da correspond to (4.17) (Figure 4.32). Subsequent peaks are (4.17) plus additional units of THF (72 Da) as shown in Figure 4.31.\n\n\n\n**Figure 4.31** MALDI-TOF-MS spectrum of (4.15) by using DHB as the matrix in the analysis\n\n\n\n**Figure 4.32** Copolymers of (2.6) and THF, (4.16) and (4.17)\n\nSimilarly to (4.12), the stacked 400 MHz $^1$H NMR spectrum of (2.6) and (4.15) shown below (Figure 4.33) shows the large amount of THF incorporated.\n\n\n\n**Figure 4.33** Stacked 400 MHz $^1$H NMR spectrum of (2.6) and (4.15) in CDCl$_3$\n\n### 4.10 COPOLYMERS OF EUPHORBIA OIL AND TETRAHYDROFURAN\n\n\n\n**Figure 4.34** Copolymerization of (2.18) with THF\n\nThe copolymerization of euphorbia oil (2.18) with THF was conducted in similar method as epoxidized soybean oil (2.6) (Figure 4.34).\n\nTable 4.10 Properties of (4.18)\n\n| Entry | Monomer ratio (g : ml) | Mol equivalent of BF₃.Et₂O | Yield (%) | Gel permeation chromatography |\n|-------|------------------------|----------------------------|-----------|------------------------------|\n| | THF : (2.18) | | | Mₜ (Da) Mₙ (Da) PDI |\n| 1 | 20 : 1 | 0.02 | Gelled | - - - |\n| 2 | 30 : 1 | 0.02 | 97 | 112000 33500 3.34 |\n\nMₜ = weight average molecular weight, Mₙ = number average molecular weight, PDI = polydispersity index\n\nThe liquid copolymers of (2.18) and THF can be produced at lower monomer ratio (THF : 2.18) as compared to (2.6) due to the lower epoxide functionality of EuO. The optimum monomer ratio was 30 : 1, which yielded 97% copolymers that have an average molecular weight of 33500 Da. The 400 MHz ¹H NMR spectrum of (4.18) shows similar peaks exhibited by previous plant oils and MALDI-TOF-MS analysis of (4.18) shows a peak at 1150 Da which corresponds to a (4.19), while peak at 1190 Da correspond to (4.20) (Figure 4.35).\n\nFigure 4.35 Copolymers of (2.18) and THF, (4.19) and (4.20)\n\n4.11 SUMMARY OF COPOLYMERIZATION OF EPOXIDIZED OILS AND TETRAHYDROFURAN\n\nThe following Table 4.11 shows the properties of copolymers of THF with epoxidized methyl oleate (2.3) and the 5 types of epoxidized plant oils (2.16, 2.17, 2.13, 2.6 and 2.18). These copolymers were produced through the optimum reaction conditions (yield) found for each type of oils. The reaction products were analyzed by $^1$H NMR and GPC.\n\nTable 4.11 Properties of copolymers from ring opened epoxidized oils and THF\n\n| EO | THF:EO | Mol eq. | Yield (%) | GPC | OHV | AV |\n|------|--------|---------|-----------|--------------|-----|----|\n| | | | | M$_w$ (Da) | M$_n$ (Da) | PDI | |\n| 2.3 | 20:1 | 0.05 | 97 | 54100 | 26100 | 2.07 | 25 | 7 |\n| 2.16 | 5:1 | 0.1 | 93 | 83200 | 29600 | 2.80 | 27 | 1 |\n| 2.17 | 30:1 | 0.02 | 97 | 366000 | 55800 | 6.56 | 40 | 1 |\n| 2.18 | 30:1 | 0.02 | 97 | 112000 | 33500 | 3.33 | 33 | 1 |\n| 2.13 | 100:1 | 0.02 | 97 | 276000 | 74300 | 3.71 | 48 | 1 |\n| 2.6 | 100:1 | 0.02 | 98 | 364000 | 115000| 3.17 | 56 | 1 |\n\nEO = epoxidized oil, THF:EO = monomer ratio (ml : g), Mol eq. = mol equivalent of BF$_3$.Et$_2$O, GPC = gel permeation chromatography, M$_w$ = weight average molecular weight, M$_n$ = number average molecular weight, PDI = polydispersity index, OHV = hydroxyl value (mg KOH/g), AV = acid value (mg KOH/g)\n\nThe copolymerization reaction of THF with epoxidized oils (2.3) and (2.16) that have one epoxy group per molecule will not form cross-linked polymer even when catalyzed by 0.05 mol equivalent of BF$_3$.Et$_2$O and both the epoxidized oils (2.3 and 2.16) gave good yield of oligomeric polyols (97%, 93% respectively) with relatively\n\nlow PDI. The relatively high AV for (2.3) indicates significant hydrolysis during the reaction. While for epoxidized plant oils with multiple epoxide groups per molecule (2.17, 2.13, 2.6 and 2.18) the amount of catalyst must be less than 0.03 mol equivalents of BF$_3$.Et$_2$O to avoid formation of cross-linked products. Furthermore, the monomer ratio (THF : EO) for epoxidized oils increases with more epoxide groups per molecule as shown in Table 4.11 to avoid formation of cross-linked products. In general, epoxidized plant oils with more epoxides per molecule lead to larger molecular weights and hydroxyl values as expected.\n\nBoth (2.18) and (2.17) have 2 epoxide groups per molecule but (2.18) has 3 alkenes while (2.17) has none. Referring to Table 4.11, the copolymers made from (2.17) has higher $M_n$ and OHV than copolymers made from (2.18). This indicates that the alkenes of (2.18) has affected the properties of the copolymers and we think that the extra ‘kink’ on the fatty acid hydrocarbon chain of (2.18) is responsible for the lower $M_n$ and OHV of copolymers from (2.18). The epoxidized oils (2.13) and (2.6) have 4 and 5 epoxide groups per molecule respectively, which are higher than the other epoxidized plant oils in this study. This high epoxide content led to higher $M_n$ value and hydroxyl values.\n\nThe acid values of the copolymers (1 mg KOH/g) are considered low and acceptable for use in PU formulation and this indicates little hydrolysis happened during the copolymerization reaction; however copolymers based on (2.3) have a higher acid value due to the relative ease of hydrolysis of the methyl ester group. The hydroxyl value of the copolymers ranges from 25 to 60 mg KOH/g sample, depending on the starting material. In general, plant oils with a higher amount of epoxide functionality\n\nwill produce a higher hydroxyl value because the hydroxyl functionality was produced from the epoxide group through epoxide ring opening reactions.\n\nIn summary, copolymers of THF and various epoxidized plant oils can be prepared through ring opening polymerization catalyzed by BF$_3$.Et$_2$O. The properties of the copolymers depend on the degree of unsaturation of the plant oils as well as the reaction conditions (monomer ratio, catalyst amount, reaction temperature and reaction time).\n\nThese copolymers have hydroxyl groups that can react with diisocyanates, therefore they can theoretically be used to make polyurethane (PU) products. In the later sections, we will evaluate the properties of PU products made from these copolymers with PU product made from homopolymerization of THF.\n\n4.12 EFFECT OF WATER CONTENT ON THE PROPERTIES OF THE COPOLYMERS\n\nFigure 4.36 Copolymerization of THF and epoxidized oils\n\nEarlier in Section 4.1 (page 131), the screening of chemical compounds as potential catalyst for the copolymerization reaction between THF and epoxidized plant oils was discussed. Two boron based compounds were identified as suitable catalysts for\n\nthe copolymerization reaction, they were $\\text{BF}_3.\\text{Et}_2\\text{O}$ and $\\text{HBF}_4$. The two boron based compounds were used to catalyze the copolymerization reaction of THF with (2.3) and (2.17) under same reaction conditions in order to evaluate the catalytic activities of both compounds (Figure 4.36). The results of this study were tabulated in Table 4.12.\n\nTable 4.12 Properties of copolymers of THF and epoxidized oils\n\n| EO | THF:EO | Mol eq. | Catalyst | Polymer content (%) | GPC |\n|------|--------|---------|--------------|---------------------|--------------|\n| | | | | | $M_w$ (Da) | $M_n$ (Da) | PDI |\n| 2.3 | 5:1 | 0.05 | $\\text{BF}_3.\\text{Et}_2\\text{O}$ | 87 | 22900 | 11400 | 2.00 |\n| 2.3 | 5:1 | 0.05 | $\\text{HBF}_4$ | 56 | 3400 | 2700 | 1.26 |\n| 2.17 | 30:1 | 0.02 | $\\text{BF}_3.\\text{Et}_2\\text{O}$ | 97 | 366000 | 55800 | 6.56 |\n| 2.17 | 30:1 | 0.02 | $\\text{HBF}_4$ | 95 | 85000 | 22500 | 3.78 |\n\n$EO = \\text{epoxidized oil}, \\text{THF}:EO = \\text{monomer ratio (ml : g)}, \\text{Mol eq.} = \\text{mol equivalent of BF}_3.\\text{Et}_2\\text{O}, \\text{GPC} = \\text{gel permeation chromatography}, M_w = \\text{weight average molecular weight}, M_n = \\text{number average molecular weight}, \\text{PDI} = \\text{polydispersity index},$\n\nReferring to Table 4.12, for both epoxidized plant oils with mono-epoxide (2.3) and multi-epoxides (2.17) group per molecule, the $\\text{BF}_3.\\text{Et}_2\\text{O}$ catalyzed reactions yielded copolymers with larger molecular weight ($M_n$) and higher polymer content. One of the main differences between $\\text{BF}_3.\\text{Et}_2\\text{O}$ and $\\text{HBF}_4$ is that $\\text{HBF}_4$ was supplied in the form of 48% in water, while $\\text{BF}_3.\\text{Et}_2\\text{O}$ was supplied in solution of 48% in ethyl ether.\n\nIt is proposed that water content of $\\text{HBF}_4$ has significant effect on the properties of the copolymers. Therefore, the effect of water content in the reaction system on the properties of copolymers was evaluated by adding specific amounts of water into the reaction system. The study was conducted with (2.17) as the epoxidized oil (Figure 4.37) and the results of this study were tabulated in Table 4.13.\n\nFigure 4.37 Copolymerization of (2.17) and THF with addition of water\n\nTable 4.13 Properties of copolymers from copolymerization reaction with addition of water\n\n| Entry | THF:EO | Mol eq. | Addition of water (µL) | Water content (% w/w) | Polymer content (%) | GPC | M<sub>w</sub> (Da) | M<sub>n</sub> (Da) | PDI |\n|-------|--------|---------|------------------------|-----------------------|---------------------|-----|-------------------|------------------|-----|\n| 1 | 10:1 | 0.02 | 0 | 0.03 | Gelled | - | - | - | - |\n| 2 | 10:1 | 0.02 | 1 | 0.04 | Gelled | - | - | - | - |\n| 3 | 10:1 | 0.02 | 5 | 0.08 | 92 | 81600 | 18700 | 4.36 | |\n| 4 | 10:1 | 0.02 | 10 | 0.13 | 78 | 12800 | 7900 | 1.62 | |\n| 5 | 10:1 | 0.02 | 100 | 1.06 | 0 | - | - | - | |\n\nTHF:EO = monomer ratio (ml : g), Mol eq. = mol equivalent of HBF<sub>4</sub>, GPC = gel permeation chromatography, M<sub>w</sub> = weight average molecular weight, M<sub>n</sub> = number average molecular weight, PDI = polydispersity index\n\nThe results in Table 4.13 clearly show that increasing the amount of water in the reaction system impeded the copolymerization reaction, in which at a low level of water content (Entry 1), the product was a cross-linked copolymer while at 1% water content (Entry 5), the reaction did not produce any copolymers. Comparing the data from Entry 3 and 4, the additional amount of water in Entry 4 significantly reduced the polymer content and molecular weight of copolymers. This information provides another method to control the molecular weight of the copolymer by addition of specific amounts of water into the reaction system.\n\n4.13 HOMOPOLYMERIZATION OF TETRAHYDROFURAN CATALYZED BY TRIFLIC ACID\n\n\\[\nn \\text{O} \\xrightarrow{\\text{CF}_3\\text{SO}_3\\text{H}} \\xrightarrow{60^\\circ\\text{C}, 8\\text{ h}} \\text{H}^+\\text{O}\\left(\\text{CH}_2\\text{CH}_2\\text{O}\\right)_n\\text{H}\n\\]\n\n(4.19)\n\nThe homopolymerization of THF was conducted according to method published by Dorai\\textsuperscript{105} et al. The purpose of this work is to prepare homopolymers of THF as a benchmark in our study on the properties of PU made from copolymers of THF and epoxidized plant oils. The homopolymer of THF (4.19) was analyzed by GPC, MALDI-TOF-MS and $^1$H NMR. The Table 4.14 shows the properties of (4.19).\n\nTable 4.14 Properties of (4.19)\n\n| Mol eq. | Polymer content (%) | GPC | OHV | AV |\n|---------|---------------------|--------------|-----|----|\n| | | M_w (Da) | M_n (Da) | PDI |\n| 0.08 | 100 | 33800 | 18000 | 1.87 |\n\nMol eq. = mol equivalent of CF$_3$SO$_3$H, GPC = gel permeation chromatography, M$_w$ = weight average molecular weight, M$_n$ = number average molecular weight, PDI = polydispersity index, OHV = hydroxyl value (mg KOH/g), AV = acid value (mg KOH/g)\n\nGPC analysis shows that the (4.19) has a M$_n$ = 18000 Da. While MALDI-TOF-MS analysis of (4.19) (Figure 4.38) shows a peak at 958 Da, which corresponds to sodium adduct of homopolymerized 13 units of THF (4.20) (Figure 4.39). The other peaks are (4.20) plus additional unit of the THF. The prepared (4.19) has hydroxyl functionality that can be used to make PU.\n\n4.14 ATTEMPTED COPOLYMERIZATION OF EPOXIDIZED PLANT OILS WITH OTHER HETEROCYCCLICS\n\nIn earlier sections, the successful copolymerization of THF with epoxidized plant oils was discussed. This prompts a study to look into the possibility of copolymerizing epoxidized plant oils with other heterocyclics by using the same optimized reaction condition for copolymerization of epoxidized plant oils and THF. The first two heterocyclics that were evaluated were the analogue of THF, namely 2-methyl tetrahydrofuran (4.21) and 3-methyl tetrahydrofuran (4.22) (Figure 4.40) in order to know whether the extra methyl group at position 2 and 3 of THF ring will\n\naffect the copolymerization reaction. The reactions were conducted with monomer ratio 20:1 (THF analogue: 2.17; ml:g) and with other reaction conditions as shown in Figure 4.40.\n\n\\[\n\\begin{align*}\n\\text{O} & \\quad + \\quad \\text{O} \\\\\n\\text{C}_3\\text{H}_6\\text{O} & \\quad + \\quad \\text{C}_5\\text{H}_8\\text{O} \\\\\n(4.21) & \\quad (2.17)\n\\end{align*}\n\\]\n\n0.1 mol eq. BF$_3$·Et$_2$O\n\n20 °C, 24 h\n\nCopolymer\n\nFigure 4.40 Copolymerization of (2.17) with (4.21) and (4.22)\n\nAfter several attempts, the reactions failed to produce any copolymers of (2.17) and (4.21) or (4.22). Literature on homopolymerization of (4.21) pointed out that the (4.21) was not able to polymerize with BF$_3$·Et$_2$O, SbCl$_5$ or 4-ClC$_6$H$_4$N$_2$PF$_6$ because of an unfavorable thermodynamic factor for ring opening of (4.21). Furthermore, during THF polymerization reaction, the attack of activated THF is at the α position of the oxygen atom, therefore, methyl substitution at the α position hinders the polymerization reaction. Chiang et al. show that (4.22) can be polymerized using high amounts (>10% mol) of catalysts such as PF$_5$ and low reaction temperature (-22 °C) for 45 days to yield 40% poly(3-methyltetrahydrofuran).\n\n4.15 COPOLYMERIZATION OF EPOXIDIZED PLANT OILS WITH ε - CAPROLACTONE\n\nThe ε-caprolactone (4.23) was copolymerized with (2.17) using the same reaction conditions employed for the synthesis of EPO-THF (4.10) (Figure 4.41) to yield copolymer (4.24). The results of the copolymerization were tabulated in Table 4.15.\n\n\n\n**Figure 4.41 Copolymerization of (4.23) with (2.17)**\n\n| Entry | (4.23 : 2.17) | Mol eq. | Polymer content (%) | GPC |\n|-------|---------------|---------|---------------------|--------------|\n| | | | | M_w (Da) | M_n (Da) | PDI |\n| 1 | 0.25 : 1 | 0.05 | 77 | 9000 | 6200 | 1.45|\n| 2 | 0.5 : 1 | 0.05 | 68 | 7700 | 5600 | 1.37|\n| 3 | 1 : 1 | 0.05 | 54 | 6400 | 5400 | 1.18|\n\n(4.23 : 2.17) = monomer ratio (mol : mol), Mol eq. = mol equivalent of BF₃.Et₂O, GPC = gel permeation chromatography, M_w = weight average molecular weight, M_n = number average molecular weight, PDI = polydispersity index.\n\nThe result in Table 4.15 shows that the average molecular weight of (4.24) as well as the polymer content decreases with increasing monomer ratio of (4.23) to (2.17) in the starting mixture. This indicates that the (4.23) retards the oligomerization of (2.17).\n\nGPC analysis shows that the average molecular weight of (4.24) was about 6200 Da. MALDI-TOF-MS analysis of (4.24) (Figure 4.42) shows a peak at 1177 Da (Figure 4.43) that correspond to structure (4.25), while additional peaks are (4.25) plus additional units of (4.23). Furthermore, oligomers of (2.17) plus a unit of (4.23) was also detected with a peak at 1953 Da, which corresponds to structure (4.26).\n\n$^1$H NMR spectroscopy (Figure 4.44) shows that copolymers of (4.24) have the ring-opened $\\varepsilon$-caprolactone moiety at 4.06 ppm ($\\varepsilon$-CH$_2$) and 3.61 ppm (HO-CH$_2$) as well as the ether and hydroxyl moiety of copolymers at 3.58 – 3.10 ppm. Furthermore, epoxide ring opening by carboxylic group of (4.23) was also detected by $^1$H NMR at 4.84 ppm.\n\nFigure 4.42 MALDI-TOF-MS spectrum of (4.24) by using DHB as the matrix of the analysis\n\nFigure 4.43 Copolymers of (4.24)\n\nFigure 4.44 400 MHz $^1$H NMR spectrum of (4.24) in CDCl$_3$\n\n4.16 POLYURETHANES MADE FROM COPOLYMERS OF EPOXIDIZED PLANT OILS AND TETRAHYDROFURAN\n\nThe prepared copolymers of epoxidized plant oils and tetrahydrofuran were used as starting materials for making polyurethane (PU) samples. These copolymers were reacted with 4,4'-diphenylmethane diisocyanate (MDI) and yielded quantitative amount of PU samples (Figure 4.45).\n\nThe ratio between the isocyanate group (NCO) and the hydroxyl group (OH) was kept at 1.05 to 1 (NCO/OH ratio = 1.05) in order to ensure that all the hydroxyl groups of copolymers were fully reacted and the PU samples were fully cured when the excess isocyanate group reacted with moisture from the air.\n\nThe PU synthesis was based on the six copolymers (4.4, 4.7, 4.10, 4.12, 4.15 and 4.18) and they were reacted with MDI according to ratio describe above. In addition, we have also included homopolymerized THF (4.19) as a control in the PU analysis. The PU samples made from these copolymers were cross-linked polymers, which\n\nindicate that all the copolymers have 2 or more hydroxyl functionality that enable the formation of cross-linked polymer.\n\nTensile testing was carried out on these PU samples in order to give a better understanding of the strength of these PU. Figure 4.46 shows the stress-strain curve of PU made from each type of copolymers. Furthermore, swelling tests was conducted on the PU samples in order to determine the cross-linking density of the PU samples by using the Flory-Rehner equation.\\textsuperscript{95} The following Table 4.16 shows the properties of the PU samples made from these copolymers.\n\n\n\n**Figure 4.46** Stress-strain curves of PU samples made from copolymers according to method EN ISO 529-4: 1997(CEN1997a)\n\n**4.19PU** – PU based on homopolymerized THF; (4.19)\n\n**4.4PU** – PU based on copolymer of epoxidized methyl oleate (2.3) and THF; (4.4)\n\n**4.7PU** – PU based on copolymer of epoxidized cocoa butter (2.16) and THF; (4.7)\n\n**4.10PU** – PU based on copolymer of epoxidized palm oil (2.17) and THF; (4.10)\n\n4.12PU – PU based on copolymer of epoxidized rapeseed oil (2.13) and THF; (4.12)\n4.15PU – PU based on copolymer of epoxidized soybean oil (2.6) and THF; (4.15)\n4.18PU – PU based on copolymer of euphorbia oil (2.18) and THF; (4.18)\n\nTable 4.16 Properties of PU samples made from copolymers\n\n| PU | Tensile strength (MPa) | Elongation at break (%) | Cross-link density x 10^{-4} (mol/cm^3) |\n|------|------------------------|-------------------------|----------------------------------------|\n| 4.19PU | 8.3 | 6 | 0.65 |\n| 4.4PU | 5.3 | 350 | 3.23 |\n| 4.7PU | 5.9 | 610 | 3.38 |\n| 4.10PU | 9.1 | 425 | 5.30 |\n| 4.12PU | 10.5 | 510 | 6.05 |\n| 4.15PU | 9.5 | 250 | 7.52 |\n| 4.18PU | 5.0 | 140 | 3.95 |\n\nReferring to Table 4.16 and Figure 4.46, the (4.19PU) shows significantly high tensile strength (8.3 MPa) but low elongation (6%). The tensile strength of (4.19PU) comes from the intermolecular force between polymer chains of (4.19) as the polymer chains of (4.19) are more regular in structure, which can form semicrystalline structure in (4.19PU) and this semicrystalline structure acts as a physical cross-link in the PU polymer matrix.\\textsuperscript{110} However, the cross-link density of (4.19PU) was low (0.65 x 10^{-4} mol/cm^3) because both the (4.19) and MDI are bifunctionals molecules that usually form linear polymers.\n\nBoth copolymers (4.4 and 4.7) were made from epoxidized oils with one epoxide group and the hydroxyl values of both copolymers were relatively lower than other copolymers. Therefore, the cross-link densities exhibited by PU made from both copolymers (4.4PU and 4.7PU) were relatively low (3.2-3.4 x 10^{-4} mol/cm^3). This\n\nrelatively low cross-link density translated to tensile strength in the region of 5.3 MPa to 5.9 MPa. However, there is a significant difference between these two PU as the elongation at break for (4.7PU) was significantly higher than (4.4PU). This better performance of (4.7PU) can be attributed to the plasticizing effect from the saturated fatty acid chains found in (4.7PU), which originated from epoxidized cocoa butter (2.16).\n\nIn comparison, (4.10PU) made from copolymers based on epoxidized palm oil (2.17), which has two epoxides functionality has a higher cross-link density and tensile strength exhibited than both (4.4PU and 4.7PU). However, the higher cross-link density also contributed to lower elongation at break as compared to (4.7PU). On the other hand, (4.18PU) made from (4.18) copolymers exhibited lower tensile strength and elongation at break as compared to (4.10PU) even though the copolymers (4.18) were made from euphorbia oil (2.18), which has the same level of epoxide functionalites as (2.17). As discussed earlier in Section 4.11 (page 156), the copolymer (4.18) has a lower hydroxyl value (33 mg KOH/g) as compared to (4.10) (40 mg KOH/g) due to the alkene groups still remaining in (4.18). The lower hydroxyl value of (4.18) contributed to lower cross-link density, tensile strength and elongation at break of (4.18PU). In addition, it is proposed that the extra ‘kink’ from alkene groups (4.18PU) also contributed to lower performance of (4.18PU) as compared to (4.10PU) by obstructing the packing of the PU polymer chains, which reduced the intermolecular force of the PU polymer chains.\n\nReferring to Figure 4.46, (4.12PU) exhibited the highest tensile strength among all the PU samples. This is due to the relatively high cross-link density of (4.12PU),\n\nwhich was contributed by the relatively higher hydroxyl value of (4.12) (48 mg KOH/g). In contrast, the (4.15PU) has a higher cross-link density than (4.12PU) due to the higher hydroxyl value of (4.15). However, the elongation at break of (4.15PU) was lower than (4.12PU) even though they have similar tensile strength. It is proposed that the cross-link density of (4.15PU) was now too high and that it made the PU (4.15PU) stiffer, which restricted the elongation of (4.15PU), resulting in lower elongation at break.\n\n4.17 POLYURETHANES MADE FROM COPOLYMERS OF EPOXIDIZED PLANT OILS AND ε - CAPROLACTONE\n\n\\[\n\\begin{align*}\n\\text{OCN} & \\quad \\text{MDI} \\\\\n& + \\\\\n\\text{HO} & \\quad \\text{R} & \\quad \\text{OH} \\\\\n(4.24)\n\\end{align*}\n\\]\n\n\\[\n\\begin{align*}\n\\left[ \\text{O} & \\quad \\text{C} & \\quad \\text{O} & \\quad \\text{N} & \\quad \\text{H} & \\quad \\text{N} & \\quad \\text{H} & \\quad \\text{O} & \\quad \\text{O} & \\quad \\text{R} & \\quad \\text{O} & \\quad \\text{O} & \\quad \\text{C} & \\quad \\text{O} & \\quad \\text{C} \\right]_n \\\\\n(4.24PU)\n\\end{align*}\n\\]\n\nFigure 4.47 Synthesis of PU from MDI and (4.24)\n\nThe copolymers of (4.24) made from epoxidized palm oil (2.17) and ε-caprolactone (4.23) were reacted with MDI (Figure 4.47) according to reaction condition described in Section 4.16 to produce (4.24PU). The (4.24PU) was subjected to tensile strength evaluation as well as swelling test in order to evaluate the physical properties of the PU. The following Figure 4.48 shows the stress-strain curve of (4.24PU).\n\nFigure 4.48 Stress-strain curve of (4.24PU) according to method EN ISO 529-4: 1997(CEN1997a)\n\nFigure 4.48 show that (4.24PU) has relatively low tensile strength and elongation at break. This may be due to the relatively low average molecular weight of (4.24), which range from 5000 Da to 6000 Da as compared to THF based copolymers which range from 26000 Da to 110000 Da. The properties of cross-linked PU, such as tensile strength and elongation generally increase with the increasing molecular weight of the polyols.\\textsuperscript{101}\n\n\\subsection*{4.18 THERMAL PROPERTIES OF POLYURETHANES MADE FROM COPOLYMERS}\n\nThermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were conducted on the prepared PU samples made from copolymers in order to evaluate the thermal properties of these PU samples. In addition, PU made from\n\nhomopolymerized THF (4.19) was also evaluated for comparison purposes. The following are the results of the thermal analysis.\n\n**Thermal gravimetric analysis (TGA)**\n\nThe following Figure 4.49 and 4.50 show the TGA analysis of PU samples made from copolymers and (4.19).\n\n\n\n*Figure 4.49 TGA analysis of PU samples (4.4PU, 4.7PU and 4.10PU) and (4.19)*\n\n\n\n*Figure 4.50 TGA analysis of PU samples (4.12PU, 4.15PU and 4.18PU)*\n\nReferring to Figure 4.49 and 4.50, the PU made from copolymers and homopolymers of THF started to degrade at about 300 °C. The TGA analysis also shows that some of the PU samples (4.4PU and 4.18PU) exhibit a minor component and a major component in the samples. The minor component could be unreacted fatty acids / triglycerides. Meanwhile, the evaluated PU samples (4.7PU, 4.10PU, 4.12PU and 4.15PU) exhibit one component in the samples. All the PU samples were thermally stable up to 300 °C before they all start degrading.\n\n**Differential Scanning Calorimetry (DSC)**\n\nThe following Figure 4.51 and 4.52 show the DSC analysis of PU samples made from the copolymers. The DSC analysis shows that all the PU made from the copolymers have glass transition temperatures (Tg) at about -70 °C. This low Tg contributed to the flexibility of the PU and they are able to remain flexible even at low temperatures. Furthermore, each of the PU samples exhibited a softening/melting point at temperature ranges from 10 °C to 45 °C, depending on the copolymers used in making the PU before they degraded at 300 °C.\n\n\n\n*Figure 4.51 DSC analysis of PU samples (4.19PU, 4.4PU, 4.7PU and 4.10PU)*\n\n4.19 SUMMARY\n\nThe prepared epoxidized plant oils (2.3, 2.16, 2.17, 2.13, 2.6 and 2.18) can be copolymerized with THF to yield copolymers polyols through cationic ring opening reaction of both epoxide and THF catalyzed by $\\text{BF}_3\\cdot\\text{Et}_2\\text{O}$. The copolymerization reaction was affected by the amount of catalyst, reaction temperature, reaction duration and the ratio between the two monomers (epoxidized plant oils and THF).\n\nThe properties of the copolymers also depended on the degree of unsaturation of the plant oils. Plant oils with low unsaturation [methyl oleate (2.8), cocoa butter (2.9)] will yield copolymers with lower molecular weights (4.4 and 4.7); while plant oils with two or more unsaturations will produce high molecular weight copolymers and higher hydroxyl values (4.10, 4.12, 4.15 and 4.18).\n\nThe prepared copolymers were used to make PU samples. PU based on copolymers made from plant oil with low levels of unsaturation (2.3, 2.16) formed PU samples (4.4PU and 4.7PU) with lower levels of tensile strength but with acceptable elongation (flexibility). In fact, (4.7PU) showed the highest elongation at break due to the plasticizing effect from the saturated fatty acid chains found in (4.7PU). These PU samples (4.4PU and 4.7PU) have suitable mechanical properties for making elastomeric PU that requires very good flexibility. On the other hand, PU samples based on copolymers made from plant oils with higher levels of unsaturation (4.10PU, 4.12PU and 4.15PU) exhibited higher tensile strength and elongation. The highest tensile strength was exhibited by (4.12PU). These PU samples have suitable mechanical properties for making semi-flexible PU elastomers that require high tensile strength with some flexibility.\n\nThermal gravimetric analysis (TGA) shows that most the PU samples made from copolymers were stable up to 300 °C. The TGA analysis also shows that PU samples (4.4PU and 4.18PU) exhibit a minor component and a major component in the samples. The minor component could be unreacted fatty acids/triglycerides. Meanwhile, PU samples (4.7PU, 4.10PU, 4.12PU and 4.15PU) exhibit one component in the samples. The DSC analyses also reveal that all the PU samples have melting/softening points between 10 °C to 45 °C, depending on the copolymers used in making the PU sample. The DSC analysis also shows that all the PU samples have glass transition temperatures at about -70 °C, which is relatively low and this makes them suitable for applications that require low temperature flexibility.\n\nCHAPTER 5 – ONE-POT OLIGOMERIZATION OF PLANT OIL DERIVATIVES\n\n5.0 INTRODUCTION\n\nOn a commercial scale, the epoxidation of unsaturated plant oil (5.1) is carried out through the Prileshajev reaction, in which a peroxy acid is the epoxidation agent generated from a short-chain organic acid such as formic acid\\textsuperscript{111} (Figure 5.1). However, the selectivity of this reaction seldomly exceeds 90% due to side reactions such as dimerization of epoxidized plant oil (5.2) through ring opening of epoxide group by hydroxylated plant oil (5.3) generated \\textit{in-situ} during the reaction (Figure 5.2). The amount of dimerized plant oil (5.4) found in the reaction products was about 2% as analyzed by the GPC method.\\textsuperscript{111} In addition, analysis results reported in Chapter 2 (page 60) show that during the epoxidation of (5.1) with a tungsten based catalyst system, the reaction produced about 4% of (5.4) as a side product. In general, the amount of oligomers generated as side products during epoxidation of (5.1) was about 2% to 4%.\n\n\\[\n\\begin{align*}\n\\text{Figure 5.1 Epoxidation of palm oil with formic acid and hydrogen peroxide}\n\\end{align*}\n\\]\n\nFigure 5.2 Dimerization of epoxidized plant oil\n\nIn comparison, more significant amount of oligomeric products were obtained during the ring-opening of epoxidized soybean oil (2.6) with water\\textsuperscript{85} catalyzed by phosphoric acid. Likewise, the ring-opening of epoxidized soybean oil in methanol\\textsuperscript{86} catalyzed by fluoroboric acid was also reported to produce about 20% oligomers of triglycerides. In addition, results in Chapter 2 (page 94) show that oligomeric plant oils can be produced from homopolymerization of epoxidized plant oils in good yield. However, this process requires two steps namely epoxidation followed by epoxide ring opening. This prompted a study to investigate the possibility of producing oligomeric plant oils using a one-pot method.\n\n5.1 DIRECT OLIGOMERIZATION OF PLANT OIL WITH TUNGSTEN BASED CATALYST\n\nFigure 5.3 Oligomerization of unsaturated plant oils\n\nHaving established that low oligomerization (2-4%) can occur during the epoxidation reaction of rapeseed oil catalyzed by tungsten powder as described in Chapter 2\n\n(page 60), the next step was to investigate how the amount of oligomers can be increased by a) changing the catalyst ($\\text{Na}_2\\text{WO}_4$) and b) changing the plant oils feedstock (rape, palm, soy etc). The effect of these changes was compared at 100 °C (Figure 5.3). The experimental conditions for this study were listed in Table 5.1 and the results of this study were tabulated in Table 5.2.\n\nTable 5.1 Experiments conducted with various plant oils and reaction conditions\n\n| Entry | Plant oil | Catalyst | Mol equivalent |\n|-------|--------------------|------------|----------------|\n| 1 | Palm | $\\text{Na}_2\\text{WO}_4$ | 100: 2: 2: 500: 0: 0 |\n| 2 | Soy | $\\text{Na}_2\\text{WO}_4$ | 100: 2: 2: 500: 0: 0 |\n| 3 | 50%Palm + 50% Soy | $\\text{Na}_2\\text{WO}_4$ | 100: 2: 2: 500: 0: 0 |\n| 4 | Rapeseed | $\\text{Na}_2\\text{WO}_4$ | 100: 2: 2: 500: 0: 0 |\n| 5 | Rapeseed | $\\text{Na}_2\\text{WO}_4$ | 100: 2: 2: 150: 0: 0 |\n| 6 | 50%Palm + 50% Soy | W powder | 100: 0.5: 0.3: 95: 65: 1450 |\n| 7 | Rapeseed | W powder | 100: 0.5: 0.3: 95: 65: 1450 |\n\nMol equivalent = (alkene:catalyst:PTC:$\\text{H}_2\\text{O}_2$:Acid:$\\text{H}_2\\text{O}$), PTC= phase transfer catalyst Adogen 464; Acid= $\\text{H}_3\\text{PO}_4$\n\nTable 5.2 Analysis results of reaction products\n\n| Entry | Oligomer (%) | $M_w$ (Da) | $M_n$ (Da) | PDI | Yield % |\n|-------|--------------|------------|------------|-----|---------|\n| 1 | 20 | 2800 | 2600 | 1.08| 85 |\n| 2 | 24 | 3100 | 2700 | 1.15| 88 |\n| 3 | 33 | 3300 | 2800 | 1.18| 85 |\n| 4 | 27 | 2900 | 2600 | 1.12| 84 |\n| 5 | 18 | 5600 | 4900 | 1.20| 83 |\n| 6 | 23 | 3600 | 3100 | 1.16| 83 |\n| 7 | 39 | 11300 | 6700 | 1.67| 81 |\n\n$M_w =$ weight average molecular weight, $M_n =$ number average molecular weight, PDI = polydispersity index\n\nReferring to Table 5.2, direct oligomerization of palm oil (Entry 1) with $\\text{Na}_2\\text{WO}_4$ yielded 19.5% oligomers and GPC analysis showed that the oligomers have a $M_n$ of about 2600 Da, which indicates the formation of mainly dimers. The low amount of oligomers could be attributed to the relatively low unsaturation in palm oil. The $^1\\text{H}$ NMR spectrum of the product shows a significant peak at 3.2 -2.8 ppm, which indicates unreacted epoxide groups. When plant oils with higher alkene contents were used as the starting material, namely soya bean oil (Exp. 2), the amount of oligomers formed (24%) in the reaction product was higher than palm oil (19%) while the $^1\\text{H}$ NMR analysis shows the complete disappearance of the epoxide moiety, which suggests more effective formation of oligomers due to the higher amount of alkene group in the starting material.\n\n**Mixture of palm and soy oil**\n\nWhen an equal mixture of palm and soy oil was used (Exp. 3) as starting material, the amount of oligomers formed in the product was measured at 32.8%. This is significantly higher than observed in experiments conducted with pure soy (Exp. 2) or pure palm oil (Exp. 1). This suggests that the combination of soy and palm oil enhances the formation of oligomers in some way and may be due to the almost equal amount of oleic and linoleic acid found in the 50:50 mixtures of soy and palm oil.\n\nIn general the highest level of oligomers was formed using our original tungsten powder procedure (Entry 7, 39%) but this was not high enough to be useful as a one pot oligomerization procedure.\n\n5.2 OLIGOMERIZATION OF OLEIC ACID\n\nDue to the complexity of the triglyceride mixtures, similar reactions were conducted on simple fatty acids as model compounds (Figure 5.4). Oleic acid (5.5) (a monounsaturated fatty acid) was subjected to the oligomerization reaction with $\\text{Na}_2\\text{WO}_4$ as the catalyst and Adogen 464 as the phase transfer catalyst (PTC). These experiments were conducted with $\\text{Na}_2\\text{WO}_4$ as opposed to W powder because of a simpler experiment procedure. The gel permeation chromatography (GPC) analysis shows that 75% of the crude product from the reaction consists of dimer and higher oligomers. A detailed analysis is shown below (Table 5.3).\n\n\n\n**Figure 5.4** Oligomerization of (5.5) with $\\text{Na}_2\\text{WO}_4$ and $\\text{H}_2\\text{O}_2$\n\n**Table 5.3** GPC analysis of crude product from oligomerization of oleic acid\n\n| Component detected | Gel permeation chromatography (GPC) | Content % |\n|--------------------|-------------------------------------|-----------|\n| | $M_w$ (Da) | $M_n$ (Da) | PDI | |\n| 1 | 2800 | 2500 | 1.12 | 38 |\n| 2 | 1400 | 1400 | 1.00 | 24 |\n| 3 | 890 | 870 | 1.02 | 27 |\n| 4 | 530 | 520 | 1.02 | 11 |\n\n$M_w =$ weight average molecular weight, $M_n =$ number average molecular weight, PDI = polydispersity index\n\nThe crude product of the oleic acid oligomerization was subjected to column chromatography. The major component (75%) was subjected analyzed by $^1$H NMR, ESI-MS and MALDI-TOF-MS in order to determine the chemical structure of the compound (assigned as 5.6). $^1$H NMR analysis of (5.6) indicates two peaks that correspond to a methine proton attached to a carbon atom of a hydroxyl group (HO-C-H) and an ester group (O=C-O-C-H) at 3.7 ppm and 4.85 ppm respectively (Figure 5.5). Furthermore, $^1$H-$^1$H COSY analysis shows that both peaks are coupled to each other, which imply that both methine protons are next to each other as depicted in the proposed chemical structure of the compound (5.6) (Figure 5.6), which is an oligomer of oleic acid linked by an ester functionality known as estolide.\n\n\n\n**Figure 5.5** 400 MHz $^1$H NMR spectrum of (5.6) in CDCl$_3$\n\n\n\n**Figure 5.6** Proposed chemical structure of (5.6)\n\nCompound (5.6) was analyzed with MALDI-TOF-MS that usually detects protonated molecular ions \\([M+H]^+\\) and also sodium adduct ions \\([M+Na]^+\\) as well as fragmentation ions. The MALDI-TOF-MS analysis of (5.6) shows molecular weight ranges from 500 Da to 2000 Da with the dominant mass peak at 1104 Da (Figure 5.7). This 1104 Da mass peak corresponds to the cleaved sodium adducts \\([M+Na]^+\\) (5.7) of tetramer \\(n=4\\) (\\(M=1233\\) Da) as shown in Figure 5.8. Furthermore, the dimer, trimer and pentamer sodium ion adduct were also detected in the mass spectra of (5.6) at 637 Da, 935 Da and 1531 Da respectively. This further confirms that the reaction produced oligomers of oleic acid linked by the ester group (estolides) and the major product was the tetramer of oleic acid.\n\n\n\n**Figure 5.7** MALDI-TOF-MS spectrum of (5.6) by using DHB as the matrix in the analysis\n\n\n\n**Figure 5.8** Cleaved sodium adduct of (5.6)\n\nThese results show that the oleic acid was oligomerized to form estolides with the proposed chemical structure (5.6). The formation of estolides from oleic acid through this one-pot oligomerization reaction is believed to occur via a two steps process. The first step is believed to be the conversion of the alkene (C=C) group to the epoxide group through $\\text{Na}_2\\text{WO}_4$ catalyzed epoxidation reaction with hydrogen peroxide and the second step involves ring opening of the newly formed epoxy group by the carboxylic acid group of another fatty acid to yield the observed estolides (Figure 5.9). Based on MALDI-TOF-MS mass spectrum, the most abundant oligomer is the tetramer of oleic acid, followed by trimer and dimer.\n\n\n\n**Figure 5.9** Proposed mechanism for epoxy ring opening by carboxylic acid group of another fatty acid to yield the estolides\n\nWhen the same reaction was conducted with methyl oleate (5.8) (in substitution of oleic acid) (Figure 5.10), no formation of oligomers was observed. The $^1\\text{H}$ NMR spectrum of the crude product (Figure 5.11) from this reaction shows a singlet at $\\delta=3.55$ ppm, which corresponds to the methyl of ester group and supports the idea that oligomerization did not take place.\n\nFurthermore, no significant peaks at $\\delta = 3.7$ ppm and $4.85$ ppm was observed, which correspond to methine proton attached to carbon atom of a hydroxyl group (HO-C-H) and an ester group (O=C-O-C-H) at $3.7$ ppm and $4.85$ ppm respectively as seen in Figure 5.5. Again, this indicates no formation of oligomerized oleate compounds (estolides). The product from this reaction is dihydroxy methyl stearate (5.9) (Figure 5.12), which shows a peak at $\\delta = 3.33$ ppm in $^1$H NMR spectrum that corresponds to the methine proton attached to carbon atom of a hydroxyl group (HO-C-H) (Figure 5.11).\n\n\n\n**Figure 5.11** 400 MHz $^1$H NMR spectrum of (5.9) in CDCl$_3$\n\nThe other chemical compound that could be produced from the oligomerization reaction of oleic acid is a polyether polyol (5.10) where an alcohol has reacted with\n\nan epoxide instead of a carboxylic acid. This alternative product will have the same mass ion as discussed above for (5.6). The possible chemical structure is illustrated in Figure 5.13, which is an oligomer of oleic acid linked by ether functionality.\n\n\\[\n\\begin{align*}\n&\\text{OH} \\\\\n&\\text{O} \\\\\n&\\text{OH} \\\\\n&\\text{CO}_2\\text{H} \\\\\n&\\left[ \\text{OH} \\right]_n\n\\end{align*}\n\\]\n\n(5.10)\n\nFigure 5.13 Oligomers of oleic acid linked by ether functionality\n\nThis oligomer could be produced when the oxirane group of epoxidized oleic acid was ring opened by water to yield initially a dihydroxyl group (HO-C-C-OH) and then one of the newly formed hydroxyl groups can attack the epoxide group of another epoxidized oleic acid molecule to form an ether linkage between the two fatty acid chains (Figure 5.14). The other hydroxyl group could repeat this process and form higher oligomers.\n\nFigure 5.14 Mechanism for the formation of oleic acid oligomers linked by ether group\n\nReduction and saponification of (5.6)\n\nIn order to further confirm the chemical structure of (5.6) and rule out the formation of (5.10), the oligomerized compound (5.6) was subjected to two reactions, namely reduction (LiAlH₄) and saponification (NaOH). LiAlH₄ is a strong reducing agent and it is capable of reducing ester bonds to alcohols. Therefore, when oligomerized product (5.6) was subjected to reduction with LiAlH₄, the ester linkages between the repeating units of oleic acid should be broken and reduced to alcohol groups (causing depolymerization). If however the linkages between the monomers were ether linked then the compound would not be reduced to monomer. The same concept applies to the saponification reaction, where the ester linkages between monomer will be cleaved by NaOH but will not be cleaved if the linkages between monomer were ether groups.\n\nWhen (5.6) was subjected to saponification and the crude product was purified by column chromatography the major product produced from the reaction was 9,10-dihydroxystearic acid (5.11). Reduction reaction of oligomerized product (5.6) with LiAlH₄ gave 1,9,10-trihydroxysterol (5.12) as the major product (Figure 5.15). Both these reactions indicate that the linkage between fatty acid units was the expected ester linkage and ruled out an ether linkage.\n\n\\[\n\\begin{align*}\n&\\text{OH} \\\\\n&\\text{OH} \\\\\n&\\text{CO}_2\\text{H} \\quad (5.11)\n\\end{align*}\n\\]\n\n\\[\n\\begin{align*}\n&\\text{OH} \\\\\n&\\text{OH} \\\\\n&\\text{OH} \\quad (5.12)\n\\end{align*}\n\\]\n\nFigure 5.15 Major products from saponification and reduction of (5.6)\n\nMinor component from saponification reaction\n\nWhile the major product isolated from the saponification reaction of (5.6) was 9,10-dihydroxy stearic acid (5.11), a minor component was also isolated from the column and identified as the alternative polyether polyol (5.13) (10% yield), in which the repeating units of oleic acid were linked by an ether group. ESI mass spectrometry of this polyether polyol shows a dominant peak at 637 [M+Na]+, which correspond to a dimer of (5.11) linked by an ether bond with molecular structure (5.13) as depicted in Figure 5.16.\n\n\n\nIn conclusion, analysis of the product arising from Na₂WO₄ reaction with oleic acid suggests a composition of 90% ester linked (5.6) and 10% ether linkage (5.13).\n\n5.3 1,9-NONANEDIOIC (AZELAIC ACID)\n\n\n\nDuring the oligomerization of oleic acid, a co-product was isolated namely 1,9-nonanedioic (5.14) (azelaic acid) (Figure 5.17). Azelaic acid dissolves in hot water; therefore it dissolved in the aqueous layer during the oligomerization reaction but crashed out from the cooled aqueous layer as a white solid during product work-up at room temperature. The yield of azelaic acid obtained in this way from the\n\noligomerization reaction was low (about 2%), however, due to its known applications in polymer (nylon 69) and anti-acne products, the renewable nature of this co-product made it a target of further study. In particular, how is the azelaic acid formed during the oligomerization of oleic acid and is it possible to maximize the yield of this co-product?\n\nThe azelaic acid could be produced from oxidative cleavage of one or more compounds involved in the oligomerization reaction, namely the starting material (oleic acid) (5.5), the intermediate product epoxidized oleic acid (5.15) or product [dihydroxystearic acid (5.11), ester linked (5.6) and ether linked (5.13) oligomers] (Figure 5.18). Therefore by subjecting these compounds individually to the same oligomerization reaction conditions, the intermediate responsible for the formation of (5.14) can be determined.\n\n\n\nFigure 5.18 Chemical compounds involved in the oligomerization reaction\n\nIn order to achieve this goal, some oleic acid model derivatives were synthesized that represented the potential intermediate compounds involved in the oligomerization reaction. The oleic acid derivatives (5.11, 5.16, 5.17, 5.18) (Figure 5.19) were synthesized and subjected to the oligomerization reaction conditions.\n\nFigure 5.19 Synthesized oleic acid model derivatives\n\nThe following Figure 5.20 – 5.23 shows the synthesis of these oleic acid derivatives. Compound (5.16) represents an intermediate in the oligomerization of oleic acid while compounds (5.11), (5.17) and (5.18) represent models of possible products from the oligomerization reaction of oleic acid. Compound (5.11) is the monomer of the oligomers while both (5.17) and (5.18) represent possible oligomers from the reaction. Compound (5.17) has a similar estolide carbon backbone structure to (5.6) with the addition of three acetyl groups to mimic further the oligomers of oleic acid linked by ester linkages (estolides oligomers). Meanwhile, the compound (5.18) has two methoxy groups that mimic the oligomers of oleic acid linked by ether linkages (polyether oligomers).\n\nFigure 5.20 Synthesis of epoxidized methyl oleate (5.16)\n\nFigure 5.21 Synthesis of 9,10-dihydroxystearic acid (5.11)\n\n\\[\n\\begin{align*}\n&\\text{1) } \\text{H}_2\\text{O}_2, \\text{ HCO}_2\\text{H, H}_2\\text{SO}_4 \\\\\n&\\quad 90^\\circ\\text{C}, 24 \\text{ h} \\\\\n&\\quad \\downarrow \\\\\n&\\quad \\text{2) NaOH, 95 }^\\circ\\text{C, 24 h} \\\\\n&\\quad \\downarrow \\\\\n&\\quad \\text{50%}\n\\end{align*}\n\\]\n\nFigure 5.22 Synthesis of triacetyl estolides (5.17)\n\n\\[\n\\begin{align*}\n&\\text{(CH}_3\\text{CO)}_2\\text{O, H}_3\\text{PO}_4 \\\\\n&\\quad 100^\\circ\\text{C, 6 h} \\\\\n&\\quad \\downarrow \\\\\n&\\quad \\text{36%}\n\\end{align*}\n\\]\n\nFigure 5.23 Synthesis of 9,10-dimethoxystearic methyl ester (5.18)\n\n\\[\n\\begin{align*}\n&\\text{MeI, KOH, THF} \\\\\n&\\quad 40^\\circ\\text{C, 24 h} \\\\\n&\\quad \\downarrow \\\\\n&\\quad \\text{50%}\n\\end{align*}\n\\]\n\nEach of the four potential precursors to azelaic acid were reacted under the original oligomerization reaction conditions (namely 5 molar equivalents of $\\text{H}_2\\text{O}_2$ at 100 °C for 8 hours, catalyzed by $\\text{Na}_2\\text{WO}_4$ and a phase transfer catalyst, Aliquat 336).\n\nBased on analysis results, the formation of azelaic acid could only be detected when (5.11) and (5.16) were subjected to the oligomerization reaction with 1% and 3% yields respectively. Both (5.17) and (5.18) did not yield any azelaic acid when subjected to the same reaction conditions. Therefore, this indicates that the oxidative cleavage is a side reaction that happens before the formation of oligomers and it is not a continuation from the oligomerization reaction.\n\n### 5.4 OPTIMIZATION OF OLEIC ACID OLIGOMERIZATION TO ESTOLIDE (5.6)\n\n**Effect of reaction temperature**\n\nThis study was conducted to determine the most appropriate temperature for the oligomerization reaction. The temperature of the reaction was varied from 60 °C to 100 °C, while the other reaction parameters were kept constant. The following Figure 5.24 shows the stacked 400 MHz $^1\\text{H}$ NMR spectrum of crude reaction products from oligomerization reaction conducted at 60 °C, 80 °C and 100 °C respectively.\n\nReferring to Figure 5.24, when the oligomerization reaction was conducted at 60 °C, the alkene groups were not fully converted to epoxide group (compared to 100 °C). The $^1\\text{H}$ NMR spectrum indicates that some of the alkene has been converted to an epoxide group ($\\delta= 2.8-2.9$ ppm) and these epoxide groups would eventually be ring\n\nopened by the carboxylic group to form estolide oligomers if the reaction time was prolonged. This indicates that at 60 °C the rate of oligomerization is very slow.\n\nWhen the reaction was conducted at 80 °C, the alkene was fully converted to other functionalities. The $^1$H NMR spectrum shows similar peaks to those observed at 100 °C ($\\delta = 3.7$ ppm, 4.85 ppm), which correspond to estolides. However, the $^1$H NMR spectrum also shows a residual peak at $\\delta = 2.85$ ppm corresponding to the epoxide group. This means that at 80 °C, the oligomerization reaction could proceed to completion if the reaction time was prolonged. Therefore, the most optimum temperature for the oligomerization reaction is 100 °C because all alkene were converted to ester linkages of estolides oligomers in the shortest time possible.\n\nFigure 5.24 Stacked 400 MHz $^1$H NMR spectrum of reaction products in CDCl$_3$ from oligomerization reaction conducted at 60 °C, 80 °C and 100 °C respectively\n\nEffect of hydrogen peroxide : alkene molar ratio on oligomerization\n\nThe objective of this study was to determine the optimum molar ratio between $\\text{H}_2\\text{O}_2$ and the alkene functionality of the fatty acid. Three ratios were chosen (5:1, 2.5:1 and 1.5:1). When the ratio was lowered from 5:1 down to 2.5:1 ($\\text{H}_2\\text{O}_2$: C=C), the $^1\\text{H}$ NMR spectrum (Figure 5.25) showed that the amount of $\\text{H}_2\\text{O}_2$ was enough to fully convert all the alkene to oligomers as the alkene peak at $\\delta = 5.35$ ppm was not visible in the spectrum. However, when the ratio was further lowered to 1.5:1 ($\\text{H}_2\\text{O}_2$: C=C), the $^1\\text{H}$ NMR spectrum showed that the amount of $\\text{H}_2\\text{O}_2$ was insufficient to fully convert all the alkene to oligomers. Therefore, the optimum molar ratio was determined as 2.5:1 ($\\text{H}_2\\text{O}_2$: C=C), which is the minimum amount of $\\text{H}_2\\text{O}_2$ needed to fully convert alkene to ester linkages of estolides oligomers.\n\n\n\nFigure 5.25 Stacked 400 MHz $^1\\text{H}$ NMR spectrum of crude reaction products in CDCl$_3$ from oligomerization reaction conducted at 1.5 mol, 2.5 mol and 5 mol of $\\text{H}_2\\text{O}_2$ respectively\n\n5.5 ONE-POT OLIGOMERIZATION OF OLEIC ACID WITHOUT CATALYST\n\nA report\\textsuperscript{112} indicated that unsaturated fatty acids such as oleic acid (5.5) can be epoxidized in the presence of $\\text{H}_2\\text{O}_2$ with enzyme (Novozym 435) as the catalyst. The enzyme catalyzed the formation of peracid from the oleic acid with $\\text{H}_2\\text{O}_2$ as the source of oxygen. The newly formed oleic peracid in turn epoxidized the alkene group of another fatty acid. Based on this procedure, a study was conducted to determine whether (5.5) can be “self-epoxidized” without any catalyst (enzymatic or chemical). Therefore, (5.5) was reacted with hydrogen peroxide at 80 °C without any catalyst for 1 day in an attempt to yield estolides (5.6) and GPC analysis of the crude product showed 43% of oligomers and $^1\\text{H}$ NMR spectrum shows some of the alkene group still remained unreacted. Then, the reaction time was prolonged to 3 days (Figure 5.26) in order to increase the oligomeric content and GPC analysis (Table 5.4) indicated that the crude product had about 71% oligomeric content.\n\nTable 5.4 GPC analysis of crude product from oligomerization of oleic acid\n\n| Component detected | Gel permeation chromatography (GPC) | Content % |\n|--------------------|------------------------------------|-----------|\n| | $M_w$ (Da) | $M_n$ (Da) | PDI | |\n| 1 | 3300 | 2800 | 1.18 | 38 |\n| 2 | 1300 | 1200 | 1.05 | 33 |\n| 3 | 480 | 440 | 1.09 | 29 |\n\n$M_w =$ weight average molecular weight, $M_n =$ number average molecular weight, PDI = polydispersity index\n\nFigure 5.26 Self-oligomerization of oleic acid in the presence of $\\text{H}_2\\text{O}_2$\n\nThe following Figure 5.27 and 5.28 are the 400 MHz $^1$H NMR spectrum and $^1$H-$^1$H COSY NMR spectrum of the product respectively. Figure 5.27 shows two peaks that correspond to a methine proton attached to a carbon atom of a hydroxyl group (HO-C-H) and an ester group (O=C-O-C-H) at 3.6 ppm and 4.82 ppm respectively. Furthermore, Figure 5.28 analysis shows that both peaks are coupled to each other, which imply that both methine protons are next to each other as depicted in the proposed structure of (5.6)\n\nFigure 5.27 400 MHz $^1$H NMR spectrum of (5.6) in CDCl$_3$\n\nMALDI-TOF-MS analysis of product (Figure 5.29) shows oligomers of oleic acid with molecular weight of 1829 Da, which corresponds to sodium adduct of hexamer of oleic acid. The repeating unit of the estolides has a molecular weight of 298 Da, which corresponds to structure (5.19) depicted in Figure 5.30.\n\nFigure 5.28 400 MHz $^1$H-$^1$H COSY NMR spectrum of (5.6) in CDCl$_3$\n\nFigure 5.29 MALDI-TOF-MS spectrum of (5.6) by using DHB as the matrix in the analysis\n\n5.6 ONE POT OLIGOMERIZATION OF PLANT OIL WITH SUCCINIC ACID\n\nThe same method (one-pot oligomerization of oleic acid) was applied to make oligomers from plant oils. The reactions were conducted with succinic acid (5.20) as the substitute for oleic acid in order to incorporate more renewable chemicals into the oligomers. The unsaturated plant oils [cocoa butter (5.21), palm oil (5.22), rapeseed oil (5.23) and soybean oil (5.24)] (Figure 5.31) were used in this study and they were reacted with (5.20) and hydrogen peroxide at 80 °C for 7 days (Figure 5.32). The following Table 5.5 shows the GPC analysis results of the reaction products. Acetic acid was included in this study as a control reaction and it was reacted with (5.24) using the same protocol.\n\n(5.21)\n\n(5.22)\n\nFigure 5.31 Plant oils used in this study\n\n\\[\n\\begin{align*}\n&\\text{H}_2\\text{O}_2, \\ 80^\\circ\\text{C}, \\ 7 \\text{ days} \\\\\n&\\downarrow \\\\\n&\\text{Oligomers (5.25)}\n\\end{align*}\n\\]\n\nFigure 5.32 Oligomerization of soybean oil (5.24) with succinic acid (5.20) and H$_2$O$_2$ as an example\n\nTable 5.5 GPC analysis of reaction products\n\n| Entry | Plant oil | Yield (%) | Gel permeation chromatography |\n|-------|-----------|-----------|------------------------------|\n| | | | M$_w$ (Da) | M$_n$ (Da) | PDI |\n| 1 | Control | 25 | 5100 | 4400 | 1.16 |\n| 2 | 5.21 | 0 | - | - | - |\n| 3 | 5.22 | 50 | 8500 | 7400 | 1.15 |\n| 4 | 5.23 | 68 | 23900 | 8900 | 2.70 |\n| 5 | 5.24 | 75 | 80800 | 11600 | 6.97 |\n\nM$_w$ = weight average molecular weight, M$_n$ = number average molecular weight, PDI = polydispersity index\n\nThe GPC analysis results show that the control reaction (Entry 1) only managed to yield 25% oligomeric products and the $^1$H NMR analysis of the products shows that (5.24) was majorly converted to epoxidized soybean oil (2.6). Next, the reaction was repeated with cocoa butter (5.21), which has one alkene group per molecule and it was reacted with (5.20) and H$_2$O$_2$. $^1$H NMR spectrum of product shows that (5.21) was epoxidized but was not oligomerized as shown by GPC analysis (Entry 2). The (5.21) with only one alkene group per molecule was not reactive to form oligomeric compounds with (5.20) due to the low level of unsaturation.\n\nPalm oil (5.22) which has two alkene groups per molecule was reacted using the same method and the GPC analysis shows that reaction product has about 50% oligomers (Entry 3). $^1$H NMR spectrum of the reaction product shows that the alkene groups of (5.22) were converted to hydroxyl groups. The higher alkene content of (5.22) as compared to (5.21) has contributed to higher amount of oligomers. When (5.22) was substituted with (5.23) which has higher alkene content, the GPC analysis (Entry 4) shows that higher amount of oligomers (68%) was produced as compared to (5.22). As expected, (5.24) produced the highest amount of oligomers (75%) as compared to other plant oils because it has the highest alkene content. This finding supports the hypothesis that plant oil with higher alkene content will produce more oligomers. In addition, the higher alkene content of a plant oil also contributed to oligomers with higher molecular weight and PDI. $^1$H NMR analysis of the oligomers (5.25) made from (5.24) (Figure 5.33) shows that all the alkene groups were converted to hydroxyl (3.4 - 3.8 ppm) and esters (4.8 – 4.9 ppm) moieties.\n\n5.7 ONE POT OLIGOMERIZATION OF PLANT OIL WITH ADIPIC ACID AND PHTHALIC ANHYDRIDE\n\nIn view that the direct oligomerization of unsaturated plant oils with succinic acid (5.20) needed 7 days of reaction time to yield significant amount of oligomers, (5.20) was substituted with other dicarboxylic acid to investigate the effect of different dicarboxylic acid on the oligomerization reaction. For this purpose, adipic acid (5.26) and phthalic anhydride (5.27) were chosen. Adipic acid was chosen because it is a C₆ linear aliphatic dicarboxylic acid, which has 2 extra -CH₂ group as compared to (5.20).\n\nThe study was conducted with (5.24) as the plant oil and it was reacted with (5.26) by using same one-pot oligomerization reaction as described in Section 5.6 (page 199) (Figure 5.34). $^1$H NMR analysis of reaction product (5.28) shows that all alkene groups of (5.24) were converted to epoxide as well as hydroxyl groups (Figure 5.35). It also shows that significant amount of epoxide group remained unreacted over the specific duration of reaction, which indicates that (5.26) is less reactive as compared to (5.20) in the oligomerization reaction. In addition, GPC analysis of reaction product shows that the oligomers content was about 40% ($M_w = 11000$ Da, $M_n = 8100$ Da, PDI = 1.36), which is significantly lower than product made with (5.20) under similar reaction condition. This may be due to the more hydrophobic nature of longer hydrocarbon chain of (5.26) as compared to (5.20) that made it less effective in an aqueous reaction system.\n\nWhen the same reaction was conducted with phthalic anhydride (5.27), the reaction was stopped after 1 day because the reaction mixture became too viscous to stir (Figure 5.36). Analysis of the reaction product (5.29) with GPC shows that the oligomeric content was about 75% ($M_w = 20100$ Da, $M_n = 10100$ Da, PDI = 1.99), which is a significant improvement from earlier studies conducted with (5.20). In addition, the reaction time was also significantly reduced from 7 days to 1 day. $^1$H NMR spectrum of (5.28) (Figure 5.37) shows the presence of aromatic ring, hydroxyl group and ester group moieties in the product.\n\n\n\n**Figure 5.35 400MHz $^1$H NMR spectrum of (5.28) in CDCl$_3$**\n\nEncouraged by this significant improvement, the same reaction was conducted with palm oil (5.22) that has lower level of unsaturation (Figure 5.38). The GPC analysis shows that the reaction product (5.30) contains about 66% oligomers ($M_w = 9200$ Da, $M_n = 7300$ Da, PDI = 1.26), which is significantly higher than oligomer content produced from reaction system using (5.20). Furthermore, the reaction time of was also reduced from 7 days to 1 days when (5.27) was used instead of (5.20).\n\n\\[\n\\begin{align*}\n&\\text{H}_2\\text{O}_2, \\ 80^\\circ\\text{C}, \\ 1 \\text{ day} \\\\\n&+ \\\\\n&\\text{Oligomers (5.30)}\n\\end{align*}\n\\]\n\nFigure 5.38 Oligomerization of (5.22) with (5.27) and $\\text{H}_2\\text{O}_2$\n\n$^1$H NMR spectrum (Figure 5.39) of (5.30) shows that all the alkene group of (5.22) was converted to hydroxyl moiety and the spectrum also shows that aromatic ring and ester group moieties were present in the product.\n\n\n\n### 5.8 POLYURETHANES MADE FROM ESTOLIDES (5.6) AND OLIGOMERS (5.25)\n\n\n\nThe prepared estolides (5.6) and oligomers (5.25) were reacted with 4,4'-diphenylmethane diisocyanate (MDI) and yielded quantitative amount of PU samples (5.31) and (5.32) respectively (Figure 5.40). The (5.31) and (5.32) were cross-linked polymers and were subjected to a tensile test in order to evaluate the strength of these PU samples and the following Figure 5.41 shows the stress-strain curve of (5.31) and (5.32).\n\n\n\n**Figure 5.41** Stress-strain curves of (5.31) and (5.32) according to method EN ISO 529-4: 1997(CEN1997a)\n\nReferring to Figure 5.41, (5.31) has high tensile strength (65 MPa) but low elongation at break (64%). These mechanical properties can be attributed to the high cross-link density ($43 \\times 10^{-4}$ mol/cm$^3$) found in (5.31), in which the highly cross-linked (5.31) requires more energy to pull it apart and at the same time restricts its elongation. The high cross-link density of (5.31) originated from high hydroxyl value of (5.6), which is 230 mg KOH/g sample. This range of hydroxyl value is suitable for making rigid PU products such as pipeline insulation materials and adhesives. On the other hand, the hydroxyl value of (5.25) was about 144 mg KOH/g sample. This\n\ncontributed to the lower cross-link density (30 x 10^{-4} \\text{ mol/cm}^3) of PU (5.32) and eventually leads to lower tensile strength (28 MPa) and elongation at break (25%).\n\n5.9 SUMMARY\n\nWhen plant oils with varying degree of unsaturation were subjected to one-pot oligomerization reaction in the presence of a tungsten based catalyst and hydrogen peroxide, the amount of oligomers generated from this process was about 20 - 40% depending on the feedstocks and the number average molecular weight of the oligomers ranges from 3000 – 6000 Da. In general, the tungsten catalyzed one-pot oligomerization was not very an effective method to prepare oligomers of plant oil derivatives.\n\nWhen the same reaction was repeated with oleic acid as the starting material, the reaction products were oligomers of oleic acid (estolides) and analysis with $^1$H NMR reveals that the estolides were linked by ester groups. Further confirmation of the estolides structure was achieved by reduction and saponification reactions. Furthermore, the one-pot oligomerization of oleic acid also yielded azelaic acid as a by-product and data from a series of investigative experiments indicated that the azelaic acid was produced mainly from epoxidized oleic acid before the oligomerization of oleic acid take place.\n\nThe oligomerization of oleic acid can also be achieved without any catalyst, in which the oleic acid was “self-epoxidized” by the peracid formed in situ from reaction\n\nbetween itself and $\\text{H}_2\\text{O}_2$. The epoxidized oleic acid was then ring opened by another oleic acid, thus forming the ester linked estolides.\n\nThis one-pot catalyst free oligomerization method was applied on various unsaturated plant oils by using renewable dicarboxylic acids such as succinic acid as the epoxidation and epoxide ring-opening agent to oligomerize the unsaturated plant oils. The results show that plant oils with two or more alkene groups per molecule can be oligomerized by succinic acid and the yield of oligomeric products were proportionate with the level of alkene group per molecule.\n\nIn comparison with succinic acid, longer chain aliphatic dicarboxylic acid (adipic acid) was less reactive in the oligomerization reaction, in which significant amount of epoxide groups remained unreacted. Meanwhile, aromatic anhydride (phthalic anhydride) was more reactive than succinic acid in the oligomerization procedure and the reaction time was reduced to only 1 day from 7 days. In addition, oligomerization with phthalic anhydride also produced higher amounts of oligomeric products as compared to succinic acid.\n\nThe estolides (5.6) and oligomers (5.25) prepared in this study were used to produce rigid PU by reaction with MDI. Both (5.6) and (5.25) have relatively high hydroxyl values and gave PU samples with relatively high cross-link density. The high cross-link density restricted the elongation of these PU and also translated to relatively high tensile strength. These PU samples are suitable for making rigid PU for thermal insulation purposes such as pipeline insulation.\n\nFuture Work\n\nThe results reported in Chapter 3 and 4 reveal that the properties of PU made from individual plant oil based polyols greatly depends on the level of unsaturation of the plant oils. Generally, plant oil with higher unsaturation level yields PU that exhibits higher tensile strength but lower elongation at break. Based on this structure-property relationship, the blending of plant oils with different level of unsaturation offers a method to tailor the properties of PU made from plant oil based polyols. In addition, the $OP$, $HP$ and copolymers of THF can be blended to produce PU with specific properties.\n\nFurthermore, the $OP$ can be subjected to saponification reaction to break the ester bond of the oligomerized plant oils and this will yield carboxylic acid groups, which can be reduced to hydroxyl, thus forming $OP$ with higher hydroxyl groups that can be used for making rigid PU. The said carboxylic acid groups can also be reacted with diamines to yield non-nylon polyamides or they can be converted to other functionalities that can be used for other applications.\n\n6.0 GENERAL INFORMATION AND PROCEDURES\n\nMaterials\n\nAll reactions were performed using commercially available chemicals and the purchased chemicals were used as received without any further purification.\n\nGeneral procedure\n\nThin layer chromatography was carried out on Merck 0.25 mm silica layer foiled-backed 60F-254 TLC sheets developed from potassium permanganate. Column chromatography was performed with Davisil silica gel Grade 633 pore size 60 Å particle size 40-63 µm.\n\nWet chemical analysis of product\n\nAll wet chemical analyses were performed according to the AOCS official\\textsuperscript{117} methods: acid value (AV), Te 1a-64 (89); hydroxyl value (OHV), Cd I3-60(89).\n\nProcedure for acid value analysis:\n\n(a) Weigh 0.5 g of sample into an Erlenmeyer flask.\n\n(b) Add approximately 100 ml of neutralized solvent (Isopropanol : Toluene, 50:50 mixture) and 3 drops of indicator (1% phenolphthalein in methanol)\n\n(c) Mix until sample completely dissolved.\n\n(d) Titrate with standardized alkali solution (0.1 N KOH in ethanol), stirring vigorously to the appearance of the first permanent pink color that persist for 1 minute.\n\nCalculation: Acid value, mg KOH per gram of sample =\n\n\\[\n\\frac{\\text{volume of alkali, mL} \\times N \\times 56.1}{\\text{mass of sample, g}}\n\\]\n\nwhere \\(N\\) = normality of alkali determined by standardization.\n\n**Procedure for hydroxyl value analysis:**\n\n(a) Weigh 1.0 g of sample into an Erlenmeyer flask.\n\n(b) Pipet 5.0 ml of pyridine-acetic anhydride reagent (pyridine : acetic anhydride, 3:1) into the flask containing the sample for acetylation. Thoroughly mix the contents by gentle swirling.\n\n(c) Pipet 5.0 ml of pyridine-acetic anhydride reagent into an empty flask for the reagent blank.\n\n(d) Place the samples and blank flasks on a hot plate, under a reflux condenser and heat at 100 °C for 1 hour.\n\n(e) Add 10 ml of water through the condenser to the flask and heat for an additional 10 minute with the reflux condenser attached.\n\n(f) Allow the flask to cool to room temperature with condenser attached.\n\n(g) Using a total of about 25 ml of neutralized butyl alcohol, wash the condenser with about 12 ml, remove the condenser and use the remaining butyl alcohol to wash the sides of the flask.\n\n(h) Add 1 ml of phenolphthalein indicator solution. Titrate to a faint pink end point with 0.5 N alcoholic KOH solution.\n\n**Calculation:** The hydroxyl value is calculated as follow:\n\n\\[\n\\text{Hydroxyl Value} = \\frac{B - S \\times N \\times 56.1}{W}\n\\]\n\nWhere\n\n\\[ B = \\text{volume, ml KOH solution required for the reagent blank} \\]\n\n\\[ S = \\text{volume, ml KOH solution required for titration of the acetylated sample} \\]\n\n\\[ N = \\text{normality of alcoholic KOH determined by standardization} \\]\n\n\\[ W = \\text{mass, gram of sample used for acetylation} \\]\n\n**Characterization**\n\nInfrared spectra were recorded as solid or liquid on Perkin-Elmer Spectrum100 FTIR spectrometer and absorption maxima (\\( \\nu_{\\text{max}} \\)) are recorded in wavenumbers (cm\\(^{-1}\\)). Solids were compressed into a thin table and non-volatile liquids were analyzed as thin film over diamond ATR top plate. Mass spectrometry of low resolution was recorded on Bruker Esquire ESI 2000 in which molecular ions, fragment ions and other major peaks are recorded as mass/charge (\\( m/z \\)) ratios. High resolution mass spectrometry was achieved by using Bruker MaXis instrument to carry out accurate ESI mass analysis. \\( ^1 \\)H and \\( ^{13} \\)C NMR spectroscopy were recorded on Bruker DPX-400 at 400 MHz and 100 MHz respectively at 298K with approximately 10% w/v solutions in deuterated NMR solvents. Chemical shifts are quoted in ppm relatively to internal standard tetramethylsilane (TMS) and reference to the residual solvent. All coupling constant are quoted in hertz (Hz). \\( ^1 \\)H and \\( ^{13} \\)C NMR assignments were routinely confirmed by \\( ^1 \\)H-\\( ^1 \\)H (COSY) and \\( ^1 \\)H-\\( ^{13} \\)C (HMQC) data. MALDI-TOF-MS measurement was performed with a Bruker Daltonics Ultraflex II TOF/TOF mass spectrometer equipped with a nitrogen laser delivering 3-ns laser pulses at 337 nm. 5 mg of sample was dissolved in 100 \\( \\mu \\)l tetrahydrofuran and 50 mg of 2,5-dihydroxybenzoic acid (DHB) as the matrix was dissolved in 200 \\( \\mu \\)l tetrahydrofuran. Sample solution (5 \\( \\mu \\)l) and matrix solution (20 \\( \\mu \\)l) were mixed and 0.5 \\( \\mu \\)l of this mixture was spotted on the target plate and analyzed. The sample was irradiated with\n\n(85%, 0.26 g, 2.24 mmol) in water (30 cm$^3$) was added into it (this is the tungsten catalyst solution). Methyl oleate (2.8) (100 g, 338 mmol) and Adogen 464 (0.45 g, 0.97 mmol) were charged into another 3-neck round bottom flask equipped with a motor stirrer. The methyl oleate mixture was heated to 50 °C and stirred vigorously. The tungsten catalyst solution was added to the methyl oleate mixture followed by deionized water (50 cm$^3$), hydrogen peroxide (65 g, 570 mmol). The temperature of the reaction mixture was kept at 70 °C for 3 hours. The reaction mixture was then poured into a separating funnel, and then saturated NaCl solution (100 cm$^3$) and diethyl ether (100 cm$^3$) were added to the reaction mixture. The aqueous layer was separated from the organic layer and the organic layer was neutralized with saturated sodium hydrogen carbonate solution (50 cm$^3$). The organic layer was again washed with NaCl solution (100 cm$^3$). The organic layer was dried over anhydrous MgSO$_4$ followed by removal of solvent *in vacuo* to yield epoxidised methyl oleate (EMO) (97 g, 311 mmol, 92% yield), which was a colorless liquid. $\\nu_{\\text{max}}$/cm$^{-1}$ 2924, 2855 (C-H) 1740 (C=O) 1170 (C-O) 825 (C-O-C) 723 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 3.60$ (3H, s, CH$_3$O), 3.20-2.80 (2H, m, CH$_2$CHOCHCH$_2$), 2.30 (2H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.67-1.54 (2H, m, O=CCH$_2$CH$_2$CH$_2$), 1.54-1.40 (4H, m, CHOCH$_2$CH$_2$), 1.37-1.15 (22H, m, CH$_2$CH$_2$), 0.87 (3H, t, $J= 7.5$ Hz, CH$_2$CH$_3$) $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 174.1$ (MeOC=O), 56.8-57.1 (CH$_2$CHOCHCH$_2$), 51.2 (CH$_3$O), 33.7 (O=CCH$_2$CH$_2$), 31.8-28.9 (CH$_2$CH$_2$), 27.7 (CHOCH$_2$CH$_2$), 24.8 (O=CCH$_2$CH$_2$CH$_2$), 22.5 (CH$_2$CH$_3$), 13.9 (CH$_2$CH$_3$); $m/z$ (ES$^+$) [M+Na$^+$] Required 335.2562, Found 335.2556\n\n184.108.40.206 Synthesis of Epoxidized Cocoa Butter (ECB, 2.16)\n\nThe experiment was conducted according to the procedure described in section 220.127.116.11. Tungsten powder (1.62 g, 8.8 mmol), hydrogen peroxide (30% w/w, 18 g, 160 mmol), deionized water (6 cm$^3$), H$_3$PO$_4$ (85%, 1 g, 8.67 mmol), deionized water (16 cm$^3$), cocoa butter (2.9) (300 g, 349 mmol), Adogen 464 (2.1 g, 4.52 mmol), deionized water (500 cm$^3$), hydrogen peroxide (96 g, 850 mmol). Epoxidised cocoa butter (ECB, 2.16) (275 g, 324 mmol, 93% yield), pale yellow liquid. $v_{\\text{max}}$/cm$^{-1}$ 2921, 2852 (C-H) 1743 (C=O) 1465 (CH$_2$) 1158 and 1113 (C-O) 820 (C-O-C) 721 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.20-5.10$ (1H, m, CHO) 4.19 (2H, dd, $J= 11.9$ Hz, 4.3 Hz, CH$_2$O), 4.02 (2H, dd, $J= 11.9$ Hz, 5.9 Hz, CH$_2$O), 2.94-2.74 (2H, m, CH$_2$CHOCHCH$_2$), 2.18 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.54-1.44 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.42-1.32 (4H, m, CHOCH$_2$CH$_2$), 1.31-1.08 (72H, m, CH$_2$CH$_2$), 0.76 (9H, t, $J= 7.5$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 172.8$, 172.4 (C=O), 68.9 (HC-O), 61.8, 61.6 (H$_2$C-O), 56.7 (CH$_2$CHOCHCH$_2$), 33.9 (O=CCH$_2$CH$_2$), 29.5-22.7 (CH$_2$CH$_2$), 27.9 (CHOCH$_2$CH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$); $m/z$ (ES$^+$) [M+Na$^+$] Required 899.7680, Found 899.7674\n\n18.104.22.168 Synthesis of Epoxidized Palm Oil (EPO, 2.17)\n\nThe experiment was conducted according to the procedure described in section 22.214.171.124. Tungsten powder (1.6 g, 8.7 mmol), hydrogen peroxide (30% w/w, 18 g, 160 mmol), deionised water (6 cm$^3$), H$_3$PO$_4$ (85%, 1 g, 8.67 mmol), deionized water (16 cm$^3$), palm oil (2.10) (300 g, 350 mmol), Adogen 464 (2 g, 4.31 mmol), deionized water (450 cm$^3$), hydrogen peroxide (90 g, 794 mmol). Epoxidised palm oil (EPO, 2.17) (296 g, 333 mmol, 95% yield), pale yellow liquid. $v_{\\text{max}}$/cm$^{-1}$ 2923, 2854 (C-H) 1742 (C=O) 1464 (CH$_2$) 1158 and 1111 (C-O) 821 (C-O-C) 722 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.28-5.21$ (1H, m, CHO) 4.30 (2H, dd, $J= 11.9$ Hz, 4.2 Hz, CH$_2$O), 4.13 (2H, dd, $J= 11.9$ Hz, 5.9 Hz, CH$_2$O), 3.10-2.80 (4H, m, CH$_2$CHOCHCH$_2$), 2.30 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.65-1.55 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.55-1.42 (8H, m, CHOCH$_2$CH$_2$), 1.42-1.20 (64H, m, CH$_2$CH$_2$), 0.89 (9H, t, $J= 7.5$ Hz CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 172.9$, 172.5 (C=O), 68.8 (HC-O), 61.8, 61.5 (H$_2$C-O), 56.5 (CH$_2$CHOCHCH$_2$), 33.7 (O=CCH$_2$CH$_2$), 29.4-22.4 (CH$_2$CH$_2$), 28.9 (CHOCH$_2$CH$_2$), 27.8 (O=CCH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$); $m/z$ (ES$^+$) [M+Na$^+$] Required 913.7467, Found 913.7467\n\n126.96.36.199 Synthesis of Epoxidized Rapeseed Oil (ERO, 2.13)\n\nThe experiment was conducted according to the procedure described in section 188.8.131.52. Tungsten powder (1.2 g, 6.52 mmol), hydrogen peroxide (30% w/w, 16 g, 141 mmol), deionized water (4 cm$^3$), H$_3$PO$_4$ (85%, 0.8 g, 6.94 mmol), deionized water (8 cm$^3$), rapeseed oil (2.11) (200 g, 227 mmol), Adogen 464 (1.6 g, 3.45\n\nmmol), deionized water (320 cm$^3$), hydrogen peroxide (120 g, 1058 mmol). Epoxidised rapeseed oil (ERO, 2.13) (200 g, 211 mmol, 93% yield), a pale yellow liquid. $v_{\\text{max}}$/cm$^{-1}$ 2924, 2854 (C-H) 1742 (C=O) 1464 (CH$_2$) 1155 and 1108 (C-O) 825 (C-O-C) 723 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.30-5.20$ (1H, m, CHO) 4.31 (2H, dd, $J= 11.9$ Hz, 4.2 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.9$ Hz, 6.0 Hz, CH$_2$O), 3.20-3.00 (2H, m, CH$_2$CHOCHCH$_2$CHOCHCH$_2$), 2.97-2.90 (2H, m, CH$_2$CHOCHCH$_2$CHOCHCH$_2$), 2.89-2.82 (4H, m, CH$_2$CHOCHCH$_2$), 2.31 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$CH$_2$), 1.82-1.68 (2H, m, CH$_2$CHOCHCH$_2$CHOCHCH$_2$), 1.66-1.56 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.56-1.42 (12H, m, CHOCH$_2$CH$_2$), 1.40-1.20 (54H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J= 7.5$ Hz, CH$_3$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 172.6$, 172.3 (C=O), 68.8 (HC-O), 61.8, 61.7 (H$_2$C-O), 56.7, 53.7 (CH$_2$CHOCHCH$_2$), 33.8 (O=CCH$_2$CH$_2$), 29.1-22.6 (CH$_2$CH$_2$), 27.7-26.5 (CHOCH$_2$CH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$); $m/z$ (ES$^+$) [M+Na$^+$] Required 969.7365, Found 969.7368\n\n### 184.108.40.206 Synthesis of Epoxidized Soybean Oil (ESO, 2.6)\n\nThe experiment was conducted according to the procedure described in section 220.127.116.11. Tungsten powder (1.8 g, 9.8 mmol), hydrogen peroxide (30% w/w, 24 g, 211 mmol), deionized water (6 cm$^3$), H$_3$PO$_4$ (85%, 1.2 g, 10.4 mmol), deionized water (12 cm$^3$), soybean oil (2.12) (300 g, 341 mmol), Adogen 464 (2.4 g, 5.17 mmol), deionized water (480 cm$^3$), hydrogen peroxide (180 g, 1588 mmol). Epoxidised\n\nsoybean oil (ESO, 2.6) (297 g, 310 mmol, 91% yield), a pale yellow liquid. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\)\n\n2923, 2854 (C-H) 1741 (C=O) 1464 (CH₂) 1154 (C-O) 823 (C-O-C) 724 (CH₂); \\( ^1 \\)H NMR (400 MHz, CDCl₃): \\( \\delta_H = 5.28-5.20 \\) (1H, m, CHO) 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.3Hz, CH₂O), 4.12 (2H, dd, \\( J = 11.9 \\) Hz, 6.0 Hz, CH₂O), 3.16-2.98 (4H, m, CH₂CHOCHCH₂CHOCHCH₂), 2.97-2.88 (4H, m, CH₂CHOCHCH₂CHOCHCH₂), 2.88-2.81 (2H, m, CH₂CHOCHCH₂), 2.30 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.82-1.66 (4H, m, CH₂CHOCHCH₂CHOCHCH₂), 1.66-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.56-1.42 (12H, m, CHOCH₂CH₂), 1.42-1.20 (48H, m, CH₂CH₂), 0.89 (9H, t, \\( J = 7.5 \\) Hz, CH₂CH₃); \\( ^{13} \\)C NMR (100 MHz CDCl₃): \\( \\delta_C = 172.5, 172.1 \\) (C=O), 68.7 (HC-O), 61.8, 61.5 (H₂C-O), 56.5-53.7 (CH₂CHOCHCH₂), 33.7 (O=CCH₂CH₂), 29.3-22.3 (CH₂CH₂), 28.8-22.4 (CHOCH₂CH₂), 24.5 (O=CCH₂CH₂CH₂), 13.6 (CH₂CH₃); \\( m/z \\) (ES⁺) [M+Na⁺] Required 983.7158, Found 983.7158\n\n6.1.2 General Procedure for Oligomerization of Epoxidized Plant Oil without Solvent\n\n18.104.22.168 Oligomerization of epoxidized methyl oleate (2.3) catalyzed by BF₃.Et₂O without solvent as an example\n\nEpoxidized methyl oleate (2.3) (5 g, 16 mmol) was weighed into a round bottom flask and was heated to 20 °C. It was stirred under N₂ atmosphere for 30 minutes before BF₃.Et₂O (0.34 g, 2.4 mmol) was added drop-wise to it. After the addition of BF₃.Et₂O was completed, the reaction temperature was maintained at 20 °C under N₂ atmosphere for 24 hours. Then, the reaction mixture was poured into separation funnel and washed with sodium bicarbonate solution (50 ml). The aqueous layer was separated from the organic layer and CHCl₃ (50 ml) was added to organic layer. The\n\norganic layer was dried over anhydrous MgSO$_4$ and CHCl$_3$ was removed in vacuo to yield a yellowish liquid (4.95 g) $v_{\\text{max}}$/cm$^{-1}$ 3358 (O-H) 2925, 2855 (C-H) 1738 (C=O) 1460 (CH$_2$) 1170 (C-O) 724 (CH$_2$). $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 3.67$ (9H, s, HCO), 3.60-3.20 (6H, m, HCO), 2.31 (6H, t, $J = 7.5$ Hz, O=CCH$_2$CH$_2$), 1.68-1.56 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.55-1.20 (72H, m, CH$_2$CH$_2$CH$_2$), 0.9 (9H, t, $J = 7.5$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.8$ (C=O) 74.0, 73.2, 71.6 (C-O), 50.8 (OCH$_3$) 33.6 (O=CCH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 31.1, 29.3, 28.9, 22.5 (CH$_2$CH$_2$CH$_2$), 13.7 (CH$_2$CH$_3$) $m/z$ (ES$^+$), [M+Na].Required 977.7991, Found 977.7991\n\n22.214.171.124 Oligomerization of epoxidized cocoa butter (2.16) catalyzed by BF$_3$.Et$_2$O without solvent\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. Epoxidized cocoa butter (2.16) (5 g, 5.7 mmol), BF$_3$.Et$_2$O (0.13 g, 0.9 mmol); a yellowish viscous liquid (4.9 g) $v_{\\text{max}}$/cm$^{-1}$ 3355 (O-H) 2916, 2849 (C-H) 1739 (C=O) 1466 (CH$_2$) 1164 (C-O) 721 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.28$-5.25 (1H, m, CHO), 4.29 (2H, dd, $J = 11.8$ Hz, 4.0 Hz, CH$_2$O), 4.14 (2H, dd, $J = 11.9$ Hz, 5.9 Hz, CH$_2$O), 3.85-3.25 (2H, m, CHO), 2.35 (6H, t, $J = 7.5$ Hz, O=CCH$_2$CH$_2$), 1.65-1.56 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.45-1.15 (72H, m, CH$_2$CH$_2$), 0.9 (9H, t, $J =$\n\n7.5 Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_{\\text{C}} = 173.3$, 172.8 (C=O) 72.5 (HC-O) 68.8 (HC-O), 61.9, 62.0 (H$_2$C-O), 33.9 (O=CCH$_2$), 24.7 (O=CCH$_2$CH$_2$CH$_2$), 29.6, 23.8 (CH$_3$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n188.8.131.52 Oligomerization of epoxidized palm oil (2.17) catalyzed by BF$_3$.Et$_2$O without solvent\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Epoxidized palm oil (2.17) (5 g, 5.6 mmol), BF$_3$.Et$_2$O (0.23 g, 1.65 mmol). The reactant mixture gel-up / polymerized as soon as BF$_3$.Et$_2$O was added to it. The polymerized product was sticky and rubbery. $v_{\\text{max}}/\\text{cm}^{-1}$ 3326 (O-H) 2916, 2849 (C-H) 1740 (C=O) 1462 (CH$_2$) 1160 (C-O) 720 (CH$_2$)\n\n220.127.116.11 Oligomerization of epoxidized rapeseed oil (2.13) catalyzed by BF$_3$.Et$_2$O without solvent\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. Epoxidized rapeseed oil (2.13) (5 g, 5.3 mmol), BF$_3$.Et$_2$O (0.45 g, 3.17 mmol). The reactant mixture gel-up / polymerized as soon as BF$_3$.Et$_2$O was added to it. The polymerized product was sticky and rubbery. $v_{\\text{max}}/\\text{cm}^{-1}$ 3348 (O-H) 2920, 2853 (C-H) 1741 (C=O) 1463 (CH$_2$) 1165 (C-O) 721 (CH$_2$)\n\n22.214.171.124 Oligomerization of epoxidized soybean oil (2.6) catalyzed by BF$_3$.Et$_2$O without solvent\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. Epoxidized soybean oil (2.6) (5 g, 5.2 mmol), BF$_3$.Et$_2$O (0.55 g, 3.9 mmol). The reactant mixture gel-up / polymerized as soon as BF$_3$.Et$_2$O was added to it. The\n\npolymerized product was sticky and rubbery. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3334 (O-H) 2922, 2856 (C-H) 1738 (C=O) 1460 (CH\\(_2\\)) 1171 (C-O) 723 (CH\\(_2\\))\n\n188.8.131.52 Oligomerization of euphorbia oil (2.18) catalyzed by BF\\(_3\\).Et\\(_2\\)O without solvent\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Euphorbia oil (2.18) (5 g, 5.5 mmol), BF\\(_3\\).Et\\(_2\\)O (0.23 g, 1.65 mmol). The reactant mixture gel-up / polymerized as soon as BF\\(_3\\).Et\\(_2\\)O was added to it. The polymerized product was sticky and rubbery. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3340 (O-H) 2924, 2855 (C-H) 1742 (C=O) 1458 (CH\\(_2\\)) 1160 (C-O) 736 (CH\\(_2\\))\n\n6.1.3 General Procedure for Oligomerization of Epoxidized Plant Oil with Solvent\n\n220.127.116.11 Oligomerization of epoxidized methyl oleate (2.3) catalyzed by BF\\(_3\\).Et\\(_2\\)O with solvent as an example\n\nEpoxidized methyl oleate (2.3) (100 g, 320 mmol) was weighed into a round bottom flask and hexane (200 ml) was added to it. The reactants mixture was stirred and heated at 20 °C under N\\(_2\\) atmosphere for 30 minutes before BF\\(_3\\).Et\\(_2\\)O (2.3 g, 16 mmol) was added drop-wise to (2.3). After the addition of BF\\(_3\\).Et\\(_2\\)O was completed, the reaction temperature was maintained at 20 °C for another 24 hours. Then, the reaction mixture was poured into separation funnel and washed with sodium bicarbonate solution (250 ml). The aqueous layer was separated from the organic layer and CHCl\\(_3\\) (500 ml) was added to organic layer. The organic layer was dried over anhydrous MgSO\\(_4\\) and CHCl\\(_3\\) was removed in vacuo to yield a yellowish liquid\n\n(2.22) (95.24 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3350 (O-H) 2922, 2853 (C-H) 1739 (C=O) 1459 (CH₂) 1169 (C-O) 723 (CH₂) \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 3.66 \\) (9H, s, HCO), 3.60-3.05 (6H, m, HCO), 2.30 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.68-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.55-1.20 (72H, m, CH₂CH₂CH₂), 0.87 (9H, t, \\( J = 7.5 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.9 \\) (C=O) 74.1, 73.4, 71.7 (C-O), 58.8 (OCH₃) 33.6 (O=CCH₂), 24.5 (O=CCH₂CH₂CH₂), 29.3, 28.9, 22.6 (CH₂CH₂CH₂), 13.7 (CH₂CH₃) \\( m/z \\) (ES⁺), [M+Na⁺], Required 977.7991, Found 977.7989\n\n18.104.22.168 Oligomerization of epoxidized cocoa butter (2.16) catalyzed by BF₃.Et₂O with solvent\n\nThe experiment was conducted according to the procedure described in section 22.214.171.124. Epoxidized cocoa butter (2.16) (50 g, 57 mmol), hexane (80 ml), BF₃.Et₂O (0.81 g, 5.7 mmol), a yellowish liquid (2.23, 49.3 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3360 (O-H) 2918, 2850 (C-H) 1740 (C=O) 1468 (CH₂) 1165 (C-O) 722 (CH₂) \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.23-5.15 \\) (1H, m, CHO), 4.24 (2H, dd, \\( J = 11.7 \\) Hz, 3.7 Hz, CH₂O), 4.07 (2H, dd, \\( J = 11.9 \\) Hz, 6.0 Hz, CH₂O), 3.60-3.10 (2H, m, HCO), 2.26 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.62-1.47 (6H, m, O=CCH₂CH₂CH₂), 1.45-1.10 (72H, m, CH₂CH₂), 0.82 (9H, t, \\( J = 7.5 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = \\)\n\n173.1, 172.6 (C=O) 72.5 (HC-O) 68.7 (HC-O), 61.9, 61.7 (H₂C-O), 33.8 (O=CCH₂), 24.6 (O=CCH₂CH₂CH₂), 29.6, 22.5 (CH₂CH₂CH₂), 13.8 (CH₂CH₃)\n\n126.96.36.199 Oligomerization of epoxidized palm oil (2.17) catalyzed by BF₃.Et₂O with solvent\n\nThe experiment was conducted according to the procedure described in section 188.8.131.52. Epoxidized palm oil (2.17) (100 g, 112 mmol), hexane (600 ml), BF₃.Et₂O (1.1g, 7.8 mmol), a yellowish liquid (2.24, 98.4 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3348 (O-H) 2921, 2851 (C-H) 1742 (C=O) 1459 (CH₂) 1158 (C-O) 722 (CH₂) \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.22-5.13 \\) (1H, m, CHO), 4.21 (2H, dd, \\( J = 11.9 \\) Hz, 4.1 Hz, CH₂O), 4.07 (2H, dd, \\( J = 11.8 \\) Hz, 5.9 Hz, CH₂O), 3.80-3.00 (4H, m, HCO), 2.23 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.60-1.47 (6H, m, O=CCH₂CH₂CH₂), 1.35-1.10 (64H, m, CH₂CH₂), 0.79 (9H, t, \\( J = 7.5 \\) Hz, CH₂CH₃); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.2, 172.5 \\) (C=O) 72.4 (HC-O) 68.8 (HC-O), 61.8, 61.6 (H₂C-O), 33.9 (O=CCH₂), 24.7 (O=CCH₂CH₂CH₂), 29.5, 22.7 (CH₂CH₂CH₂), 13.9 (CH₂CH₃)\n\n184.108.40.206 Oligomerization of epoxidized rapeseed oil (2.17) catalyzed by BF₃.Et₂O with solvent\n\nThe experiment was conducted according to the procedure described in section 220.127.116.11. Epoxidized rapeseed oil (2.13) (50 g, 53 mmol), dry dichloromethane (500 ml), BF₃.Et₂O (0.60 g, 4.24 mmol), a yellowish liquid (2.25, 49.5 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3355 (O-H) 2920, 2851 (C-H) 1728 (C=O) 1459 (CH₂) 1072 (C-O) 752 (CH₂) \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.35-5.21 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.0 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.6 \\) Hz, 5.6 Hz, CH₂O), 3.80-3.05 (8H, m, HCO), 2.35 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.70-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.42-1.12 (54H, m,\n\nCH\\textsubscript{2}CH\\textsubscript{2}), 0.88 (9H, t, $J = 7.5$ Hz, CH\\textsubscript{2}CH\\textsubscript{3}); $^{13}$C NMR (100 MHz CDCl\\textsubscript{3}): $\\delta_C =$ 173.1, 172.7 (C=O), 68.8 (HC-O), 65.6 (HC-O), 61.2, 61.8 (H\\textsubscript{2}C-O), 33.8 (O=CCH\\textsubscript{2}), 24.6 (O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 31.1, 29.4, 22.6 (CH\\textsubscript{3}CH\\textsubscript{2}CH\\textsubscript{2}), 13.8 (CH\\textsubscript{2}CH\\textsubscript{3})\n\n18.104.22.168 Oligomerization of epoxidized soybean oil (2.6) catalyzed by BF\\textsubscript{3}.Et\\textsubscript{2}O with solvent\n\nThe experiment was conducted according to the procedure described in section 22.214.171.124. Epoxidized soybean oil (2.6) (50 g, 53 mmol), dry dichloromethane (500 ml), BF\\textsubscript{3}.Et\\textsubscript{2}O (1.01 g, 7.1 mmol), a yellowish liquid (2.26, 49 g) $v_{\\text{max}}$/cm\\textsuperscript{-1} 3360 (O-H) 2922, 2853 (C-H) 1740 (C=O) 1458 (CH\\textsubscript{2}) 1075 (C-O) 754 (CH\\textsubscript{2}) $^1$H NMR (400 MHz, CDCl\\textsubscript{3}): $\\delta_H =$ 5.29-5.20 (1H, m, CHO), 4.30 (2H, dd, $J = 11.7$ Hz, 3.9 Hz, CH\\textsubscript{2}O), 4.14 (2H, dd, $J = 11.3$ Hz, 5.6 Hz, CH\\textsubscript{2}O), 3.90-3.05 (10H, m, HCO), 2.31 (6H, t, $J = 7.5$ Hz, O=CCH\\textsubscript{2}CH\\textsubscript{2}), 1.70-1.51 (6H, m, O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 1.50-1.20 (48H, m, CH\\textsubscript{2}CH\\textsubscript{2}), 0.88 (9H, t, $J = 7.5$ Hz, CH\\textsubscript{2}CH\\textsubscript{3}); $^{13}$C NMR (100 MHz CDCl\\textsubscript{3}): $\\delta_C =$ 172.9, 172.5 (C=O), 73.4 (HC-O), 68.7 (HC-O), 61.7, 61.9 (H\\textsubscript{2}C-O), 33.7 (O=CCH\\textsubscript{2}), 24.5 (O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 29.1, 22.4, 15.5 (CH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 13.7 (CH\\textsubscript{2}CH\\textsubscript{3})\n\n126.96.36.199 Oligomerization of euphorbia oil (2.18) catalyzed by BF\\textsubscript{3}.Et\\textsubscript{2}O with solvent\n\nThe experiment was conducted according to the procedure described in section 188.8.131.52. Euphorbia oil (2.18) (70 g, 77 mmol), dry dichloromethane (140 ml), BF\\textsubscript{3}.Et\\textsubscript{2}O (0.7 g, 5.0 mmol), a yellowish liquid (2.27, 50 g); $v_{\\text{max}}$/cm\\textsuperscript{-1} 3481 (O-H) 2924, 2854 (C-H) 1742 (C=O) 1464 (CH\\textsubscript{2}) 1161 (C-O) 756 (CH\\textsubscript{2}); $^1$H NMR (400 MHz, CDCl\\textsubscript{3}): $\\delta_H =$ 5.58-5.29 (6H, m, CH=CH), 5.28-5.23 (1H, m, CHO), 4.29 (2H,\n\ndd, $J = 11.8$ Hz, 3.9 Hz, CH$_2$O), 4.14 (2H, dd, $J = 11.7$ Hz, 5.5 Hz, CH$_2$O), 3.75 – 3.10 (4H, m, HCO), 2.30 (6H, t, $J = 7.5$ Hz, O=CCH$_2$CH$_2$), 2.10-1.95 (12H, m, CH$_2$CH=CH) 1.67-1.54 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.50-1.20 (50H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J = 6.9$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.2$, 172.8 (C=O), 129.7, 125.5 (HC=CH), 74.6, 73.7 (HC-O), 68.8 (HC-O), 62.0, 61.9 (H$_2$C-O), 33.9 (O=CCH$_2$), 27.1 (CH$_2$CH=CH), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 29.4, 22.7 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$)\n\n### 6.1.4 Synthesis of dihydroxy methyl stearate (2.32) (DHMS)\n\nEpoxidized methyl oleate (2.3) (57.6 g, 184 mmol) was weighed into a round bottom flask. Deionized water (50 ml) and H$_3$PO$_4$ (1 g, 10 mmol) were added to (2.3). The mixture was stirred and heated to 80 °C for 12 hours. The reaction mixture was poured into a separating funnel and was washed with NaCl solution (100 ml), NaHCO$_3$ (100 ml) and NaCl (100 ml). The aqueous layer was discarded and CHCl$_3$ (100 ml) was added to the organic layer. The organic layer was dried over anhydrous MgSO$_4$ and CHCl$_3$ was removed in vacuo to yield a colorless liquid. The colorless liquid was dissolved in hot hexane (60 °C, 60 ml) and the mixture was left to cool to room temperature. White precipitate was formed from the mixture upon cooling and was filtered and washed with hexane to yield white solid (2.32, 33.0 g, 100 mmol, 54% yield). $\\nu_{\\text{max}}/\\text{cm}^{-1}$ 3342 (O-H) 2912, 2846 (C-H) 1742 (C=O) 1467 (CH$_2$) 1166, 1038 (C-O) 720 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 3.67$ (3H, s, HCO), 3.46-3.35 (2H, m, HCO), 2.31 (2H, t, $J = 7.5$ Hz O=CCH$_2$CH$_2$), 1.68-1.56 (2H, m, O=CCH$_2$CH$_2$CH$_2$), 1.55-1.39 (4H, m, HOCH$_2$), 1.37-1.20 (20H, m, CH$_2$CH$_2$CH$_2$), 0.88 (3H, t, $J = 7.0$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 174.4$ (C=O) 74.3 (C-O), 51.3 (OCH$_3$) 33.8 (O=CCH$_2$), 33.2 (HOCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$),\n\n31.3, 29.4, 22.9 (CH₂CH₂CH₂), 13.9 (CH₂CH₃); \\( m/z \\) (ES⁺) [M+Na⁺] Required 353.2662, Found 353.2662; Melting point: 65-67 °C (literature\\(^{118}\\) 67-68 °C).\n\n\\[ \\text{HO} \\quad \\text{OH} \\quad \\text{CO}_2\\text{Me} \\quad (2.32) \\]\n\n### 6.1.5 General Procedure for Ring Opening of Epoxidized Plant Oil with Polyhydric Alcohol\n\n#### 184.108.40.206 Ring opening of epoxidized methyl oleate (2.3) with ethylene glycol as an example\n\nEthylene glycol (1.5 g, 24 mmol) was stirred and heated to 60 °C in a round bottom flask for 30 minutes before BF₃.Et₂O (0.34 g, 2.4 mmol) was added to it. The mixture was stirred and heated at 60 °C for another 30 minutes. Epoxidized methyl oleate (2.3) (5 g, 16 mmol) was stirred and heated to 60 °C in another round bottom flask. The mixture of ethylene glycol / BF₃.Et₂O was added drop-wise to (2.3). After the addition was completed, the reaction temperature was maintained at 60 °C for 24 hours. Then, the reaction mixture was poured into separation funnel and washed with sodium bicarbonate solution (50 ml). The aqueous layer was separated from the organic layer and CHCl₃ (50 ml) was added to organic layer. The organic layer was dried over anhydrous MgSO₄ and CHCl₃ was removed *in vacuo* to yield a yellowish liquid (2.34, 5.1 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3431 (O-H) 2924, 2854 (C-H) 1738 (C=O) 1457 (CH₂) 1076 (C-O) 723 (CH₂) \\( ^1\\text{H} \\) NMR (400 MHz, CDCl₃): \\( \\delta_{\\text{H}} = 4.19 \\) (2H, t, \\( J = 7.5 \\) Hz, H₂CO), 3.80 (2H, t, \\( J = 7.5 \\) Hz, H₂CO), 3.68 (6H, s, H₃CO), 3.60-3.10 (4H, m, HCO), 2.32 (4H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.70-1.56 (4H, m, O=CCH₂CH₂CH₂), 1.55-1.20 (48H, m, CH₂CH₂CH₂), 0.87 (6H, t, \\( J = 7.5 \\) Hz, CH₂CH₃) \\( ^{13}\\text{C} \\) NMR (100 MHz\n\nCDCl$_3$): $\\delta_C = 174.1$ (C=O), 72.5, 71.5 (C-O), 65.6 (H$_2$C-O), 60.6 (H$_2$C-O), 51.2 (H$_3$C-O) 33.8 (O=CCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 31.4, 29.3, 28.9, 22.6 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$); $m/z$ (ES$^+$), [M+Na$^+$], Required 709.5589 Found 709.5589\n\n\n\n### 220.127.116.11 Ring opening of epoxidized cocoa butter (2.16) with ethylene glycol\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. Ethylene glycol (0.56 g, 9 mmol), BF$_3$.Et$_2$O (0.13 g, 0.9 mmol), epoxidized cocoa butter (2.16) (5 g, 6 mmol), a viscous yellowish liquid (4.95 g) $v_{\\text{max}}$/cm$^{-1}$ 3380 (O-H) 2916, 2850 (C-H) 1742 (C=O) 1467 (CH$_2$) 1162 (C-O) 719 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.21-5.11$ (1H, m, CHO), 4.30 (2H, dd, $J= 11.9$ Hz, 4.2 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.8$ Hz, 5.9 Hz, CH$_2$O), 3.90-3.25 (4H, m, HCO), 2.23 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.60-1.45 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.42-0.95 (72H, m, CH$_2$CH$_2$), 0.79 (9H, t, $J = 7.0$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.1$, 172.7 (C=O) 72.9, 72.6, 71.8 (HC-O) 68.5 (HC-O), 61.8, 61.9 (H$_2$C-O), 33.9 (O=CCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 29.5, 22.5 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n### 22.214.171.124 Ring opening of epoxidized palm oil (2.17) with ethylene glycol\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. Ethylene glycol (1.05 g, 17 mmol), BF$_3$.Et$_2$O (0.23 g, 1.65 mmol), epoxidized palm oil (2.17) (5 g, 5.6 mmol), a viscous yellowish liquid (2.35, 4.9 g). $v_{\\text{max}}$/cm$^{-1}$ 3450 (O-H) 2922, 2854 (C-H) 1742 (C=O) 1465 (CH$_2$) 1161, 1096 (C-O)\n\n755 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.30-5.20$ (1H, m, CHO), 4.30 (2H, dd, $J= 11.7$ Hz, 3.6 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.8$ Hz, 5.8 Hz, CH$_2$O), 3.90-3.25 (8H, m, HCO), 2.31 (6H, t, $J= 7.0$ Hz, O=CCH$_2$CH$_2$), 1.67-1.55 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.54-1.15 (64H, m, CH$_2$CH$_2$), 0.86 (9H, t, $J= 7.5$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.2$, 172.8 (C=O) 72.6, 72.2, 71.6, 68.7, (HC-O), 62.0, 61.8 (H$_2$C-O), 33.8 (O=CCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 29.5, 22.6 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n188.8.131.52 Ring opening of epoxidized rapeseed oil (2.13) with ethylene glycol\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Ethylene glycol (2.79 g, 45 mmol), BF$_3$.Et$_2$O (0.64 g, 4.5 mmol), epoxidized rapeseed oil (2.13) (5 g, 5.3 mmol), a viscous yellowish liquid (5.5 g) $v_{\\text{max}}$/cm$^{-1}$ 3430 (O-H) 2925, 2856 (C-H) 1739 (C=O) 1463 (CH$_2$) 1162, 1097 (C-O) 754 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.30-5.21$ (1H, m, CHO), 4.30 (2H, dd, $J= 11.9$ Hz, 4.0 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.6$ Hz, 5.7 Hz, CH$_2$O), 3.90-3.30 (8H, m, HCO), 2.33 (6H, t, $J= 7.0$ Hz, O=CCH$_2$CH$_2$), 1.70-1.55 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.52-1.18 (54H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J= 7.0$Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.0$, 172.3 (C=O) 72.7, 69.8, 68.7, 60.8 (HC-O), 62.2, 61.8 (H$_2$C-O), 33.9 (O=CCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 31.3, 29.4, 28.8, 22.7 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n220.127.116.11 Ring opening of epoxidized soybean oil (2.6) with ethylene glycol\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. Ethylene glycol (4.65 g, 75 mmol), BF$_3$.Et$_2$O (1.06 g, 7.5 mmol), epoxidized soybean oil (2.6) (10 g, 10.4 mmol). The reaction mixture polymerized overnight.\n\n22.214.171.124 Ring opening of epoxidized methyl oleate (2.3) with glycerol\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. Glycerol (9 g, 98 mmol), BF₃.Et₂O (1.2 g, 8.5 mmol), epoxidized methyl oleate (2.3) (20 g, 64 mmol), a yellowish liquid (2.36, 17.3 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3460 (O-H) 2924, 2854 (C-H) 1739 (C=O) 1458 (CH₂) 1170, 1075 (C-O) 723 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 3.67 \\) (9H, s, HCO), 3.57-3.10 (11H, m, HCO), 2.28 (6H, t, \\( J = 7.0 \\) Hz, O=CCH₂CH₂), 1.66-1.51 (6H, m, O=CCH₂CH₂CH₂), 1.49-1.15 (72H, m, CH₂CH₂CH₂), 0.85 (9H, t, \\( J = 7.0 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 174.3 \\) (C=O) 74.2, 73.2, 71.5, 65.1, 63.4, 61.4 (C-O), 51.2 (OCH₃) 33.8 (O=CCH₂), 24.7 (O=CCH₂CH₂CH₂), 31.3, 29.4, 22.6 (CH₂CH₂CH₂), 13.8 (CH₂CH₃); \\( m/z \\) (ES⁺), [M+Na⁺] Required 1051.8359 Found 1051.8359\n\n\n\n188.8.131.52 Ring opening of epoxidized cocoa butter (2.16) with glycerol\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Glycerol (0.83 g, 9 mmol), BF₃.Et₂O (0.13 g, 0.9 mmol), epoxidized cocoa\n\nbutter (2.16) (5 g, 6 mmol), a viscous yellowish liquid (5 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3360 (O-H) 2920, 2851 (C-H) 1742 (C=O) 1466 (CH₂) 1163 (C-O) 721 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.29-5.22 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.8 \\) Hz, 3.6 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH₂O), 3.9 – 3.2 (4H, m, HCO), 2.32 (6H, t, \\( J = 7 \\) Hz O=CCH₂CH₂), 1.55-1.67 (6H, m, O=CCH₂CH₂CH₂), 1.20-1.54 (72H, m, CH₂CH₂), 0.9 (9H, t, \\( J = 7.5 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 174.3 \\) (C=O) 74.2, 72.8, 61.4 (C-O), 51.2 (OCH₃) 33.8 (O=CCH₂), 24.7 (O=CCH₂CH₂CH₂), 31.3, 29.4, 22.6 (CH₂CH₂CH₂), 13.8 (CH₂CH₃).\n\n**220.127.116.11 Ring opening of epoxidized palm oil (2.17) with glycerol**\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. Glycerol (1.56 g, 17 mmol), BF₃.Et₂O (0.23 g, 1.65 mmol), epoxidized palm oil (2.17) (5 g, 5.6 mmol), the reaction mixture polymerized 10 minutes later. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3295 (O-H) 2923, 2851 (C-H) 1742 (C=O) 1415 (CH₂) 1033 (C-O).\n\n**22.214.171.124 Ring opening of epoxidized rapeseed oil (2.13) with glycerol**\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. Glycerol (4.14 g, 45 mmol), BF₃.Et₂O (0.64 g, 4.5 mmol), epoxidized rapeseed oil (2.13) (5 g, 5.3 mmol), the reaction mixture polymerized 5 minutes later. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3440 (O-H) 2925, 2855 (C-H) 1738 (C=O) 1464 (CH₂) 1163 (C-O) 753 (CH₂).\n\n**188.8.131.52 Ring opening of epoxidized soybean oil (2.6) with glycerol**\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Glycerol (17.3 g, 0.19 mol), BF₃.Et₂O (2.7 g, 18.8 mmol), epoxidized\n\nsoybean oil (2.6) (25 g, 26.4 mmol), the reaction mixture polymerized 5 minutes later.\n\n\\[ \\nu_{\\text{max}}/\\text{cm}^{-1} \\quad 3332 \\ (\\text{O-H}) \\quad 2924, \\ 2855 \\ (\\text{C-H}) \\quad 1739 \\ (\\text{C=O}) \\quad 1457 \\ (\\text{CH}_2) \\quad 1161, \\ 1041 \\ (\\text{C-O}) \\quad 755 \\ (\\text{CH}_2). \\]\n\n### 220.127.116.11 Ring opening of epoxidized methyl oleate (2.3) with dihydroxy methyl stearate (2.32) (DHMS)\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. DHMS (7.9 g, 24 mmol), BF$_3$.Et$_2$O (0.34 g, 2.4 mmol), epoxidized methyl oleate (2.3) (5 g, 16 mmol), a yellowish liquid (2.37, 12.5 g) \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3354 (O-H) 2923, 2853 (C-H) 1736 (C=O) 1458 (CH$_2$) 1169 (C-O) 723 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): \\( \\delta_H = \\) 3.67 (6H, s, HCO), 3.60-3.25 (4H, m, HCO), 2.30 (4H, t, \\( J= 7.0 \\) Hz, O=CCH$_2$CH$_2$), 1.68-1.56 (4H, m, O=CCH$_2$CH$_2$CH$_2$), 1.55-1.20 (48H, m, CH$_2$CH$_2$CH$_2$), 0.88 (6H, t, \\( J= 7.0 \\) Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): \\( \\delta_C = \\) 174.1 (C=O) 74.3, 71.5 (C-O), 51.1 (OCH$_3$) 33.8 (O=CCH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 31.2, 29.2, 22.6 (CH$_2$CH$_2$CH$_2$), 13.7 (CH$_2$CH$_3$); \\( m/z \\) (ES$^+$) [M+Na$^+$] Required 665.5327, Found 665.5327\n\n\n\n### 22.214.171.124 Ring opening of epoxidized cocoa butter (2.16) with dihydroxy methyl stearate (2.32) (DHMS)\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. DHMS (2.97 g, 9 mmol), BF$_3$.Et$_2$O (0.13 g, 0.9 mmol), epoxidized cocoa\n\nbutter (2.16) (5 g, 6 mmol), a yellowish liquid (7.1 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3345 (O-H) 2921, 2852 (C-H) 1740 (C=O) 1459 (CH₂) 1163 (C-O) 722 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.22 \\) (2H, m, CHO), 4.31 (2H, dd, \\( J = 11.8 \\) Hz, 4.0 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.7 \\) Hz, 5.8 Hz, CH₂O), 3.67 (3H, s, HCO), 3.60-3.25 (4H, m, HCO), 2.30 (14H, t, \\( J = 7.0 \\) Hz, O=CCH₂CH₂), 1.66-1.55 (14H, m, O=CCH₂CH₂CH₂), 1.54-1.20 (176H, m, CH₂CH₂), 0.9 (21H, t, \\( J = 7.0 \\) Hz, CH₂CH₃);\n\n\\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 174.1 \\) (C=O) 74.3, 72.1 (C-O), 68.7 (OCH), 61.9, 61.7 (CH₂O) 51.1 (OCH₃) 33.8 (O=CCH₂), 24.5 (O=CCH₂CH₂CH₂), 31.2, 29.2, 22.5 (CH₂CH₂CH₂), 13.8 (CH₂CH₃)\n\n### 188.8.131.52 Ring opening of epoxidized palm oil (2.17) with dihydroxy methyl stearate (2.32) (DHMS)\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. DHMS (5.45 g, 16.5 mmol), BF₃.Et₂O (0.23 g, 1.65 mmol), epoxidized palm oil (2.17) (5 g, 5.6 mmol), a yellowish liquid (2.38, 10.7 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3438 (O-H) 2921, 2852 (C-H) 1736 (C=O) 1459 (CH₂) 1166 (C-O) 722 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.39-5.23 \\) (2H, m, CHO), 4.30 (2H, dd, \\( J = 11.8 \\) Hz, 3.6 Hz, CH₂O), 4.15 (2H, dd, \\( J = 11.7 \\) Hz, 5.8 Hz, CH₂O), 3.66 (3H, s, HCO), 3.60-3.26 (8H, m, HCO), 2.30 (18H, t, \\( J = 7.0 \\) Hz, O=CCH₂CH₂), 1.68-1.56 (18H, m, O=CCH₂CH₂CH₂), 1.54-1.20 (144H, m, CH₂CH₂), 0.87 (18H, t, \\( J = 7.5 \\) Hz, CH₂CH₃);\n\n\\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.7 \\) (C=O) 74.3, 72.1 (C-O), 68.8 (OCH), 62.0, 61.8 (CH₂O) 51.2 (OCH₃) 33.8 (O=CCH₂), 24.6 (O=CCH₂CH₂CH₂), 29.5, 29.1, 22.6 (CH₂CH₂CH₂), 13.8 (CH₂CH₃)\n\n220.127.116.11 Ring opening of epoxidized rapeseed oil (2.13) with dihydroxy methyl stearate (2.32) (DHMS)\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. DHMS (14.9 g, 45 mmol), BF$_3$.Et$_2$O (0.64 g, 4.5 mmol), epoxidized rapeseed oil (2.13) (5 g, 5.3 mmol), a yellowish liquid (18.7 g), $v_{\\text{max}}$/cm$^{-1}$ 3440 (O-H) 2922, 2853 (C-H) 1735 (C=O) 1459 (CH$_2$) 1168 (C-O) 723 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.29-5.22$ (1H, m, CHO), 4.31 (2H, dd, $J= 11.6$ Hz, 4.0 Hz, CH$_2$O), 4.15 (2H, dd, $J= 11.7$ Hz, 5.7 Hz, CH$_2$O), 3.64 (3H, s, HCO), 3.62-3.20 (4H, m, HCO), 2.31 (8H, t, $J= 7.0$ Hz, O=CCH$_2$CH$_2$), 1.72-1.56 (8H, m, O=CCH$_2$CH$_2$CH$_2$), 1.55-1.18 (92H, m, CH$_2$CH$_2$), 0.88 (12H, t, $J= 6.5$Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 174.3$ (C=O) 74.4, 72.2 (C-O), 68.6 (OCH), 62.2, 61.8 (CH$_2$O) 51.2 (OCH$_3$) 33.8 (O=CCH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 31.2, 29.3, 28.9, 22.6 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$).\n\n22.214.171.124 Ring opening of epoxidized soybean oil (2.6) with dihydroxy methyl stearate (2.32) (DHMS)\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. DHMS (12.4 g, 37 mmol), BF$_3$.Et$_2$O (0.45 g, 3.8 mmol), epoxidized soybean oil (2.6) (5 g, 5.2 mmol), a yellowish liquid (15.7 g) $v_{\\text{max}}$/cm$^{-1}$ 3354 (O-H) 2923, 2853 (C-H) 1736 (C=O) 1458 (CH$_2$) 1169 (C-O) 723 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.27-5.22$ (1H, m, CHO), 4.30 (2H, dd, $J= 11.9$ Hz, 3.9 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.8$ Hz, 5.7 Hz, CH$_2$O), 3.66 (3H, s, HCO), 3.62-3.20 (4H, m, HCO), 2.30 (8H, t, $J= 7.0$ Hz, O=CCH$_2$CH$_2$), 1.68-1.55 (8H, m, O=CCH$_2$CH$_2$CH$_2$), 1.55-1.20 (88H, m, CH$_2$CH$_2$), 0.86 (12H, t, $J= 7.0$ Hz, CH$_2$CH$_3$);\n\n$^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 174.1$ (C=O) 74.3, 72.1, 61.3 (C-O), 68.7 (OCH), 62.2, 61.8 (CH$_2$O) 51.1 (OCH$_3$) 33.8 (O=CCH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 29.3, 28.9, 22.5 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$)\n\n### 188.8.131.52 Ring opening of epoxidized methyl oleate (2.3) with glucose\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Glucose (4.32 g, 24 mmol), dry DMSO (10 ml), BF$_3$.Et$_2$O (0.34 g, 2.4 mmol), epoxidized methyl oleate (2.3) (5 g, 16 mmol), a white solid (4.92 g)\n\n$v_{\\text{max}}/\\text{cm}^{-1}$ 3349 (O-H) 2925, 2853 (C-H) 1740 (C=O) 1467 (CH$_2$) 1168 (C-O) 721 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 3.67$ (3H, s, HCO), 3.43-3.37 (2H, m, HCO), 2.31 (2H, t, $J= 7.0$ Hz, O=CCH$_2$CH$_2$), 1.68-1.54 (2H, m, O=CCH$_2$CH$_2$CH$_2$), 1.53-1.39 (4H, m, HOCCCH$_2$), 1.38-1.19 (20H, m, CH$_2$CH$_2$CH$_2$), 0.87 (3H, t, $J= 7.0$ Hz, CH$_2$CH$_3$), $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 174.3$ (C=O) 74.2 (C-O), 51.2 (OCH$_3$) 33.7 (O=CCH$_2$), 33.2 (HOCCCH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 29.3, 22.6 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$); $m/z$ (ES$^+$) [M+Na$^+$] Required 353.2662, Found 353.2664; Melting point: 65-67 °C (literature$^{118}$ 67-68 °C).\n\n### 220.127.116.11 Ring opening of epoxidized cocoa butter (2.16) with glucose\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. Glucose (Glu) (1.62 g, 9 mmol), dry DMSO (5 ml), BF$_3$.Et$_2$O (0.13 g, 0.9 mmol), epoxidized cocoa butter (ECB) (5 g, 6 mmol), a yellowish liquid (4.1 g),\n\n$v_{\\text{max}}/\\text{cm}^{-1}$ 2916, 2850 (C-H) 1739 (C=O) 1470 (CH$_2$) 1172 (C-O) 757 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.30-5.22$ (1H, m, CHO), 4.30 (2H, dd, $J= 11.9$ Hz, 4.3 Hz, CH$_2$O), 4.15 (2H, dd, $J= 11.8$ Hz, 5.8 Hz, CH$_2$O), 3.52-3.36 (2H, m, HCO),\n\n2.33 (6H, t, $J=7.6$ Hz, O=CCH$_2$CH$_2$), 1.68-1.53 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.52-1.19 (76H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J=7.0$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.6$, 172.6 (C=O) 74.1 (HC-O), 68.8 (HC-O), 61.9, 61.8 (H$_2$C-O), 33.7 (O=CCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 29.4, 22.5 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$)\n\n**22.214.171.124 Ring opening of epoxidized palm oil (2.17) with glucose**\n\nThe experiment was conducted according to the procedure described in section 126.96.36.199. Glucose (Glu) (3.0 g, 16.8 mmol), dry DMSO (10 ml), BF$_3$.Et$_2$O (0.24 g, 1.7 mmol), epoxidized palm oil (2.17) (5 g, 5.8 mmol), a yellowish liquid (4.7 g) $v_{\\text{max}}$/cm$^{-1}$ 3450 (O-H) 2921, 2852 (C-H) 1738 (C=O) 1466 (CH$_2$) 1174 (C-O) 755 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.29$-5.22 (1H, m, CHO), 4.29 (2H, dd, $J=11.8$ Hz, 4.1 Hz, CH$_2$O), 4.13 (2H, dd, $J=11.9$ Hz, 5.8 Hz, CH$_2$O), 3.55-3.35 (2H, m, HCO), 2.31 (6H, t, $J=7.5$ Hz, O=CCH$_2$CH$_2$), 1.67-1.55 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.54-1.19 (72H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J=7.0$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.8$, 172.8 (C=O) 74.3, 72.4, 62.8 (HC-O) 68.7 (HC-O), 62.1, 61.8 (H$_2$C-O), 33.8 (O=CCH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 29.4, 22.5 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$)\n\n**188.8.131.52 Ring opening of epoxidized rapeseed oil (2.13) with glucose**\n\nThe experiment was conducted according to the procedure described in section 184.108.40.206. Glucose (Glu) (8.1 g, 45 mmol), dry DMSO (10 ml), BF$_3$.Et$_2$O (0.64 g, 4.5 mmol), a yellowish liquid (4.7 g) $v_{\\text{max}}$/cm$^{-1}$ 3353 (O-H) 2924, 2854 (C-H) 1741 (C=O) 1465 (CH$_2$) 1165 (C-O) 755 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.30$-5.22 (1H, m, CHO), 4.29 (2H, dd, $J=11.9$ Hz, 4.0 Hz, CH$_2$O), 4.14 (2H, dd, $J=11.7$\n\nHz, 5.9 Hz, CH₂O), 3.75–3.36 (8H, m, HCO), 2.34 (6H, t, J= 7.3 Hz, O=CCH₂CH₂), 1.70-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.53-1.19 (68H, m, CH₂CH₂), 0.88 (9H, t, J = 7.6 Hz, CH₂CH₃); \\(^{13}\\)C NMR (100 MHz CDCl₃): δ_c = 173.6, 172.7 (C=O) 74.1, 72.2, 71.8 (HC-O) 68.7 (HC-O), 62.0, 61.7 (H₂C-O), 33.7 (O=CCH₂), 24.5 (O=CCH₂CH₂CH₂), 31.1, 29.3, 22.6 (CH₂CH₂CH₂), 13.8 (CH₂CH₃).\n\n### 220.127.116.11 Ring opening of epoxidized soybean oil (2.6) with glucose\n\nThe experiment was conducted according to the procedure described in section 18.104.22.168. Glucose (Glu) (6.75 g, 37.5 mmol), dry DMSO (10 ml), BF₃.Et₂O (0.53 g, 3.75 mmol), epoxidized soybean oil (2.6) (5 g, 5.7 mmol), a yellowish liquid (4.5 g)\n\n\\(v_{\\text{max}}/\\text{cm}^{-1}\\) 3440 (O-H) 2924, 2855 (C-H) 1740 (C=O) 1464 (CH₂) 1162 (C-O) 755 (CH₂); \\(^1\\)H NMR (400 MHz, CDCl₃): δ_H = 5.30-5.20 (1H, m, CHO), 4.29 (2H, dd, J= 11.9 Hz, 4.0 Hz, CH₂O), 4.14 (2H, dd, J= 11.7 Hz, 5.8 Hz, CH₂O), 3.80–3.20 (10H, m, HCO), 2.32 (6H, t, J= 7.0 Hz, O=CCH₂CH₂), 1.72-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.45-1.15 (64, m, CH₂CH₂), 0.88 (9H, t, J= 7.5 Hz, CH₂CH₃);\n\n\\(^{13}\\)C NMR (100 MHz CDCl₃): δ_c = 173.1, 172.6 (C=O) 74.1, 73.0, 71.8 (HC-O) 68.7 (HC-O), 61.9, 61.7 (H₂C-O), 33.6 (O=CCH₂), 24.5 (O=CCH₂CH₂CH₂), 29.3, 25.5, 22.4 (CH₂CH₂CH₂), 13.7 (CH₂CH₃)\n\n6.1.6 General Procedure for Ring Opening of Epoxidized Plant Oil with Water\n\n22.214.171.124 Ring opening of epoxidized palm oil (2.17) by water\n\nEpoxidized palm oil (2.13) (50 g, 56 mmol) was weighed into a round bottom flask. Deionized water (500 ml) and para-toluene sulfonic acid (21.5 g, 113 mmol) were added to (2.13). The mixture was stirred and heated to 100 °C for 7 hours. The reaction mixture was poured into a separating funnel and was washed with NaCl solution (100 ml), NaHCO₃ (100 ml) and NaCl (100 ml). The aqueous layer was discarded and CHCl₃ (100 ml) was added to the organic layer. The organic layer was dried over anhydrous MgSO₄ and CHCl₃ was removed in vacuo to yield a yellowish liquid (2.39, 51.6 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3355 (O-H) 2922, 2853 (C-H) 1742 (C=O) 1464 (CH₂) 1164 (C-O) 722 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.22 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.8 \\) Hz, 3.8 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.7 Hz, CH₂O), 3.80-3.20 (4H, m, HCO), 2.30 (6H, t, \\( J = 6.5 \\) Hz O=CCH₂CH₂), 1.69-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.51-1.44 (8H, m, CH₂COH) 1.43-1.20 (64H, m, CH₂CH₂), 0.88 (9H, t, \\( J = 6.5 \\) Hz, CH₂CH₃); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.3, 172.8 \\) (C=O) 74.3, 72.3, 62.9 (C-O), 68.7 (OCH), 62.1, 61.8 (CH₂O), 33.8 (O=CCH₂), 24.6 (O=CCH₂CH₂CH₂), 31.3, 29.4, 29.5, 25.1, 22.5 (CH₂CH₂CH₂), 13.9 (CH₂CH₃).\n\n126.96.36.199 Ring opening of epoxidized soybean oil (2.6) by water\n\nThe experiment was conducted according to the procedure described in section 188.8.131.52. Epoxidized soybean oil (2.6) (5 g, 5 mmol), deionized water (15 ml), phosphoric acid (1 g, 10 mmol), a yellowish liquid (2.40, 5.4 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3358 (O-H) 2923, 2853 (C-H) 1743 (C=O) 1459 (CH₂) 1170 (C-O) 723 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.29-5.22 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.0 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.5 \\) Hz, 5.7 Hz, CH₂O), 3.80-3.20 (10H, m, HCO), 2.31\n\n(6H, t, $J= 6.5$ Hz O=CCH$_2$CH$_2$), 1.70-1.55 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.52-1.44 (14H, m, CH$_2$COH) 1.43-1.20 (50H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J = 6.5$Hz, CH$_2$CH$_3$);\n\n$^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.2$, 172.8 (C=O) 74.2, 72.5, 65.9 (C-O), 68.7 (OCH), 62.0, 61.8 (CH$_2$O), 33.8 (O=CCH$_2$), 24.6 (O=CCH$_2$CH$_2$CH$_2$), 31.3, 29.4, 29.2, 25.0, 22.7 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$).\n\n### 6.2 GENERAL PROCEDURES FOR SUBSTRATES SYNTHESIZED IN CHAPTER 3\n\n#### 6.2.1 General procedure for polyurethanes synthesized with oligomeric polyols\n\n**Polyurethane (3.3) based on oligomeric polyol (2.24) as an example**\n\nOligomeric polyol (2.24) (1 g, hydroxyl value = 35.7 mg KOH/g sample) was weighed into a round bottom flask and chloroform (2 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. Then, 4,4’-methylene diphenyl diisocyanate (MDI) (0.07 g) was added to the dissolved polyol. The NCO/OH ratio index was 1.02. The reaction mixture was heated to 60 °C under reflux condition for 24 hours. After 24 hours, some of the chloroform was removed by using a rotary evaporator and then polyurethane product was poured into a pre-heated mold at 60 °C. The polyurethane (3.3) was cured at 60 °C for 24 hours in an oven. $v_{\\text{max}}/\\text{cm}^{-1}$ 2916, 2849 (C-H) 1725 (C=O) 1530 (aromatic =CH) 1173 (C-O) 721 (CH$_2$);\n\n6.2.2 General procedure for polyurethanes synthesized with oligomeric polyols and 1,4-butanediol\n\nPolyurethane based on oligomeric polyol (2.24) as an example\n\nOligomeric polyol (2.24) (1 g, hydroxyl value = 35.7 mg KOH/g sample) and 1,4-butane diol (92 mg) were weighed into a round bottom flask and chloroform (7 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. Then, 4,4'-methylene diphenyl diisocyanate (MDI) (0.33 g) was added to the dissolved polyol. The NCO/OH ratio index was 1.02. The reaction mixture was heated to 60 °C under reflux condition for 24 hours. After 24 hours, some of the chloroform was removed by using a rotary evaporator and then polyurethane product was poured into a pre-heated mold at 60 °C. The polyurethane was cured at 60 °C for 24 hours in an oven. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 2915, 2849 (C-H) 1726 (C=O) 1527 (aromatic =CH) 1095 (C-O) 721 (CH₂);\n\n6.2.3 General procedure for polyurethanes synthesized with oligomeric polyols and polyethylene glycol\n\nPolyurethane (3.10) based on oligomeric polyol (2.24) as an example\n\nOligomeric polyol (2.24) (5 g, hydroxyl value = 35.7 mg KOH/g sample) and polyethylene glycol (average molecule weight = 3350) (6.5 g) were weighed into a round bottom flask and chloroform (25 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. Then, 4,4'-methylene diphenyl diisocyanate (MDI) (1.7 g) was added to the dissolved polyol. The NCO/OH ratio index was 1.02. The reaction mixture was heated to 60 °C under reflux condition for 24 hours. After 24 hours, some of the\n\nchloroform was removed by using a rotary evaporator and then polyurethane product was poured into a pre-heated mold at 60 °C. The polyurethane (3.10) was cured at 60 °C for 24 hours in an oven. $v_{\\text{max}}/\\text{cm}^{-1}$ 2922, 2853 (C-H) 1743 (C=O) 1597 (aromatic =CH) 1095 (C-O) 721 (CH$_2$);\n\n6.2.4 General procedure for polyurethanes synthesized with oligomeric polyols, glycerol and polyethylene glycol\n\nPolyurethane (3.18) based on oligomeric polyol (2.23) as an example\n\nOligomeric polyol (2.23) (7 g, hydroxyl value = 31 mg KOH/g sample), polyethylene glycol (average molecule weight = 3350) (6.5 g) and glycerol (0.42 g) were weighed into a round bottom flask and chloroform (70 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. Then, 4,4'-methylene diphenyl diisocyanate (MDI) (3.6 g) was added to the dissolved polyol. The NCO/OH ratio index was 1.02. The reaction mixture was heated to 60 °C under reflux condition for 24 hours. After 24 hours, some of the chloroform was removed by using a rotary evaporator and then polyurethane product was poured into a pre-heated mold at 60 °C. The polyurethane (3.18) was cured at 60 °C for 24 hours in an oven. $v_{\\text{max}}/\\text{cm}^{-1}$ 2916, 2850 (C-H) 1734 (C=O) 1597 (aromatic =CH) 1014 (C-O) 793 (CH$_2$);\n\n6.3 General Procedures for Substrates Synthesized in Chapter 4\n\n184.108.40.206 General procedure for copolymerization of epoxidized plant oils with tetrahydrofuran [epoxidized cocoa butter (2.16) as an example]\n\nEpoxidized cocoa butter (2.16) (50 g, 57 mmol) was weighed into a round bottom flask and dry tetrahydrofuran (250 ml) was added to it. The reactants mixture was stirred and heated at 20 °C under N₂ atmosphere for 30 minutes. Then BF₃.Et₂O (0.81 g, 5.7 mmol) was added drop-wise to the epoxidized cocoa butter (2.16) / tetrahydrofuran mixture. After the addition of BF₃.Et₂O was completed, the reaction temperature was maintained at 20 °C under N₂ atmosphere for another 24 hours. Then, the reaction mixture was poured into separation funnel and then saturated NaCl solution (200 cm³) and chloroform (300 cm³) were added to the reaction mixture. The aqueous layer was separated from the organic layer and the organic layer was neutralized with saturated sodium hydrogen carbonate solution (100 cm³). The organic layer was again washed with NaCl solution (200 cm³). The organic layer was dried over anhydrous MgSO₄ followed by removal of solvent *in vacuo* to yield a clear viscous liquid (4.7) (120 g) \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3360 (O-H) 2921, 2850 (C-H) 1742 (C=O) 1105 (C-O) 754 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_{\\text{H}} = 5.24-5.28 \\) (1H, m, CHO) 4.25 (2H, dd, \\( J = 11.9 \\) Hz, 4.4Hz, CH₂O), 4.10 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH₂O), 3.43 – 3.30 (64H, m, HCO), 2.26 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.62-1.50 (72H, m, O=CCH₂CH₂CH₂, CH₂CH₂O), 1.30-1.18 (72H, m, CH₂CH₂), 0.83 (9H, t, \\( J = 6.8 \\) Hz, CH₂CH₃); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_{\\text{C}} = 173.2, 172.8 \\) (C=O) 70.4 (HC-O) 68.9 (HC-O), 62.0, 61.8 (H₂C-O), 33.9 (O=CCH₂), 26.3 (O=CCH₂CH₂CH₂, CH₂CH₂O), 29.5, 22.4 (CH₂CH₂CH₂), 13.9 (CH₂CH₃)\n\n220.127.116.11 Copolymerization of epoxidized methyl oleate (2.3) with tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 18.104.22.168. Epoxidized methyl oleate (2.3) (50 g, 160 mmol), dry tetrahydrofuran (1000 ml), BF$_3$.Et$_2$O (1.13 g, 8 mmol), clear viscous liquid (4.4) (78 g) $\\nu_{\\text{max}}/\\text{cm}^{-1}$ 3353 (O-H) 2924, 2852 (C-H) 1739 (C=O) 1105 (C-O) 755 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 3.66$ (3H, s, CH$_3$O), 3.62-3.50 (2H, m, CHO), 3.46-3.34 (92H, m, CH$_2$O), 2.29 (2H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.69-1.55 (94H, m, O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 1.50-1.20 (24H, m, CH$_2$CH$_2$), 0.87 (3H, t, $J= 7.0$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.4$ (C=O) 72.0, 70.1 (HC-O) 50.7 (H$_3$C-O), 33.4 (O=CCH$_2$), 26.0 (O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 31.1, 29.2, 22.4 (CH$_2$CH$_2$CH$_2$), 13.6 (CH$_2$CH$_3$)\n\n22.214.171.124 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. Epoxidized palm oil (2.17) (50 g, 56 mmol), tetrahydrofuran (2000 ml), BF$_3$.Et$_2$O (0.32 g, 2.3 mmol), clear viscous liquid (4.10) (403 g) $\\nu_{\\text{max}}/\\text{cm}^{-1}$ 3355 (O-H) 2918, 2851 (C-H) 1742 (C=O) 1103 (C-O) 746 (CH$_2$) $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H =$ 5.27-5.20 (1H, m, CHO), 4.27 (2H, dd, $J= 11.9$ Hz, 4.1Hz, CH$_2$O), 4.12 (2H, dd, $J= 11.9$ Hz, 5.9 Hz, CH$_2$O), 3.45-3.32 (400H, m, HCO), 2.31 (6H, t, $J= 7.8$ Hz, O=CCH$_2$CH$_2$), 1.68-1.52 (406H, m, O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 1.35-1.20 (64H, m, CH$_3$CH$_2$), 0.86 (9H, t, $J= 6.8$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C =$ 173.2, 172.8 (C=O) 70.6 (HC-O) 68.9 (HC-O), 62.2, 62.0 (H$_2$C-O), 33.9 (O=CCH$_2$), 26.3 (O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 29.6, 22.5 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n188.8.131.52 Copolymerization of epoxidized rapeseed oil (2.13) with tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 184.108.40.206.\n\nEpoxidized rapeseed oil (2.13) (10 g, 10 mmol), tetrahydrofuran (1000 ml), BF$_3$.Et$_2$O (0.13 g, 0.9 mmol), clear viscous liquid (4.12) (80 g) $v_{\\text{max}}$/cm$^{-1}$ 3353 (O-H) 2922, 2854 (C-H) 1740 (C=O) 1106 (C-O) 755 (CH$_2$), $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H =$ 5.8-5.22 (1H, m, CHO), 4.29 (2H, dd, $J=$ 11.8 Hz, 4.2Hz, CH$_2$O), 4.14 (2H, dd, $J=$ 11.9 Hz, 5.9 Hz, CH$_2$O), 3.48-3.33 (400H, m, HCO), 2.31 (6H, t, $J=$ 7.4 Hz, O=CCH$_2$CH$_2$), 1.68-1.54 (406H, m, O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 1.53-1.39 (12H, m, CHOCH$_2$CH$_2$), 1.38-1.22 (54H, m, CH$_2$CH$_2$), 0.87 (9H, t, $J=$ 6.4 Hz, CH$_2$CH$_3$);\n\n$^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C =$ 173.0, 172.6 (C=O) 70.4 (HC-O) 68.9 (HC-O), 62.3, 62.1 (H$_2$C-O), 33.8 (O=CCH$_2$), 26.3 (O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 29.5, 22.5 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n220.127.116.11 Copolymerization of epoxidized soybean oil (2.6) with tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 18.104.22.168.\n\nEpoxidized soybean oil (2.6) (10 g, 10 mmol), tetrahydrofuran (800 ml), BF$_3$.Et$_2$O (0.14 g, 1 mmol) clear viscous liquid (4.15) (85 g) $v_{\\text{max}}$/cm$^{-1}$ 3355 (O-H) 2940, 2858 (C-H) 1742 (C=O) 1105 (C-O) 746 (CH$_2$), $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H =$ 5.28-5.22 (1H, m, CHO), 4.30 (2H, dd, $J=$ 11.7 Hz, 3.2 Hz, CH$_2$O), 4.14 (2H, dd, $J=$ 11.9 Hz, 5.9 Hz, CH$_2$O), 3.46-3.35 (244H, m, HCO), 2.31 (6H, t, $J=$ 7.4 Hz, O=CCH$_2$CH$_2$), 1.67-1.56 (250H, m, O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 1.53-1.39 (10H, m, CHOCH$_2$CH$_2$), 1.40-1.24 (46H, m, CH$_2$CH$_2$), 0.89 (9H, t, $J=$ 6.8 Hz, CH$_2$CH$_3$);\n\n$^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C =$ 173.3, 172.9 (C=O) 70.3 (HC-O) 68.8 (HC-O),\n\n61.9, 61.6 (H\\textsubscript{2}C-O), 33.6 (O=CCH\\textsubscript{2}), 26.2 (O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}, CH\\textsubscript{2}CH\\textsubscript{2}O), 29.3, 22.4 (CH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 13.8 (CH\\textsubscript{2}CH\\textsubscript{3})\n\n22.214.171.124 Copolymerization of euphorbia oil (2.18) with tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. Euphorbia oil (2.18) (50 g, 55 mmol), tetrahydrofuran (1500 ml), BF\\textsubscript{3}.Et\\textsubscript{2}O (0.31 g, 2.2 mmol) clear viscous liquid (4.18) (175 g), \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3350 (O-H) 2941, 2861 (C-H) 1744 (C=O) 1107 (C-O) 745 (CH\\textsubscript{2}), \\( ^1\\text{H NMR} \\) (400 MHz, CDCl\\textsubscript{3}): \\( \\delta_H = 5.56-5.30 \\) (6H, m, CH\\textsubscript{2}=CH), 5.28-5.23 (1H, m, CHO), 4.30 (2H, dd, \\( J= 11.9 \\) Hz, 4.0 Hz, CH\\textsubscript{2}O), 4.14 (2H, dd, \\( J= 11.9 \\) Hz, 5.9 Hz, CH\\textsubscript{3}O), 3.48-3.35 (254H, m, HCO), 2.31 (6H, t, \\( J= 7.5 \\) Hz, O=CCH\\textsubscript{2}CH\\textsubscript{2}), 2.09-1.97 (12H, m, CH\\textsubscript{2}CH=CH) 1.68-1.56 (260H, m, O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}, CH\\textsubscript{2}CH\\textsubscript{2}O), 1.52-1.23 (48H, m, CH\\textsubscript{2}CH\\textsubscript{2}), 0.89 (9H, t, \\( J= 7.0 \\) Hz, CH\\textsubscript{2}CH\\textsubscript{3}); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl\\textsubscript{3}): \\( \\delta_C = 173.0, 172.6 \\) (C=O) 129.6, 125.3 (HC=CH), 70.4 (HC-O) 68.6 (HC-O), 62.1, 61.7 (H\\textsubscript{2}C-O), 33.7 (O=CCH\\textsubscript{2}), 26.3 (O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}, CH\\textsubscript{2}CH\\textsubscript{2}O), 29.1, (CH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 13.9 (CH\\textsubscript{2}CH\\textsubscript{3})\n\n188.8.131.52 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by AlCl\\textsubscript{3}\n\nThe experiment was conducted according to the procedure described in 184.108.40.206. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), AlCl\\textsubscript{3} (0.29 g, 2.2 mmol), yellowish liquid (6 g) \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3560 (O-H) 2924, 2854 (C-H) 1742 (C=O) 1163 (C-O) 723 (CH\\textsubscript{2}) \\( ^1\\text{H NMR} \\) (400 MHz, CDCl\\textsubscript{3}): \\( \\delta_H = 5.25-5.20 \\) (1H, m, CHO), 4.27 (2H, dd, \\( J= 11.9 \\) Hz, 4.3 Hz, CH\\textsubscript{2}O), 4.11 (2H, dd, \\( J= 11.9 \\) Hz, 5.9 Hz, CH\\textsubscript{2}O), 3.65-3.35 (4H, m, HCO), 2.29 (6H, t, \\( J= 7.5 \\) Hz, O=CCH\\textsubscript{2}CH\\textsubscript{2}), 1.64-1.54 (6H, m, O=CCH\\textsubscript{2}CH\\textsubscript{2}CH\\textsubscript{2}), 1.36-1.19 (64H, m, CH\\textsubscript{2}CH\\textsubscript{2}), 0.86 (9H, t, \\( J= 7.0 \\)\n\nHz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.1$, 172.7 (C=O) 73.3, 70.6 (HC-O), 68.7 (HC-O), 62.0, 61.8 (H$_2$C-O), 33.9 (O=CCH$_2$), 24.7 (O=CCH$_2$CH$_2$CH$_2$), 29.3, 22.8 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$)\n\n220.127.116.11 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by FeCl$_3$\n\nThe experiment was conducted according to the procedure described in 18.104.22.168. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), FeCl$_3$ (0.35 g, 2.2 mmol) yellowish liquid (25 g) $v_{\\text{max}}/\\text{cm}^{-1}$ 3351 (O-H) 2934, 2853 (C-H) 1743 (C=O) 1104 (C-O) 725 (CH$_2$) $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.25-5.15$ (1H, m, CHO), 4.31 (2H, dd, $J= 11.7$ Hz, 4.3 Hz, CH$_2$O), 4.13 (2H, dd, $J= 11.9$ Hz, 5.9 Hz, CH$_2$O), 3.60-3.10 (180H, m, HCO), 2.28 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.75-1.40 (186H, m, O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 1.35-1.15 (64H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J= 7.0$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.3$, 172.9 (C=O) 70.5 (HC-O) 68.9 (HC-O), 62.2, 61.8 (H$_2$C-O), 33.9 (O=CCH$_2$), 26.3 (O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 29.2, 22.4 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n22.214.171.124 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by SnCl$_4$\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), SnCl$_4$ (0.58 g, 2.3 mmol) yellowish liquid (43 g) $v_{\\text{max}}/\\text{cm}^{-1}$ 3336 (O-H) 2919, 2852 (C-H) 1741 (C=O) 1107 (C-O) 746 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.28-5.23$ (1H, m, CHO), 4.29 (2H, dd, $J= 11.8$ Hz, 4.2Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.9$ Hz,\n\n5.9 Hz, CH₂O), 3.47-3.35 (252H, m, HCO), 2.30 (6H, t, J= 7.4 Hz, O=CCH₂CH₂), 1.67-1.57 (258H, m, O=CCH₂CH₂CH₂, CH₂CH₂O), 1.40-1.20 (64H, m, CH₂CH₂), 0.88 (9H, t, J = 6.8 Hz, CH₂CH₃); \\(^{13}\\)C NMR (100 MHz CDCl₃): \\(δ_C\\) = 172.9, 172.4 (C=O) 70.6 (HC-O) 68.9 (HC-O), 62.3, 61.9 (H₂C-O), 33.9 (O=CCH₂), 26.5 (O=CCH₂CH₂CH₂, CH₂CH₂O), 29.5, 22.5 (CH₂CH₂CH₂), 13.9 (CH₂CH₃)\n\n188.8.131.52 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by TiCl₄\n\nThe experiment was conducted according to the procedure described in 184.108.40.206. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), TiCl₄ (0.29 g, 2.2 mmol), yellowish liquid (10 g) \\(ν_{\\text{max}}/\\text{cm}^{-1}\\) 3563 (O-H) 2927, 2855 (C-H) 1741 (C=O) 1162 (C-O) 724 (CH₂) \\(^1\\)H NMR (400 MHz, CDCl₃): \\(δ_H\\) = 5.29-5.22 (1H, m, CHO), 4.30 (2H, dd, J= 11.9 Hz, 4.2 Hz, CH₂O), 4.13 (2H, dd, J= 11.9 Hz, 5.9 Hz, CH₂O), 3.74-3.37 (4H, m, HCO), 2.31 (6H, t, J= 7.5 Hz, O=CCH₂CH₂), 1.67-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.54-1.20 (64H, m, CH₂CH₂), 0.89 (9H, t, J = 7.0 Hz, CH₂CH₃); \\(^{13}\\)C NMR (100 MHz CDCl₃): \\(δ_C\\) = 173.3, 172.9 (C=O) 73.4, 72.3, 70.7 (HC-O), 68.8 (HC-O), 62.3, 61.9 (H₂C-O), 33.8 (O=CCH₂), 24.5 (O=CCH₂CH₂CH₂), 28.9, 22.5 (CH₂CH₂CH₂), 13.9 (CH₂CH₃)\n\n220.127.116.11 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by HBF₄\n\nThe experiment was conducted according to the procedure described in 18.104.22.168. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), HBF₄ (80 mg, 0.45 mmol) clear viscous liquid (38 g) \\(ν_{\\text{max}}/\\text{cm}^{-1}\\) 3360 (O-H) 2930, 2858 (C-H)\n\n1740 (C=O) 1105 (C-O) 744 (CH$_2$) $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.29-5.22$ (1H, m, CHO), 4.29 (2H, dd, $J= 11.9$ Hz, 4.1 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.9$ Hz, 5.9 Hz, CH$_2$O), 3.45-3.32 (160H, m, HCO), 2.31 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.68-1.54 (166H, m, O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 1.53-1.20 (64H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J= 6.8$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.1$, 172.7 (C=O) 70.5 (HC-O) 68.8 (HC-O), 62.1, 62.0 (H$_2$C-O), 33.9 (O=CCH$_2$), 26.3 (O=CCH$_2$CH$_2$CH$_2$, CH$_2$CH$_2$O), 29.5, 22.4 (CH$_2$CH$_2$CH$_2$), 13.9 (CH$_2$CH$_3$)\n\n### 22.214.171.124 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by HBF$_4$ with addition of water\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (100 ml), de-ionised water (1 ml), HBF$_4$ (80 mg, 0.45 mmol) clear liquid (9 g), $v_{\\text{max}}/\\text{cm}^{-1}$ 3461 (O-H) 2922, 2853 (C-H) 1742 (C=O) 1160 (C-O) 722 (CH$_2$) $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.29-5.23$ (1H, m, CHO), 4.30 (2H, dd, $J= 11.9$ Hz, 4.0 Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.8$ Hz, 5.9 Hz, CH$_2$O), 3.65-3.30 (2H, m, HCO), 3.15-2.80 (2H, m, CH$_2$CHOCHCH$_2$), 2.31 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.64-1.50 (6H, m, O=CCH$_2$CH$_2$CH$_2$), 1.48-1.36 (4H, m, CHOCH$_2$CH$_2$), 1.35-1.15 (64H, m, CH$_2$CH$_2$), 0.88 (9H, t, $J= 6.8$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.1$, 172.6 (C=O) 74.1, 70.4 (HC-O), 68.7 (HC-O), 62.0, 61.7 (H$_2$C-O), 56.9 (CH$_2$CHOCHCH$_2$) 33.7 (O=CCH$_2$), 28.2 (CHOCH$_2$CH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 29.4, 22.4 (CH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$)\n\n188.8.131.52 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by triflic acid\n\nThe experiment was conducted according to the procedure described in 184.108.40.206. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), trifluoromethane sulfonic acid (0.34 g, 2.3 mmol) yellowish liquid (49 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3460 (O-H) 2919, 2852 (C-H) 1742 (C=O) 1106 (C-O) 745 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.20 \\) (1H, m, CHO), 4.29 (2H, dd, \\( J = 11.8 \\) Hz, 4.1 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH₂O), 3.50-3.30 (230H, m, HCO), 2.31 (6H, t, \\( J = 7.4 \\) Hz, O=CCH₂CH₂), 1.70-1.53 (236H, m, O=CCH₂CH₂CH₂, CH₂CH₂O), 1.40-1.20 (64H, m, CH₂CH₂), 0.88 (9H, t, \\( J = 7.0 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.3, 172.7 \\) (C=O) 70.4 (HC-O) 68.8 (HC-O), 62.3, 61.7 (H₂C-O), 33.7 (O=CCH₂), 26.3 (O=CCH₂CH₂CH₂, CH₂CH₂O), 29.5, 22.6 (CH₂CH₂CH₂), 13.9 (CH₂CH₃)\n\n220.127.116.11 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by sulfuric acid\n\nThe experiment was conducted according to the procedure described in 18.104.22.168. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), sulfuric acid (0.22 g, 2.2 mmol), yellowish liquid (9 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3465 (O-H) 2922, 2853 (C-H) 1743 (C=O) 1159 (C-O) 722 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.22 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.3 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH₂O), 3.76-3.34 (2H, m, HCO), 3.14-2.82 (2H, m, CH₂CHOCHCH₂), 2.31 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.67-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.55-1.44 (4H, m, CHOCH₂CH₂), 1.43-1.19 (64H, m, CH₂CH₂), 0.89 (9H, t, \\( J = 6.8 \\) Hz,\n\n22.214.171.124 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by chlorosulfonic acid\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), chlorosulfonic acid (0.29 g, 2.2 mmol), yellowish liquid (10 g) \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3563 (O-H) 2927, 2853 (C-H) 1740 (C=O) 1160 (C-O) 721 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.29-5.22 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.0 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH₂O), 3.65-3.35 (2H, m, HCO), 3.15-2.85 (2H, m, CH₂CHOCHCH₂), 2.31 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.68-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.54-1.45 (4H, m, CHOCH₂CH₂), 1.40-1.20 (64H, m, CH₂CH₂), 0.89 (9H, t, \\( J = 7.0 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 172.7, 172.3 \\) (C=O) 74.2, 72.6 (HC-O), 68.9 (HC-O), 62.1, 61.7 (H₂C-O), 56.6 (CH₂CHOCHCH₂) 34.1 (O=CCH₂), 28.3 (CHOCH₂CH₂), 24.8 (O=CCH₂CH₂CH₂), 29.7, 22.7 (CH₂CH₂CH₂), 14.0 (CH₂CH₃)\n\n188.8.131.52 Copolymerization of epoxidized palm oil (2.17) with tetrahydrofuran catalyzed by trifluoroacetic acid\n\nThe experiment was conducted according to the procedure described in 184.108.40.206. Epoxidized palm oil (2.17) (10 g, 11 mmol), dry tetrahydrofuran (200 ml), trifluoroacetic acid (0.25 g, 2.2 mmol) yellowish liquid (7 g) \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3620 (O-H) 2923, 2853 (C-H) 1741 (C=O) 1161 (C-O) 823 (CHOCHCH₂) 724 (CH₂) \\( ^1 \\text{H NMR} \\)\n\n(400 MHz, CDCl₃): δ_H = 5.30-5.22 (1H, m, CHO), 4.30 (2H, dd, J= 11.9 Hz, 4.2 Hz, CH₂O), 4.14 (2H, dd, J= 11.9 Hz, 5.9 Hz, CH₂O), 3.73-3.41 (2H, m, HCO), 2.95-2.73 (2H, m, CH₂CHOCHCH₂), 2.32 (6H, t, J= 7.5 Hz, O=CCH₂CH₂), 1.67-1.57 (6H, m, O=CCH₂CH₂CH₂), 1.56-1.50 (4H, m, CHOCH₂CH₂), 1.49-1.24 (64H, m, CH₂CH₂), 0.89 (9H, t, J = 7.0 Hz, CH₂CH₃);¹³C NMR (100 MHz CDCl₃): δ_C = 173.1, 172.7 (C=O) 73.6, 71.8 (HC-O), 68.7 (HC-O), 62.0, 61.8 (H₂C-O), 57.3 (CH₂CHOCHCH₂) 33.9 (O=CCH₂), 27.9 (CHOCH₂CH₂), 24.6 (O=CCH₂CH₂CH₂), 29.3, 22.5 (CH₂CH₂CH₂), 13.7 (CH₂CH₃)\n\n220.127.116.11 Attempted copolymerization of epoxidized palm oil (2.17) with 2-methyl tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 18.104.22.168. Epoxidized palm oil (2.17) (1 g, 1.1 mmol), 2-methyl tetrahydrofuran (20 ml), BF₃.Et₂O (3 mg, 0.022 mmol) yield back starting material epoxidised palm oil (2.17) (0.7 g).\n\n22.214.171.124 Attempted copolymerization of epoxidized palm oil with 3-methyl tetrahydrofuran\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. Epoxidized palm oil (2.17) (0.1 g, 0.11 mmol), 3-methyl tetrahydrofuran (1 ml), BF₃.Et₂O (3 mg, 0.022 mmol) yield back starting material epoxidised palm oil (2.17) (95 mg).\n\n6.3.3 Homopolymerization of tetrahydrofuran catalyzed by triflic acid\n\nTetrahydrofuran (THF) (150 g, 2.1 mol) was weighed into a round bottom flask and was stirred and heated at 60 °C under N₂ atmosphere for 30 minutes. Then triflic acid (CF₃SO₃H) (24.0 g, 0.16 mol) was added drop-wise to the THF. After the addition of triflic acid was completed, the reaction temperature was maintained at 60 °C under N₂ atmosphere for another 8 hours. Then, the reaction mixture was poured into separation funnel. Cyclohexane (300 ml) and deionized water (300 ml) were added to it. The aqueous layer was discarded and the organic layer was washed with sodium bicarbonate solution (300 ml). The organic layer was separated from the aqueous layer. The organic layer was again washed with deionized water (300 ml). The organic layer was separated from the aqueous and was dried over anhydrous MgSO₄. The cyclohexane was removed in vacuo to yield homopolymer of THF (4.19) (61.4 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3462 (O-H) 2924, 2854 (C-H) 1741 (C=O) 1464 (CH₂) 1088 (C-O) 723 (CH₂); \\( ^1\\text{H} \\) NMR (400 MHz, CDCl₃): \\( \\delta_H = 3.43 \\) (4H, t, \\( J = 7.7 \\) Hz, CH₂O), 1.68-1.56 (4H, m, CH₂); \\( ^{13}\\text{C} \\) NMR (100 MHz CDCl₃): \\( \\delta_C = 70.3, \\) (HC-O), 26.2 (CH₂CH₂)\n\n6.3.4 Copolymerization of ε-caprolactone with epoxidized palm oil (2.17)\n\nEpoxidized palm oil (2.17) (40 g, 45 mmol) and ε-caprolactone (10.2, 90 mmol) were weighed into a round bottom flask and dry dichloromethane (200 ml) was added to it. The reactants mixture was stirred and heated at 20 °C under N₂ atmosphere for 30 minutes. Then BF₃.Et₂O (640 mg, 4.5 mmol) was added drop-wise to the epoxidized palm oil / ε-caprolactone mixture. After the addition of BF₃.Et₂O was completed, the reaction temperature was maintained at 20 °C under N₂ atmosphere for another 24 hours. Then, the reaction mixture was poured into\n\nseparation funnel and CHCl₃ (100 ml) was added to it. The organic layer was washed with sodium bicarbonate solution (50 ml). The organic layer was separated from the aqueous layer. The organic layer was dried over anhydrous MgSO₄ and CHCl₃ was removed *in vacuo* to yield copolymers (4.24) (50 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3475 (O-H) 2923, 2853 (C-H) 1737 (C=O) 1461 (CH₂) 1164 (C-O) 722 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.29-5.22 \\) (1H, m, CHO), 4.87-4.80(1H, m, CHOC=O), 4.30 (2H, dd, \\( J = 11.8 \\) Hz, 3.8 Hz , CH₂O), 4.14 (2H, dd, \\( J = 11.8 \\) Hz, 5.8 Hz, CH₂O), 4.06 (2H, t, \\( J = 6.5 \\) Hz, O=COCH₂) 3.61 (2H, t, \\( J = 6.4 \\) Hz, HOCH₂ ), 3.58-3.10 (4H, m, HCO), 2.32 (8H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.71-1.52(10H, m, O=CCH₂CH₂CH₂), 1.53-1.39 (4H, m, CH₂CH₂), 1.36-1.18 (64H, m, CH₂CH₂), 0.88 (9H, t, \\( J = 6.6 \\) Hz, CH₂CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.1, 172.6 \\) (C=O) 76.2, 74.3, 72.0 (HC-O), 68.7 (HC-O), 63.7, 62.2, 61.8 (H₂C-O), 61.9 (H₂C-OH), 33.8 (O=CCH₂), 24.6 (O=CCH₂CH₂CH₂), 29.4, 22.6 (CH₂CH₂CH₂), 13.8 (CH₂CH₃)\n\n**6.3.5 General Procedure for Polyurethanes Synthesized with Copolymers Polyol**\n\n**188.8.131.52 Polyurethane made from copolymerized epoxidized palm oil and tetrahydrofuran (4.10) as an example.**\n\nCopolymerized epoxidized palm oil and tetrahydrofuran (4.10) (10 g, hydroxyl value = 30.5 mg KOH/g sample) was weighed into a round bottom flask and chloroform (150 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. Then, 4,4'-methylene diphenyl diisocyanate (MDI) (1.7 g) was added to the dissolved polyol. The NCO/OH ratio index was 1.02. The reaction mixture was heated to 60 °C under reflux condition for 24 hours. After 24 hours, some of the chloroform was removed by using a rotary\n\nevaporator and then polyurethane product was poured into a pre-heated mold at 60 °C. The polyurethane (4.10PU) was cured at 60 °C for 24 hours in an oven.\n\n\\[ \\nu_{\\text{max}}/\\text{cm}^{-1} \\]\n3308 (O=CNH) 2915, 2849 (C-H) 1729 (C=O) 1595 (aromatic =CH) 1098 (C-O) 721 (CH₂)\n\n### 6.3.6 Differential Scanning Calorimetric (DSC) and Thermogravimetric (TGA) method\n\nDSC and TGA of polyurethane samples were conducted in a Mettler Toledo TGA/DSC 1 system. For DSC analysis, the samples were scanned from -100 °C to 600 °C at a heating rate of 10 K per minute in the presence of nitrogen. For TGA analysis, the samples were scanned from 25 °C to 600 °C at a heating rate of 10 K per minute in the presence of nitrogen.\n\n### 6.3.7 Tensile test method\n\nTensile strength and elongation at break of polyurethane samples were determined according to EN ISO 529-4: 1997 (CEN1997a). This is the European standard test method for the determination of tensile properties of polymeric materials. Testing was conducted with an Instron 5800 universal testing machine with an initial cross-head speed of 1 mm/minute for 2 minutes and then 50 mm/minute. The test specimens were of the type 1BA.\n\n6.4 General Procedures for Substrates Synthesized in Chapter 5\n\n184.108.40.206 General procedure for one-pot oligomerization of unsaturated plant oil with Na₂WO₄\n\n[Rapeseed oil (2.11) as an example]\n\nRapeseed oil (70 g, 80 mmol), Na₂WO₄·2H₂O (3 g, 9 mmol), Aliquat 336 (4 g, 9 mmol) and H₂O₂ (30% w/w, 257 g, 2270 mmol) were charged into a 3-neck round bottom flask equipped with magnetic stirrer bar and reflux condenser. The mixture was heated to 100 °C and stirred vigorously for 8 hours. The mixture was then poured into a separating funnel and was left to cool. The aqueous layer was separated from the organic layer. The organic layer was diluted with equal amount of dichloromethane (100 ml) and neutralized with saturated Na₂CO₃ (50 ml). The organic layer was again washed with NaCl solution (100 cm³). The organic layer was dried over anhydrous MgSO₄ followed by removal of solvent *in vacuo* to yield a viscous pale yellow liquid (68.1 g).\n\n\\[ \\nu_{\\text{max}}/\\text{cm}^{-1} \\quad 2926, \\quad 2856 \\ (\\text{C-H}) \\quad 1738 \\ (\\text{C=O}) \\quad 1459 \\ (\\text{CH}_2) \\quad 1165 \\ (\\text{C-O}) \\quad 754 \\ (\\text{CH}_2); \\]\n\n¹H NMR (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.20 \\ (1\\text{H}, \\ m, \\ \\text{CHO}), \\ 4.32 \\ (2\\text{H}, \\ dd, \\ J= 11.9 \\ \\text{Hz}, \\ 3.7 \\ \\text{Hz}, \\ \\text{CH}_2\\text{O}), \\ 4.16 \\ (2\\text{H}, \\ dd, \\ J= 11.9 \\ \\text{Hz}, \\ 5.9 \\ \\text{Hz}, \\ \\text{CH}_2\\text{O}), \\ 3.75-3.30 \\ (4\\text{H}, \\ m, \\ \\text{CHO}), \\ 2.34 \\ (6\\text{H}, \\ t, \\ J= 7.5 \\ \\text{Hz}, \\ \\text{O=CCH}_2\\text{CH}_2), \\ 1.68-1.56 \\ (6\\text{H}, \\ m, \\ \\text{O=CCH}_2\\text{CH}_2\\text{CH}_2), \\ 1.39-1.21 \\ (54\\text{H}, \\ m, \\ \\text{CH}_2\\text{CH}_2), \\ 0.90 \\ (9\\text{H}, \\ t, \\ J= 7.5 \\ \\text{Hz}, \\ \\text{CH}_2\\text{CH}_3); \\]\n\n¹³C NMR (100 MHz CDCl₃): \\( \\delta_C = 173.1, \\ 172.7 \\ (\\text{C=O}), \\ 72.2 \\ (\\text{HC-O}), \\ 68.7 \\ (\\text{HC-O}), \\ 62.1, \\ 61.7 \\ (\\text{H}_2\\text{C-O}), \\ 33.7 \\ (\\text{O=CCH}_2\\text{CH}_2), \\ 31.2, \\ 29.2, \\ 22.6 \\ (\\text{CH}_2\\text{CH}_2), \\ 24.3 \\ (\\text{O=CCH}_2\\text{CH}_2\\text{CH}_2), \\ 13.7 \\ (\\text{CH}_2\\text{CH}_3). \\]\n\n220.127.116.11 One-pot oligomerization of palm oil (2.10) with sodium tungstate\n\nThe experiment was conducted according to the general procedure described in 18.104.22.168. Palm oil (2.10) (100 g, 116 mmol), Na₂WO₄·2H₂O (2.7 g, 8 mmol), Aliquat 336 (3.6 g, 8 mmol) and H₂O₂ (30% w/w, 224 g, 1976 mmol) viscous pale yellow liquid (95.8 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 2929, 2858 (C-H) 1741 (C=O) 1461 (CH₂) 1165 (C-O) 754 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.20 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.2 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH₂O), 3.70-3.56 (2H, m, CHO), 2.35 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.69-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.53-1.21 (64H, m, CH₂CH₂), 0.90 (9H, t, \\( J = 7.5 \\) Hz, CH₃CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.3, 172.9 \\) (C=O), 72.5 (HC-O), 68.9 (HC-O), 62.3, 61.9 (H₂C-O), 33.9 (O=CCH₂CH₂), 31.1, 29.3, 22.5 (CH₂CH₂), 24.4 (O=CCH₂CH₂CH₂), 13.8 (CH₂CH₃).\n\n22.214.171.124 One-pot oligomerization of soybean oil (2.12) with sodium tungstate\n\nThe experiment was conducted according to the general procedure described in 126.96.36.199. The experiment was conducted according to the general procedure described above. Soybean oil (2.12) (70 g, 80 mmol), Na₂WO₄·2H₂O (3.4 g, 10 mmol), Aliquat 336 (4 g, 9 mmol) and H₂O₂ (30% w/w, 267 g, 2355 mmol) viscous pale yellow liquid (67.5 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 2930, 2860 (C-H) 1742 (C=O) 1455 (CH₂) 1160 (C-O) 752 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.23 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.9 \\) Hz, 4.1 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.9 \\) Hz, 5.8 Hz, CH₂O), 3.80-3.30 (4H, m, CHO), 2.34 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.70-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.54-1.21 (48H, m, CH₂CH₂), 0.90 (9H, t, \\( J = 6.8 \\) Hz, CH₃CH₃); \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.2, 172.8 \\) (C=O), 72.6 (HC-O), 68.8 (HC-O), 62.1, 61.8 (H₂C-O),\n\n33.5 (O=CCH₂CH₂), 31.2, 29.5, 22.3 (CH₂CH₂), 24.5 (O=CCH₂CH₂CH₂), 13.9 (CH₂CH₃).\n\n188.8.131.52 One-pot oligomerization of soybean oil (2.12) and palm oil (2.10) with sodium tungstate\n\nThe experiment was conducted according to the general procedure described in 184.108.40.206. The experiment was conducted according to the general procedure described above. Soybean oil (2.12) (50 g, 57 mmol), palm oil (2.10) (50 g, 57 mmol), Na₂WO₄·2H₂O (2.6 g, 8 mmol), Aliquat 336 (3.5 g, 8 mmol) and H₂O₂ (30% w/w, 220 g, 1941 mmol) viscous pale yellow liquid (97.8 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 2929, 2859 (C-H) 1740 (C=O) 1460 (CH₂) 1160 (C-O) 752 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.31-5.23 \\) (1H, m, CHO), 4.30 (2H, dd, \\( J = 11.7 \\) Hz, 4.1 Hz, CH₂O), 4.15 (2H, dd, \\( J = 11.8 \\) Hz, 6.0 Hz, CH₂O), 3.80-3.35 (4H, m, CHO), 2.33 (6H, t, \\( J = 7.6 \\) Hz, O=CCH₂CH₂), 1.70-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.53-1.21 (56H, m, CH₃CH₂), 0.90 (9H, t, \\( J = 7.0 \\) Hz, CH₂CH₃); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.1, 172.7 \\) (C=O), 72.1 (HC-O), 68.6 (HC-O), 62.0, 61.7 (H₂C-O), 33.7 (O=CCH₂CH₂), 31.0, 29.1, 22.2 (CH₂CH₂), 24.2 (O=CCH₂CH₂CH₂), 13.8 (CH₂CH₃).\n\n220.127.116.11 General procedure for the oligomerization of unsaturated plant oil with tungsten powder\n\n[Rapeseed oil (2.11) as an example]\n\nTungsten powder (12 \\( \\mu \\text{m}, 99.99\\%, 0.9 \\) g, 4.9 mmol), hydrogen peroxide (30% w/w, 8 g, 61.8 mmol) and deionised water (3.5 cm³) were charged into a round bottom flask equipped with a magnetic stirrer and reflux condenser. The mixture was stirred and heated up to 50 °C until the tungsten powder was totally dissolved, then H₃PO₄\n\n(85%, 0.65 g, 5.6 mmol) in water (7 cm$^3$) was added into it (this is the tungsten catalyst solution). Rapeseed oil (170 g, 0.21 mol) and Adogen 464 (1.2 g, 3 mmol) were charged into another 3-neck round bottom flask equipped with a motor stirrer. The oil mixture was heated to the desired temperature and stirred vigorously. The tungsten catalyst solution was added to the oil mixture followed by water (300 cm$^3$), hydrogen peroxide (115 g, 0.97 mol) and H$_3$PO$_4$ (101.1 g, 0.877 mol). The temperature of the oil mixture was kept at 100 °C for 8 hours. The oil mixture was then poured into a separating funnel, and then saturated NaCl solution (100 cm$^3$) and dichloromethane (100 cm$^3$) were added to the oil mixture. The aqueous layer was separated from the organic layer. The organic layer was neutralized with saturated sodium hydrogen carbonate solution (100 cm$^3$). The organic layer was again washed with NaCl solution (100 cm$^3$). The organic layer was dried over anhydrous MgSO$_4$ followed by removal of solvent \\textit{in vacuo} to yield a viscous pale yellow liquid (165 g).\n\n$\\nu_{\\text{max}}$/cm$^{-1}$ 2924, 2854 (C-H) 1740 (C=O) 1460 (CH$_2$) 1164 (C-O) 752 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.29-5.22$ (1H, m, CHO), 4.27 (2H, dd, $J= 11.9$ Hz, 4.4Hz, CH$_2$O), 4.14 (2H, dd, $J= 11.6$ Hz, 5.8 Hz, CH$_2$O), 3.60-3.40 (1H, m, CHO), 2.36 (6H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.70-1.55 (6H, m, O=CCH$_3$CH$_2$CH$_2$), 1.38-1.20 (54H, m, CH$_2$CH$_2$), 0.92 (9H, t, $J= 7.5$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 173.3$, 172.9 (C=O), 74.3 (HC-O), 68.8 (HC-O), 62.1, 61.8 (H$_2$C-O), 33.8 (O=CCH$_2$CH$_2$), 31.3, 28.9, 22.5 (CH$_2$CH$_2$), 24.5 (O=CCH$_2$CH$_2$CH$_2$), 13.8 (CH$_2$CH$_3$).\n\n18.104.22.168 One-pot oligomerization of soybean oil (2.12) and palm oil (2.10) with tungsten powder\n\nThe experiment was conducted according to the general procedure described in 22.214.171.124. Tungsten powder (12 µm, 99.99%, 0.3 g, 1.6 mmol), hydrogen peroxide (30% w/w, 43 g, 380 mmol), deionised water (101.5 g), H₃PO₄ (85%, 28 g, 0.3 mol), soybean oil (50 g, 57 mmol), palm oil (50 g, 57 mmol), Adogen 464 (0.4 g, 1 mmol), a viscous pale yellow liquid (97.3 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 2920, 2850 (C-H) 1740 (C=O) 1465 (CH₂) 1168 (C-O) 751 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.29-5.21 \\) (1H, m, CHO), 4.29 (2H, dd, \\( J = 11.9 \\) Hz, 4.3 Hz, CH₂O), 4.14 (2H, dd, \\( J = 11.8 \\) Hz, 5.9 Hz, CH₂O), 3.76-3.33 (2H, m, CHO), 2.31 (6H, t, \\( J = 7.5 \\) Hz, O=CCH₂CH₂), 1.67-1.54 (6H, m, O=CCH₂CH₂CH₂), 1.53-1.21 (54H, m, CH₂CH₂), 0.88 (9H, t, \\( J = 6.8 \\) Hz, CH₂CH₃); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 173.5, 172.8 \\) (C=O), 73.5 (HC-O), 68.8 (HC-O), 62.1, 61.9 (H₂C-O), 33.8 (O=CCH₂CH₂), 31.0, 29.5, 22.3 (CH₂CH₂), 24.6 (O=CCH₂CH₂CH₂), 13.8 (CH₂CH₃).\n\n6.4.3 Synthesis of oleic acid based oligomers (5.6)\n\nOleic acid (5.5) (100 g, 0.354 mol), Na₂WO₄·2H₂O (2.5 g, 7.5 mmol), Aliquat 336 (3.4 g, 7.7 mmol), H₂O₂ (30% w/w, 215 g, 1.9 mol) were charged into a 3-neck round bottom flask equipped with magnetic stirrer bar and reflux condenser. The mixture was heated to 100 °C and stirred vigorously for 24 hours. The mixture was then poured into a separating funnel and was left to cool. The mixture separated into an organic and aqueous layer, with some white precipitate in the aqueous layer. The aqueous layer together with the white precipitate was separated from the organic layer. The white precipitate was filtered from the aqueous and washed with deionised water (3 x 100 ml) to remove any aqueous residual. Then it was dried in oven and\n\nwas characterized to be 1,9-nonanedioic acid (azelaic acid) (1.5 g, 7.98 mmol, 2.3%) (5.14). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 1695 (C=O) 2932, 2856 (C-H) 1684 (C=O) 1468 (CH₂) 1251 (C-O) 912 (CH₂); \\( ^1 \\text{H NMR} \\) (400 MHz, DMSO-d₆): \\( \\delta_H = 12.0 \\) (2H, s, COOH), 2.20 (4H, t, \\( J = 7.5 \\text{Hz}, \\ O=C\\text{CH}_2\\text{CH}_2\\)), 1.46-1.53 (4H, m, \\( \\ O=C\\text{CH}_2\\text{CH}_2\\text{CH}_2\\)), 1.08-1.40 (6H, m, CH₂CH₂CH₂) \\( ^{13} \\text{C NMR} \\) (100 MHz DMSO-d₆): \\( \\delta_C = 174.4 \\) (C=O), 34.0 (O=CCH₂), 28.8 (CH₂CH₂CH₂), 24.4 (O=CCH₂CH₂CH₂); \\( m/z \\) (ES⁺) [M+Na⁺] Required 211.0941, Found 211.0941; melting point = 106 - 108 °C ( literature¹¹³: 105 – 107 °C) [Found: C, 58.0; H, 8.7; C₉H₁₆O₄ Required C, 57.4; H, 8.6; O, 34].\n\nThe organic layer was diluted with equal amount of dichloromethane (100 ml) and dried over MgSO₄. It was filtered and the solvent removed in vacuo to yield crude product (5.6) (95 g) as a viscous pale yellow liquid. A small amount of (5.6) (250 mg) was purified by column chromatography R_f 0.3 (petroleum ether (40-60°C)/ethyl acetate, 8:2) to yield purified (5.6) (190 mg, 0.157 mmol, 64%) as a viscous liquid. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3354 (O-H), 2924, 2854 (C-H) 1708 (C=O) 1175 (C-O); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 4.86-4.80 \\) (2H, m, HCOC=O), 3.61-3.56 (2H, m, HCO) 3.44-3.39 (2H, m, HCO), 2.33 (6H, t, \\( J= 7.5 \\text{ Hz}, \\ O=C\\text{CH}_2\\text{CH}_2\\)), 1.70-1.55 (6H, m, O=CCH₂CH₂CH₂), 1.51-1.21 (72H, m, CH₂CH₂CH₂), 0.9 (9H, t, \\( J= 7.5 \\text{ Hz}, \\ CH_2CH_3 \\)) \\( ^{13} \\text{C NMR} \\) (100 MHz, CDCl₃): \\( \\delta_C = 179.7 \\) (C=O), 77.4, 77.6, 72.7 (C-O), 34.0 (O=CCH₂), 29.2 (O=CCH₂CH₂CH₂), 33.0, 29.2, 29.0, 22.6 (CH₂CH₂CH₂), 15.0 (CH₂CH₃); \\( m/z \\) (ES⁺) [M+Na⁺] Required 935.7527, Found 935.7522.\n\n6.4.4 Saponification of estolides (5.6)\n\n2.5 g (2.06 mmol) of (5.6) was dissolved in 20 ml tetrahydrofuran in a 100 ml round bottom flask equipped with a magnetic stirrer. Then 1.3 g (32.5 mmol) of sodium hydroxide was dissolved in 20 ml deionised water and this sodium hydroxide solution was added to the round bottom flask. The mixture was heated to 80 °C for 12 hour under reflux, which was then acidify to pH=1 with 2 M HCl. The reaction mixture was poured into a separating funnel and the aqueous layer was separated from the organic layer. The aqueous layer was extracted with CHCl₃ (100 ml) and the CHCl₃ was combined with the organic layer, which was dried over MgSO₄. The organic layer was filtered and the solvent removed *in vacuo* to yield crude product (2.05 g). A small amount of crude product (250 mg) was purified by column chromatography (petroleum ether (40-60°C)/ethyl acetate, 7:3) to yield purified (5.11) (182 mg, 0.576 mmol, 57%) as a white solid. R_f 0.3 (petroleum ether (40-60°C)/ethyl acetate, 7:3); ν_max/cm⁻¹ 3292 (O-H) 2915, 2847 (C-H) 1716 (C=O) 1467 (CH₂) 1076 (C-O) 719(CH₂) ¹H NMR (400 MHz, DMSO-d₆): δ_H = 12.0 (1H, s, COOH), 3.24-3.18 (2H, m, HCOH), 2.2 (2H, t, J= 7.5 Hz, O=CCH₂), 1.65-1.55 (2H, m, HOOCCH₂CH₂), 1.50-1.35 (2H, m, HOCHCH₂), 1.35-1.20 (20H, m, CH₂CH₂CH₂), 0.85 (3H, t, J= 7.5 Hz, CH₂CH₃) ¹³C NMR (100 MHz DMSO-d₆): δ_C = 174.5 (C=O), 73.1 (C-OH), 33.6 (O=CCH₂), 31.3 (HOCHCH₂), 24.3 (O=CCH₂CH₂CH₂), 29.1, 28.0, 22.6 (CH₂CH₂CH₂), *m/z* (ES⁺), [M+Na⁺] Required 339.2511, Found 339.2506; melting point = 95 - 96 °C (literature¹¹⁴: 94 °C) [Found: C, 68.3; H, 11.5; C₁₈H₃₆O₄ Required C, 68.3; H, 11.5; O, 20.2].\n\n6.4.5 Reduction of estolides (5.6)\n\n2.5g (2.06 mmol) of (5.6) was dissolved in 25 ml dry tetrahydrofuran in a 100 ml round bottom flask equipped with a magnetic stirrer under nitrogen gas atmosphere. The reactant was cooled to 0 °C with an ice bath. Then, 40 ml of LiAlH₄ (1M, 40 mmol) was slowly added to the reactant while the reactant was being stirred. After the addition has finished, the reaction temperature was raised to room temperature and held for 24 hours. After 24 hours, the excess LiAlH₄ was decomposed with deionised water and 20 ml of H₂SO₄ (10% concentration) was added to reactant mixture. The reaction mixture was poured into separating funnel and the aqueous layer was separated from the organic layer. The aqueous layer was extracted with CHCl₃ (2 x 100 ml) and the CHCl₃ was combined with the organic layer, which was dried over MgSO₄. The organic layer was filtered and the solvent removed *in vacuo* to yield crude product (1.63 g). A small amount of crude product (250 mg) was purified by column chromatography (petroleum ether (40-60°C)/ethyl acetate, 8:2) to yield purified (5.12) (175 mg, 0.58 mmol, 46%) as a white solid. R_f 0.3 (petroleum ether (40-60°C)/ethyl acetate, 8:2); ν_max/cm⁻¹ 3340 (O-H) 2915, 2847 (C-H) 1463 (CH₂) 1057(C-O) 723 (CH₂); ¹H NMR (400 MHz, CDCl₃): δ_H = 3.60 (2H, t, J= 6.6 Hz, HCOH), 3.43-3.38 (2H, m, HCOH), 1.64-1.51 (2H, m, HOCH₂), 1.50-1.42 (2H, m, HOCH₂) 1.40-1.20 (22H, m, CH₂CH₂CH₂), 0.87 (3H, t, J= 7.5 Hz, CH₂CH₃) ¹³C NMR (100 MHz CDCl₃): δ_C = 72.7, 62.4 (C-OH), 33.0 (HOCHCH₂), 29.2 (O=CCH₂CH₂CH₂), 29.0, 28.7, 25.1, 22.6 (CH₂CH₂CH₂), 15.0 (CH₂CH₃); m/z (ES⁺),[M+Na⁺] Required 325.2713, Found 325.2714; melting point = 70 - 82 °C (literature¹¹⁵: 82 °C) [Found: C, 71.3; H, 12.4; C₁₈H₃₆O₄ requires C, 71.5; H, 12.7; O, 15.9].\n\n6.4.6 Synthesis of 9,10-dihydroxystearic acid (5.11) from oleic acid\n\nOleic acid (5.5) (250 g, 708 mmol), H$_2$O$_2$ (10 g, 88 mmol), H$_2$SO$_4$ (0.6 g, 6 mmol) and HCOOH (41.4 g, 900 mmol) were weighed into a 3-neck round bottom flask. The mixture was stirred without heating as this is an exothermic reaction and when the temperature of the mixture reaches 40 °C, another portion of H$_2$O$_2$ (80 g, 706 mmol) was added drop-wise to the mixture while maintaining the reaction temperature at 60 °C. Once the addition of H$_2$O$_2$ was completed, the reaction temperature was raised and maintained at 90 °C for 24 hour. Then, the reaction mixture was poured into separating funnel and the organic layer was separated from the aqueous layer. Then 150 ml of NaOH solution (50% concentration) was added to the organic layer and the mixture was heated to 100 °C under reflux for 8 hour. Then the mixture was acidify to pH=1 with 2 M HCl and poured into separating funnel, where the organic layer was separated from the aqueous layer. The organic layer was dissolved in hot n-hexane at 60 °C and was left to recrystalize overnight. The white precipitate was filtered and washed with n-hexane to yield about 140 g of (5.11) (440 mmol, 62% yield).\n\n6.4.7 Synthesis of diacetate estolides (5.17)\n\nThe compound (5.11) (31.6 g, 100 mmol), acetic anhydride (31 g, 304 mmol) and H$_3$PO$_4$ (1 g, 10 mmol) were weighed into a round bottom flask and was heated to 100 °C for 6 hour. Then, the mixture was poured into separating funnel and 100 ml of CHCl$_3$ was added to the mixture. The organic layer was separated from the aqueous layer and the aqueous layer was again extracted with 100 ml of CHCl$_3$. The organic layer was combined, dried over MgSO$_4$ and was filtered. The solvent was removed *in vacuo* to yield (5.17) (26.7 g, 360 mmol, 36% yield). $\\nu_{\\text{max}}/\\text{cm}^{-1}$ 2925, 2855 (C-H)\n\n1737, 1710 (C=O) 1465 (CH$_2$) 1371 (O=CCH$_3$) 1225 (C-O-C) 1022 (C-O) $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H = 5.03-4.96$ (4H, m, HCOC=O), 2.43 (2H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 2.33 (2H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 2.06 (9H, s, O=CCH$_3$), 1.69-1.57 (4H, m, O=CCH$_2$CH$_2$CH$_2$), 1.56-1.47 (8H, m, OCHCH$_2$), 1.38-1.18 (40H, m, CH$_2$CH$_2$), 0.87 (6H, t, $J= 6.8$ Hz, CH$_2$CH$_3$); $^{13}$C NMR (100 MHz CDCl$_3$): $\\delta_C = 179.3$, 173.3, 170.6 (C=O) 73.2, 72.9 (C-O), 35.1, 34.2 (O=CCH$_2$), 29.1 (CH$_2$CHO), 24.1 (O=CCH$_2$CH$_2$CH$_2$), 22.6 (O=CCH$_3$), 28.6, 24.1, 22.6, 20.6 (CH$_2$CH$_2$CH$_2$), 14.1 (CH$_2$CH$_3$); $m/z$ (ES$^+$),[M+Na$^+$] Required 763.5336, Found 763.5333.\n\n6.4.8 Synthesis of 9,10-dimethoxy methyl stearate (5.18)\n\nPotassium hydroxide (KOH) (20 g, 357 mmol) was grounded to powder and was charged into a round bottom flask. Then, 9,10-dihydroxy methyl stearate (5.9) (30 g, 91 mmol) and anhydrous tetrahydrofuran (50 ml) were added to this mixture with stirring and the temperature was maintained at 40 °C for another an hour. Thereafter, methyl iodide (50 g, 350 mmol) was added drop-wise to the mixture and the reaction temperature was maintained at 40 °C for 24 hour. Then, the mixture was poured into separating funnel. 200 ml of NaCl solution and 300 ml of CHCl$_3$ was added to the mixture. The organic layer was separated from the aqueous layer and the aqueous layer was again extracted with 300 ml of CHCl$_3$. The organic layer was combined, dried over MgSO$_4$ and was filtered. The solvent was removed in vacuo to yield (5.18) as a pale yellow oil (16.3 g, 45.5 mmol, 50% yield). $\\nu_{\\text{max}}$/cm$^{-1}$ 2922, 2853 (C-H) 1741 (C=O) 1455 (CH$_2$) 1094 (C-O) 722 (CH$_2$); $^1$H NMR (400 MHz, CDCl$_3$): $\\delta_H =$ 3.63 (3H, s, HCO), 3.40 (6H, s, HCO), 3.30-3.20 (2H, m, HCO) 2.30 (2H, t, $J= 7.5$ Hz, O=CCH$_2$CH$_2$), 1.60-1.50 (2H, m, O=CCH$_2$CH$_2$CH$_2$), 1.50-1.40 (4H, m, MeOCCH$_2$), 1.35-1.25 (22H, m, CH$_2$CH$_2$CH$_2$), 0.88 (3H, t, $J= 7.5$ Hz, CH$_2$CH$_3$); $^{13}$C\n\nNMR (100 MHz CDCl₃): \\( \\delta_C = 174.1 \\) (C=O), 81.9 (HC-OMe), 57.1 (OCH₃), 49.5 (O=CCH₃), 39.1 (O=CCH₂), 30.3 (CH₂CHO), 27.1 (O=CCH₂CH₂CH₂), 26.6, 23.7 (CH₂CH₂CH₂), 14.5 (CH₃CH₃); \\( m/z \\) (ES⁺), [M+Na⁺] Required 381.2981, Found 381.2975.\n\n### 6.4.9 General procedure for oxidative cleavage of fatty acid derivatives\n\n#### 126.96.36.199 Oxidative cleavage of epoxidized methyl oleate (5.16) as an example\n\nEpoxidised methyl oleate (5.16) (50 g, 160 mmol), Na₂WO₄ (1.25 g, 3.79 mmol), Aliquat 336 (1.7 g, 3.85 mmol) and H₂O₂ (30% w/v) (100 g, 880 mmol) were weighed into a round bottom flask and the reaction mixture was stirred and heated to 100 °C for 24 hour. After 24 hour, 100 ml deionised water and 4 g H₃PO₄ were added to the reaction mixture. The reaction mixture was stirred and heated at 100 °C for another 24 hour. The reaction mixture was poured into separating funnel after 24 hour of reaction and 100 ml of NaCl solution was added to the separating funnel, then the mixture was left overnight for any azelaic acid to precipitate from the aqueous layer. The precipitated azelaic acid (5.14) in the aqueous layer was filtered and washed with deionised water, then dried overnight in oven. The weight of (5.14) collected is 0.92 g (4.9 mmol, 3% yield).\n\n#### 188.8.131.52 Oxidative cleavage of 9,10-dihydroxystearic acid (5.11)\n\nThe experiment was conducted according to the procedure described in 184.108.40.206. The compound (5.11) (12 g, 38 mmol), Na₂WO₄ (0.22 g, 0.68 mmol), Aliquat 336 (0.3 g, 0.68 mmol) and H₂O₂ (30% w/v) (19.3 g, 170 mmol). The weight of azelaic acid (5.14) collected is 70 mg (0.37 mmol, 0.98% yield).\n\n220.127.116.11 Oxidative cleavage of diacetate estolides (5.17)\n\nThe experiment was conducted according to the procedure described in 18.104.22.168. The compound (5.17) (25 g, 33.7 mmol), Na₂WO₄ (0.41 g, 1.24 mmol), Aliquat 336 (0.55 g, 1.24 mmol), H₂O₂ (30% w/v) (35.5 g, 313 mmol). No precipitation was observed in the aqueous layer and the major compounds in the crude organic layer were identified as (5.11) and (5.17).\n\n22.214.171.124 Oxidative cleavage of 9,10-dimethoxy methyl oleate (5.18)\n\nThe experiment was conducted according to the procedure described in 126.96.36.199. The compound (5.18) (20 g, 55.9 mmol), Na₂WO₄ (0.4 g, 1.2 mmol), Aliquat 336 (0.53 g, 1.2 mmol), H₂O₂ (30% w/v) (32 g, 282 mmol). No precipitation was observed in the aqueous layer and the major compound in the crude organic layer was identified as (5.18).\n\n6.4.10 Oligomerization of oleic acid without catalyst\n\nOleic acid (5.5) (50 g, 177 mmol) and hydrogen peroxide (30% w/w, 100 g, 890 mmol) were weighed into a round bottom flask. The mixture was stirred and heated at 80 °C for 3 days. The mixture was poured into a separating funnel and CHCl₃ (50 ml) was added to it. The organic layer was separated from the aqueous layer. The organic layer was dried over anhydrous MgSO₄ and CHCl₃ was removed *in vacuo* to yield a colorless liquid (5.6) (50 g) \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3467 (OH) 2923, 2854 (C-H) 1708 (C=O) 1174 (C-O) 723 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 4.87-4.80 \\) (2H, m, HCOC=O), 3.63-3.55 (2H, m, HCO) 3.45-3.38 (2H, m, HCO), 2.32 (6H, t, \\( J=7.1 \\) Hz, O=CCH₂CH₂), 1.68-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.54-1.20 (72H, m,\n\nCH₂CH₂CH₂), 0.88 (12H, t, $J=6.0$ Hz, CH₂CH₃), $^{13}$C NMR (100 MHz CDCl₃): $\\delta_C =$ 179.2, 173.9 (C=O), 76.1 (HCOC=O), 74.4, 72.4 (HC-O), 33.9 (O=CCH₂), 24.4 (O=CCH₂CH₂CH₂), 31.3, 29.5, 24.6, 22.8 (CH₂CH₂CH₂), 13.8 (CH₂CH₃); $m/z$ (ES⁺) [M+Na⁺] (n=3) Required 935.7527, Found 935.7519\n\n6.4.11 General procedure for oligomerization of plant oil with succinic acid\n\n188.8.131.52 Oligomerization of soybean oil (5.24) with succinic acid as an example\n\nSoybean oil (5.24) (5 g, 5.3 mmol), succinic acid (2.5 g, 21 mmol) and hydrogen peroxide (30% w/w, 30 g, 0.26 mol) were weighed into a round bottom flask. The mixture was stirred and heated at 80 °C for 7 days. The mixture was poured into a separating funnel and CHCl₃ (50 ml) was added to it. The organic layer was separated from the aqueous layer. The organic layer was dried over anhydrous MgSO₄ and CHCl₃ was removed in vacuo to yield a yellowish liquid (5.25) (6.5 g).\n\n$v_{\\text{max}}/\\text{cm}^{-1}$ 3446 (OH) 2923, 2856 (C-H) 1736 (C=O) 1163 (C-O) 754 (CH₂); $^1$H NMR (400 MHz, CDCl₃): $\\delta_H = 5.30-5.22$ (1H, m, CHO), 4.31 (2H, dd, $J=11.9$ Hz, 4.5 Hz, CH₂O), 4.15 (2H, dd, $J=11.9$ Hz, 5.9 Hz, CH₂O), 3.85-3.37 (4H, m, HCO), 2.63 (2H, t, $J=7.4$ Hz O=CCH₂CH₂), 2.33 (6H, t, $J=7.5$ Hz O=CCH₂CH₂), 1.66-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.52-1.20 (48H, m, CH₂CH₂), 0.89 (9H, t, $J=7.5$Hz, CH₂CH₃). $^{13}$C NMR (100 MHz CDCl₃): $\\delta_C =$ 177.9, 175.7, 173.2, 172.8 (C=O) 78.7, 76.9, 74.3, 72.3 (HC-O), 68.8 (HC-O), 62.1, 61.7 (H₂C-O), 33.7, 28.3 (O=CCH₂), 24.4 (O=CCH₂CH₂CH₂), 29.4, 22.5 (CH₂CH₂CH₂), 13.7 (CH₂CH₃)\n\n184.108.40.206 Oligomerization of rapeseed oil (5.23) with succinic acid\n\nThe experiment was conducted according to the procedure described in 220.127.116.11.\n\nRapeseed oil (5.23) (5 g, 5.3 mmol), succinic acid (2.7 g, 23 mmol) and hydrogen peroxide (30% w/w, 26 g, 0.23 mol), yellowish liquid (6.9 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3450 (OH) 2924, 2854 (C-H) 1710 (C=O) 1164 (C-O) 755 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.30-5.22 \\) (1H, m, CHO), 5.12-5.04 (1H, m, CHO), 4.90-4.78 (1H, m, CHO), 4.29 (2H, dd, \\( J = 11.8 \\) Hz, 4.5 Hz, CH₂O), 4.15 (2H, dd, \\( J = 11.7 \\) Hz, 5.8 Hz, CH₂O), 3.80-3.30 (4H, m, HCO), 2.66 (2H, t, \\( J = 7.5 \\) Hz O=CCH₂CH₂), 2.33 (6H, t, \\( J = 7.0 \\) Hz O=CCH₂CH₂), 1.70-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.54-1.20 (54H, m, CH₂CH₂), 0.88 (9H, t, \\( J = 6.8 \\) Hz, CH₂CH₃); \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 178.6, 176.3, 173.3, 172.1 \\) (C=O) 77.0, 74.4, 72.5 (HC-O), 68.8 (HC-O), 62.1, 61.9 (H₂C-O), 33.9, 28.6 (O=CCH₂), 24.6 (O=CCH₂CH₂CH₂), 29.5, 25.1, 22.7 (CH₂CH₂CH₂), 13.9 (CH₂CH₃)\n\n18.104.22.168 Oligomerization of palm oil (5.22) with succinic acid\n\nThe experiment was conducted according to the procedure described in 22.214.171.124.\n\nPalm oil (5.22) (5 g, 5.6 mmol), succinic acid (1.39 g, 11.7 mmol) and hydrogen peroxide (30% w/w, 13.4 g, 0.118 mol), a yellowish liquid (4.5 g); \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3451 (OH) 2925, 2856 (C-H) 1725 (C=O) 1125 (C-O) 744 (CH₂); \\( ^1\\text{H NMR} \\) (400 MHz, CDCl₃): \\( \\delta_H = 5.29-5.22 \\) (1H, m, CHO), 4.92-4.78 (2H, m, CHO), 4.30 (2H, dd, \\( J = 11.8 \\) Hz, 4.6 Hz, CH₂O), 4.13 (2H, dd, \\( J = 11.9 \\) Hz, 5.8 Hz, CH₂O), 3.78-3.30 (4H, m, HCO), 2.63 (2H, t, \\( J = 7.5 \\) Hz O=CCH₂CH₂), 2.29 (6H, t, \\( J = 7.5 \\) Hz O=CCH₂CH₂), 1.68-1.56 (6H, m, O=CCH₂CH₂CH₂), 1.54-1.20 (64H, m, CH₂CH₂), 0.87 (9H, t, \\( J = 7.5 \\) Hz, CH₂CH₃). \\( ^{13}\\text{C NMR} \\) (100 MHz CDCl₃): \\( \\delta_C = 176.9, 173.6, 172.6 \\) (C=O) 78.2,\n\n126.96.36.199 Oligomerization of cocoa butter (5.21) with succinic acid\n\nThe experiment was conducted according to the procedure described in 188.8.131.52. Cocoa butter (5.21) (5 g, 5.8 mmol), succinic acid (5.21) (0.70 g, 5.8 mmol) and hydrogen peroxide (30% w/w, 6.6 g, 58 mmol), a yellowish liquid (4.7 g) which was characterized by $^1$H NMR to be epoxidized cocoa butter.\n\n6.4.12 Oligomerization of soybean oil (5.24) with adipic acid\n\nThe experiment was conducted according to the procedure described in 184.108.40.206. Soybean oil (5.24) (5 g, 5.3 mmol), adipic acid (4 g, 28 mmol) and hydrogen peroxide (30% w/w, 32 g, 0.28 mol), a yellowish liquid (4.8 g) which was characterized by $^1$H NMR to be epoxidized soybean oil.\n\n6.4.13 General procedure for oligomerization of plant oil with phthalic anhydride\n\n220.127.116.11 Oligomerization of soybean oil (5.24) with phthalic anhydride as an example\n\nSoybean oil (5.24) (5 g, 5.3 mmol), phthalic anhydride (4 g, 28 mmol) and hydrogen peroxide (30% w/w, 15 g, 0.138 mol) were weighed into a round bottom flask. The mixture was stirred and heated at 80 °C for 1 day. The mixture was poured into a separating funnel and CHCl$_3$ (50 ml) was added to it. The organic layer was separated from the aqueous layer. The organic layer was dried over anhydrous MgSO$_4$ and CHCl$_3$ was removed *in vacuo* to yield a yellowish liquid (5.29) (6.5 g).\n\n\\( \\nu_{\\text{max}}/\\text{cm}^{-1} 3449 \\) (OH) 2924, 2854 (C-H) 1720 (C=O) 1599 (Ar-CH) 1069 (C-O) 743 (CH\\(_2\\)); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl\\(_3\\)): \\( \\delta_H = 7.90-7.60 \\) (2H, m, Ar-H) 7.60-7.45 (2H, m, Ar-H), 5.32-5.22 (1H, m, CHO), 5.19-5.06 (1H, m, CHO) 4.29 (2H, dd, \\( J = 11.9 \\) Hz, 4.5 Hz, CH\\(_2\\)O), 4.15 (2H, dd, \\( J = 11.9 \\) Hz, 5.9 Hz, CH\\(_2\\)O), 3.90-3.35 (4H, m, HCO), 2.31 (6H, t, \\( J = 7.5 \\) Hz O=CCH\\(_2\\)CH\\(_2\\)), 1.72-1.56 (6H, m, O=CCH\\(_2\\)CH\\(_2\\)CH\\(_2\\)), 1.54-1.17 (48H, m, CH\\(_2\\)CH\\(_2\\)), 0.87 (9H, t, \\( J = 6.9 \\) Hz, CH\\(_2\\)CH\\(_3\\)). \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl\\(_3\\)): \\( \\delta_C = 178.3, 173.3, 172.9 \\) (C=O) 131.2, 129.2 (Ar-C) 83.1, 78.5, 74.4, 72.8 (HC-O), 68.7 (HC-O), 62.2, 61.9 (H\\(_2\\)C-O), 33.8 (O=CCH\\(_2\\)), 24.5 (O=CCH\\(_2\\)CH\\(_2\\)CH\\(_2\\)), 29.5, 22.7 (CH\\(_2\\)CH\\(_2\\)CH\\(_2\\)), 13.8 (CH\\(_2\\)CH\\(_3\\))\n\n### 18.104.22.168 Oligomerization of palm oil (5.22) with phthalic anhydride\n\nThe experiment was conducted according to the procedure described in 22.214.171.124. Palm oil (5.22) (5 g, 5.6 mmol), phthalic anhydride (1.72 g, 21 mmol), hydrogen peroxide (30% w/w, 6.6 g, 58 mmol), a yellowish liquid (5.30) (6.7 g). \\( \\nu_{\\text{max}}/\\text{cm}^{-1} 3441 \\) (OH) 2922, 2853 (C-H) 1738 (C=O) 1601 (Ar-CH) 1070 (C-O) 755 (CH\\(_2\\)); \\( ^1 \\text{H NMR} \\) (400 MHz, CDCl\\(_3\\)): \\( \\delta_H = 7.85-7.67 \\) (2H, m, Ar-H) 7.58-7.47 (2H, m, Ar-H), 5.32-5.24 (1H, m, CHO), 5.17-5.04 (1H, m, CHO) 4.31 (2H, dd, \\( J = 11.9 \\) Hz, 4.6 Hz, CH\\(_2\\)O), 4.15 (2H, dd, \\( J = 11.9 \\) Hz, 6.0 Hz, CH\\(_2\\)O), 3.80-3.37 (4H, m, HCO), 2.31 (6H, t, \\( J = 7.3 \\) Hz O=CCH\\(_2\\)CH\\(_2\\)), 1.80-1.56 (6H, m, O=CCH\\(_2\\)CH\\(_2\\)CH\\(_2\\)), 1.54-1.15 (64H, m, CH\\(_2\\)CH\\(_2\\)), 0.88 (9H, t, \\( J = 6.4 \\) Hz, CH\\(_2\\)CH\\(_3\\)). \\( ^{13} \\text{C NMR} \\) (100 MHz CDCl\\(_3\\)): \\( \\delta_C = 177.9, 173.7, 172.7, 170.3 \\) (C=O) 131.1, 129.1 (Ar-C) 78.4, 74.3, 72.5 (HC-O), 68.7 (HC-O), 62.0, 61.7 (H\\(_2\\)C-O), 33.7 (O=CCH\\(_2\\)), 24.5 (O=CCH\\(_2\\)CH\\(_2\\)CH\\(_2\\)), 29.4, 22.6 (CH\\(_2\\)CH\\(_2\\)CH\\(_2\\)), 13.8 (CH\\(_2\\)CH\\(_3\\))\n\n6.4.14 Polyurethane synthesized from estolides (5.6)\n\nEstolides (5.6) (10 g, hydroxyl value = 230 mg KOH/g sample) was weighed into a round bottom flask and chloroform (50 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. Then, 4,4'-methylene diphenyl diisocyanate (MDI) (7.7 g) was added to the dissolved polyol. The NCO/OH ratio index was 1.02. The reaction mixture was heated to 60 °C under reflux condition for 24 hours. After 24 hours, some of the chloroform was removed by using a rotary evaporator and then polyurethane product was poured into a pre-heated mold at 60 °C. The polyurethane (5.31) was cured at 60 °C for 24 hours in an oven. \\( \\nu_{\\text{max}}/\\text{cm}^{-1} \\) 3337 (O=CNH) 2924, 2854 (C-H) 1727 (C=O) 1597 (aromatic =CH) 1095 (C-O) 721 (CH₂)\n\n6.4.15 Polyurethane synthesized from oligomerized soybean oil with succinic acid (5.25)\n\nPolyol (5.25) (10 g, hydroxyl value = 144 mg KOH/g sample) was weighed into a round bottom flask and chloroform (50 ml) was added to dissolve it. The round bottom flask was purged with dry nitrogen gas to remove any moisture from the system. 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The club was launched two years ago, attracting 800,000 members which immediately caused a drop in pricing of club CDs as a direct result of the newly created competitive arena.\n\n\"The only conclusion one can make on Warner's renegeing on its initial agreement to supply BMG with product is that it wants to have exclusive control over the flow of music to record club members in Canada,\" stated George McMillan, president and CEO of BMG Direct Ltd. \"Warner's behaviour is harmful to over 2 million Canadian record club members. They are being treated like second class citizens by being denied the benefits of competition enjoyed by US consumers.\"\n\nFor its part, Warner Music claims that the remedy being sought by the Bureau will lead to automatic compulsory licensing, something which would violate intellectual property rights of the artists and cripple their economic well-being.\n\nBut McMillan is accusing the label of employing \"scare tactics\" and of creating a \"smokescreen to hide the real issue.\"\n\n\"Bertelsmann is a leader in the music industry and would not, out of concern for its artists, support compulsory licensing for music or any other intellectual property.\"\n\nHMV’s Superstore to fete Yo-Yo Ma’s Bach series\n\nInternationally-acclaimed cellist Yo-Yo Ma has brought the Suites for Cello Solo by J.S. Bach into prominence in a film series titled Inspired by Bach. The series pairs Ma with six artists, each of whom has chosen one of the Bach Suites to explore in collaboration with Ma; choreographer Mark Morris, filmmakers Atom Egoyan and Francois Girard, ice dancers Torvill & Dean, garden designer Julie Moir Messervy and Kabuki actor Tamasaburo Bando.\n\nMa will be on hand for an exclusive performance and meet and greet at HMV’s Toronto Superstore (333 Yonge Street) on Oct. 24 from 12:30 to 2 pm to celebrate the release of the films’ soundtrack, an all-new recording of the Suites by Ma.\n\nMa’s first recording of the Bach Cello Suites, released on Sony Classical, won a 1984 Grammy Award. His interest in exploring the Suites again, in this unique manner, came after he took part in a 1991 symposium on Bach scholar Albert Schweitzer. He was apparently so fascinated by Schweitzer’s description of Bach’s music as “painterly” and “pictorial”, that he began planning his Inspired by Bach project. The series of six short films that came out of this vision will be aired over six weeks on TVO, with the first film’s premiere scheduled for Sunday, Oct. 26.\n\nTower in-store for Jethro Tull’s Toronto date\n\nFrom Noon until 1 pm on Oct. 20, Ian Anderson, Martin Barre and Andrew Giddings of Jethro Tull will be on hand at Tower Records in downtown Toronto.\n\nThe trio will perform three acoustic songs on the main floor, followed by a question and answer session open to the public and media. Vince Parr, Director of Marketing for Tower Records, is requesting that those wishing to take part should fax their questions to the marketing department, at 416-593-7995, ten of which will be chosen for the floor. After the Q&A session, the trio will sign autographs.\n\nThe Tower in-store is part of Jethro Tull’s 1997 North American Tour, promoting the EMI release of the Special 25th Anniversary Thick As A Brick. The band appears in concert at Massey Hall that same evening.\n\nCash injection extends life of Quality Dino\n\nLouis Kircos, CEO of Quality Dino Entertainment, has announced that the company will receive an additional $10 million in cash from its existing investors to provide for the same conversion terms as the new investment. The company is currently developing a new line of products including performing Chris Sheppard's Destination Dancefloor, and the 9th volume of the successful Don Cherry's Rock'Em Sock'Em hockey action figures.\n\nWALT SAYS . . . !\n\nAttitudes are changing!!! It's taken a long time, but there appears to be a whole new respect for country music from the multi-nationals in particular, and with some retailers. And you can see why. Gold and multi-platinum certifications for country albums have been on the increase, ever since Garth Brooks and Shania Twain led the way. Every multi-national, without exception, have a full roster of country acts. Attitudes have been difficult to change however. It's one thing to have a large country roster, but if there's resistance down the line at the label, the country act isn't going anywhere, and there's been a lot of proof of this over the past dozen months. Competition in country is keener than ever. No sooner does a pretty face hit #1 and another one is bidding for that slot. Now, if we can only convince retailers to boot out some of the pop and rock crap and front-rack country, we'd see a major chain in customer buying habits. I wonder if anyone at retail ever monitors how many calls they get for country records? (EC: Are you kidding???)\n\nThere's more to Q than Stern!!! They say \"as the morning goes, so goes the rest of the day,\" which is the case most of the time. When you have a shock-jock like Howard Stern opening the day, how do you program the rest of the day? Very carefully, I would imagine. So, it's been very interesting listening to what Pat Cardinal is doing with Q107. There's that feel of the old rock powerhouse, but with a difference. Cardinal is layering his music with a bit of his own shock and he's building a very entertaining format. It will be interesting to see just how the rest of the day is going. (EC: It's that western influence!!!)\n\nRewriting history!!! There are too many books coming out on the early evolution of Cancon that rewrite the facts and unfortunately there are many who will read this stuff and believe that it really happened. The truth is that many of the writers weren't there physically or mentally. The research is done by interviewing artists who they revere and believe anything they're told. The great book on early Cancon hasn't been written and it won't be by any of the current sycophants and free-loaders. Our doors are closed to researchers. We send them to the Toronto Music Library whose mandate is to use the public purse to store this Canadiana (EC: That's another story!!!) I've been writing the history of the industry for 33 1/3 years. This is Volume 66 Number 7, for those who are keeping track. Someday I'll condense it all into a book. (EC: Meanwhile, we'll have to live with the trash from L.L., M.M., R.F. and that ilk!!!)\n\nNow that's an awards show!! We predicted that the MuchMusic Video Awards would be a big ratings winner. But can you believe more than three million Canadian viewers? This is almost triple last year's audience and the highest rating ever for the show. And the demographics were between 12 and 34, pretty key when it comes to consumer buying, and you have to admit that some record sales must have been realized. That Denise Donlon sure knows how to get to the heart of the matter. (EC: Other awards shows producers should take Denise to lunch!!!)\n\nThe cart or the horse??? There's a radio station out west that's letting their attitude hang out for everyone to interpret, and not very positively from the people who have called me. The station will no longer break new songs or artists. These artists and/or songs \"must become chart items before consideration is given.\" Now, tell me, how do the artists and/or records become chart items if radio doesn't break them? (EC: Another reason for the CRTC to begin monitoring!!!)\n\nPeople are asking!!! Without looking, how many sprockets are there in the hole of a CD? (EC: Is there a hole???) At what speed does a CD revolve? At what speed did the old 78s revolve? Is the mouse looking for a hole to be more whole? If he got trapped into a bad company would that be a mousetrap? What record company doesn't have corporate citizenship in its bottom line? What ever happened to \"payola\"? (EC: He means how its done now as opposed to back then!!!) Why was there such a lack of press coverage of the CCMA Awards and why are photogs complaining? (EC: Who was to blame???)\n\nCelebrity roll call!!! With the new awakening at the Toronto Star, expect to see more photos of film celebrities in those colour spreads rumoured to be coming. Watch the Toronto Sun accelerate their celebrity coverage. The sports fans apparently love it and the entertainment advertisers are getting real excited. Watch the Globe and Mail to hire a photographer. Rumour has it they're looking for a younger readership.(EC: Photos in the dailies??? You must be dreaming . . . and IN COLOUR???)\n\nA cliff hanger!!! The Warner Warriors are the proud holders of the RPM Cup, beating out the Warner Wackers. The Warriors looked like they would take it in a two-game sweep, but the Wackers staged a pretty dramatic comeback, thanks to John Robbie's three run, two-out homer. Universal Music won the CRIA Trophy, sweeping PolyGram. It's Universal's first trophy win. (EC: Until next year!!!)\n\nEd Preston, then president of RCA Records Canada, and the recently deceased John Denver and his 1974 gold award for his Greatest Hits album. CHUM's J. Robert Wood was instrumental in taping a special on Denver which remains a classic. (photo by John Rowlands)\n\nCMAW'09\n\n| TW | LW | WO | TRACKS & WHERE TO FIND THEM |\n|----|----|----|-----------------------------|\n| 1 | 1 | 11 | FLY Sugar Ray - Floored Universal (promo CD) - P |\n| 2 | 3 | 5 | ANYBODY SEEN MY BABY? The Reflex Stunes - Bridges To Babylon Virgin 44712 (promo CD)-F |\n| 3 | 2 | 17 | BUILDING A MYSTERY Sarah McLachlan - Surfacing Nettwerk 39709 (promo CD)-F |\n| 4 | 5 | 7 | FOOLISH GAMES Jewel - Pieces Of You Warner Bros. 3301-F |\n| 5 | 10 | 6 | THE SOUND OF Jack Johnson - Happy? A&M 5207892 (promo CD) - Q |\n| 6 | 27 | 6 | PUSH Matchbox 20 - Yourself Or Someone Like You Lava/Atlantic (comp 97315 vol. 315) |\n| 7 | 7 | 4 | I DON'T WANT TO WAIT Paul Cole - I Don't Want Warner Bros. (promo CD) - P |\n| 8 | 4 | 7 | INVISIBLE MAN The Dap-Kings Columbia 530 796 (comp 61)-D |\n| 9 | 15 | 5 | ON MY OWN Peach Unison - Audiobeach Warner Bros. 33039 (promo CD)-H |\n| 10 | 9 | 24 | IF YOU COULD ONLY SEE Toric - The Lemon Parade Polydor 31543 1042-D |\n| 11 | 21 | 3 | SHOW ME LOVE The Black Keys - Rockin' In The Arista (promo CD) - N |\n| 12 | 35 | 2 | TUBTHUMPING The Prodigy - Tubthumping Universal 53099-J |\n| 13 | 18 | 11 | WALKIN' ON THE SUN Smokie Moon - Tush Yu Man Mercury 50101 (promo CD) - J |\n| 14 | 25 | 5 | 4 SEASONS OF LONELINESS Boyz II Men - Evolution Motown (promo CD) - Q |\n| 15 | 13 | 15 | I BECOME 1 Simple Plan - Simple Plan Virgin 42174-F |\n| 16 | 8 | 9 | HONEY Enya - Butterfly Polydor 31543 1042-D |\n| 17 | 24 | 21 | ALL FOR YOU Sister Hazel - Middle Nowhere More Familiar Atlantic 53035-J |\n| 18 | 11 | 12 | IT COULD HAPPEN TO YOU Blue Riders - I'm Here Now EMI (promo CD) - H |\n| 19 | 19 | 3 | SOMETHING ABOUT THE WAY... Elton John - Something About The Way Mercury 314 588 109-Q |\n| 20 | 12 | 25 | SEMI-CCHARMED LIFE The Black Keys - Third Eye Blind Elektra 52012-E |\n| 21 | NEW | 1 | DON'T GO AWAY Oasis - Be Here Now EMI (promo CD) - H |\n| 22 | 22 | 6 | MOST PRECIOUS Blues Traveler - Shining On Warner Bros. 3301-F |\n| 23 | NEW | 1 | HITCHIN' A RIDE Green Day - Nimmo Reprise (comp 335)-P |\n| 24 | 18 | 22 | OUR PLAYIN' GAMES WITH... Matchbox 20 - Playtime: Boys Jive/Zomba 15981-N |\n| 25 | 14 | 7 | TAKES A LITTLE TIME Amy Grant - Behind The Eyes Capitol 3301-F |\n| 26 | 28 | 8 | TRUST ME Amanda Marshall - Amanda Marshall Columbia 530 796 (comp 61)-D |\n| 27 | 27 | 7 | THE IMPRESSION THAT I GET Mighty Mighty Bosstones - Let's Face It Mercury (comp 520) - Q |\n| 28 | 30 | 2 | YOUR BOY You Me At Six - Flaming Pie EMI (comp 161)-F |\n| 29 | 43 | 2 | LEGEND OF A COWGIRL Shania Twain - Come Cloppola Columbia 58851-H |\n| 30 | 32 | 3 | AUTOMATIC FLOWERS Our Lady Peace - Clumsy Columbia 530 796 (comp 61)-H |\n| 31 | 45 | 6 | MY ADDICTION Dylana Manning - Volume 1 EMI 53852 (comp 17) - F |\n| 32 | 20 | 5 | CANDLE IN THE WIND '97 Whitney Houston - The album Rocket (promo CD) - Q |\n| 33 | 47 | 3 | BLAME Colbie Caillat - Disappointed Breakdown Atlantic (promo 395)-P |\n| 34 | 33 | 7 | BARBIE GIRL Aqua - Aquarama Universal (promo CD) - J |\n| 35 | 2 | 3 | THREE MARLENAS The Wallflowers - Bringing Down The Horse Universal (comp 17) - F |\n| 36 | 23 | 12 | EVERYBODY Backstreet Boys - Backstreet's Back Jive/Zomba 41617-N |\n| 37 | 31 | 24 | THE DIFFERENCE The Wallflowers - Bringing Down The Horse Interscope 80059-J |\n| 38 | 60 | 15 | TO THE MOON AND BACK Savage Garden - Savage Garden Columbia 58854 (comp 17) - H |\n| 39 | 71 | 14 | MORE THAN THIS 10,000 Maniacs - Lost Among The Ruins Geffen (comp 17) - F |\n| 40 | 17 | 15 | WHERE'S THE LOVE Hanson - Middle Of Nowhere Music 534615 |\n| 41 | NEW | 1 | DO WHAT I CAN Justin Timberlake - Present Aquarius 6075 (promo CD) - F |\n| 42 | 42 | 4 | PINK Aerosmith - Nine Lives Columbia (promo CD) - H |\n| 43 | 26 | 6 | HOW DO I LIVE LeAnn Rimes - I Can't Fight Up My Life Epic (promo CD) - F |\n| 44 | 44 | 27 | THE FRESHMEN Verve Poe - Villains RCA 688029-N |\n| 45 | 36 | 7 | SHED A LIGHT Nickelback - Kissing Rain RV International 43978 (promo CD) - N |\n| 46 | 81 | 8 | I AM THE MAN Phil Collins - Kings Are The Man Columbia (comp 128) - H |\n| 47 | 28 | 10 | CONGO Genesis - Calling All Stations Atlantic (comp 330) - F |\n| 48 | NEW | 1 | SURROUNDED Chantal Kreviazuk - Under These Rocks And Stones Columbia 87926 (promo CD) - H |\n| 49 | NEW | 1 | TOUCH PEEL STAND Talk Of The Town - Days Of The New Outlook 30004-J |\n| 50 | NEW | 1 | CRIMINAL Fabolous - Tell It Sony 67439-H |\n| 51 | 29 | 9 | TURN MY HEAD Live - Secret Sessions Retrospect 41609 (comp 10) - J |\n| 52 | NEW | 1 | ORDINARY DAY Great Big Sea - Play WEA 50101 (promo CD) - P |\n| 53 | 37 | 19 | WHEN I'M UP (I CAN'T GET DOWN) Great Big Sea - Play Warner 18992 (comp 323) - P |\n| 54 | 53 | 15 | DO YOU KNOW WHAT IT TAKES Razorlight - Run In Here EMI 64985-5 |\n| 55 | 64 | 2 | ALL THAT YOU ARE Echobelly - Crush - The Devil You Know EMI 314 588 109-Q |\n| 56 | 50 | 5 | GOT TIL IT'S GONE James Blunt - Reckless Virgin 44783 (promo CD) - F |\n| 57 | 66 | 4 | IT'S OK, IT'S ALRIGHT Gavin Hoyle - I'm Popular (promo CD) - P |\n| 58 | 55 | 3 | HEAVY Gazelle Twin - Zuchercabaty Mercury (comp 520) - Q |\n| 59 | 72 | 26 | BITCH Miley Cyrus - Blurring The Edges Capitol 31014 (promo CD) - F |\n| 60 | 54 | 16 | THIRD OF JUNE Corey Hart - Corey Hart Columbia 530 796 (comp 61)-H |\n| 61 | 38 | 7 | SILVER SPRINGS Pavement Inc. - The Dance Reprise (comp 311) - F |\n| 62 | 41 | 2 | YOU SHOULD BE HAVING FUN Bon Jovi - Last Call - I'll Tomorrow Columbia (comp 084) - H |\n| 63 | 70 | 6 | DOWNTIME The Generals - Sold For A Smile Virgin 18970 (promo CD) - J |\n| 64 | 48 | 3 | LAST OF THE BIG GAME HUNTERS Bastille Prophets - Last Of The Big Game Hunters Mercury (comp 520) - Q |\n| 65 | 52 | 4 | OPEN UP BABY Big Sugar - Harm-Vision A&M (comp 7) - F |\n| 66 | 63 | 2 | SIDE BLUE 38 Special - Flash Back A&M 39749-D |\n| 67 | 76 | 25 | SUNNY CAME HOME The Beach Boys - Two Small Repairs Columbia 87119 (comp 60) - H |\n| 68 | 46 | 3 | PEARLY WHITE Junoshine - Fuzz Columbia 53096 (promo 084) - H |\n| 69 | 85 | 28 | CLUMSY Our Lady Peace - Clumsy Columbia 80242-H |\n| 70 | 51 | 2 | HAVE YOU SEEN ME LATELY? The Wallflowers - Recovering The Satellites Universal (comp 12) - F |\n| 71 | 58 | 2 | BLUE BOY The Fogerty - Blue Moon Swirls Warner Bros. 54203-P |\n| 72 | 87 | 16 | NUMBER Holly Michael - Stuff Universal 53075 (promo CD) - J |\n| 73 | 75 | 1 | LAZY EYE Goo Goo Dolls - Batman and Robin D.S.T. Warner Bros. 46202-F |\n| 74 | NEW | 1 | STILL WATERS Lee Seals - Still Waters Polydor 3145373022-Q |\n| 75 | 57 | 2 | WHAT I THINK SHE SEES Our Lady Peace - Sweet Sucker's Parade A&M 215407052-Q |\n| 76 | 39 | 8 | MARCHING TO MARS Simple Plan - Marching To Mars Track Factory 53096 |\n| 77 | 73 | 15 | MEN IN BLACK THEME Will Smith - Men In Black D.S.T. Columbia 681119 (promo CD) - H |\n| 78 | 88 | 31 | I WANT YOU The Dap-Kings - Savage Garden Columbia 9435 (promo CD) - H |\n| 79 | 80 | 4 | SMILE AND WAVE The Dap-Kings - Smile And Wave Universal (promo CD) - J |\n| 80 | 40 | 2 | CRY LOVE Sugar Cain - Diamonds and Debris Columbia 68019-H |\n| 81 | NEW | 1 | ONE DAY OF KISSES Carol Medina - N/A Polydor 314 588 109-Q |\n| 82 | 65 | 10 | NO TENGO DINERIO Los Umbriellos - Red Hot Latin Hits EMI 57398-F |\n| 83 | 62 | 13 | DRIVING IN' L.A. Ben Van 50307 - Uber AudioGram 10105-Select |\n| 84 | 74 | 7 | MAKING LOVE OUT OF NOTHING AT ALL M-Aposis - N/A Third World Entertainment |\n| 85 | 59 | 17 | TEMPTATION The Part Time - Transgression EMI 68370 (promo CD) - F |\n| 86 | 83 | 7 | JANIE, DON'T TAKE YOUR LOVE TO TOWN Jon Bon Jovi - Destination Anywhere Mercury (comp 507) - Q |\n| 87 | 87 | 13 | FOUR LEAF CLOVER Arctic Monkeys - Strongest Places Arista 185392-N |\n| 88 | 95 | 1 | AU NATUREL See Spun Hun - Au Naturel High Longplay 1138 (promo CD) - Q |\n| 89 | 69 | 2 | GOOD ENOUGH Dodgy - Good Enough Swirls A&M 314 540 373 (promo 5) - Q |\n| 90 | 56 | 12 | D'YOU KNOW WHAT I MEAN? Oasis - D'You Know What I Mean? Columbia 3289-H |\n| 91 | 79 | 28 | CHANGE Scott Stapp - Sheryl Crow A&M 314 540 587-Q |\n| 92 | 77 | 11 | MO MONEY MO PROBLEMS The Neptunes - Mo Money After Death Asylum 79100 (comp 30) - H |\n| 93 | 82 | 13 | I'LL BE MISSING YOU Put Daddy - With Faith Evans - No Way Out Bad Boy 50102 (comp 19) - N |\n| 94 | 68 | 23 | WAYNE Chantel Kreviazuk - Under These Rocks And Stones Columbia 802246 (comp 61) - H |\n| 95 | 78 | 6 | LOST HIGHWAY Lori Yester - Lost Highway Virgin (promo CD) - F |\n| 96 | 81 | 9 | FOR YOU I WILL Monica - Space Jam O.S.T. Atlantic (comp 310) - F |\n| 97 | 86 | 27 | MMMBOP Hanson - Middle Of Nowhere Mercury (comp 507) - Q |\n| 98 | 89 | 13 | RETURN OF THE MACK Mark Morrison - Mark Morrison WEA 17286 |\n| 99 | 92 | 12 | BREAK MY STRIDE Usher - Level II Columbia 91161 (comp 62) - H |\n| 100| 84 | 18| LAST NIGHT ON EARTH U2 Island 504334 (comp 4) - J |\n\nA Present from Sass Jordan -- in the Present\n\nby Rod Cardine\n\n\"Something good did come out of all that,\" she says. \"It was very dark and difficult but I'm really glad because I learned so much. I wouldn't have been able to do it without my family, my friends and my fans.\"\n\nKACY CROWLEY - Pop/Rock\nAnchorless\nAtlantic 13038-P\n\nThis former deadhead plays the guitar and sings but hang on a sec, we mean sing. Here's a sample: \"Will I surrender and learn to fight/ Like camouflage through the dark and the light/ From the bottom of my dreams comes the sound/I wear my music like a broken crown.\" Kacy Crowley was signed to Atlantic because her music is all about sincerity and plaintive emotion. She's a thinker who seems to elude the people who try most to achieve them. A native of Northampton Massachusetts, the singer/songwriter was baptised into popular music by the likes of John Denver and John Cougar Mellencamp. And despite the Grateful Dead period that followed her into late adolescence, she has managed to hold on to the fiery, groovy roots that marked her earlier influences. In Singers Are Ugly, Crowley makes cracks about people like Mick Jagger and... herself: \"My dreams become bone thin/Bone dust indie my skin/in the city.\" Atlantic and Warner Bros. are planning a big push for the musician and are expecting a big reception in North America. For that reason, you will hear Hand To Mouth on your local radio where it will be a strong contender for the big CHR hit. Comparisons to Sheryl Crow might be informative but are ultimately pointless; this girl is dominating her very own corner in the pop world, a corner that stands to get a hell of a lot bigger in the months to come.\n\nTHE VERVE\nUrban Hymns\nVirgin 44913-F\n\nIn the seven years since their crash into the British music scene, The Verve have elicited all sorts of conflicting responses, turning them into a type of pop pariah par excellence. Much has been said -- for example, of the grandiose comments -- a la Oasis -- to a less than impressed media, of their hotel room antics and of their drug fuelled spats. And then there's the music. But before we go on to explain why Urban Hymns is a fantastically achieved pop album, we are obliged to refer to the past, when three singles, notably All In The Mind, She's A Superstar and Gravity Grave made this band a reference point for much of the stuff this decade has cranked out. Now back to Urban Hymns. The album has had an early introduction on CHR with Bitter Sweet Symphony, a tune that excludes the consequence that The Verve are accused of being arrogant for continually pointing out. In truth, Urban Hymns progresses to a semblance of their elder brothers in Oasis by concentrating guitar pop and breathy ballads into a '90s psychedelia that inexplicably makes this pop music a little sinister, a brittle and edgy piece of work. Talk about pa d'olive. Songs like Sonnet, which showcase strong words in a framework of perfect melody structure and playful delivery will ensure that this album will be canonsed among the best the period -- and the country -- has produced. Single to follow will be The Drugs Don't Work.\n\nPOP CAN\n- Pop/Alternative\nVarious Artists\nAlert 81033-Q\n\nThis cleverly titled release purports to contain some of the most refreshing indie pop currently fizzling in Toronto. Alert Music, who threw a nice little soiree for this thing last week sometime, is the one putting the compilation together under what must have been the guiding philosophy of any independent pop that works. The triumph of the release, and what it claims over other releases that try to bring together unknown bands, is that if the music has the stamp of commercial radio despite (or because of) its independent freshness, there is a lot to quench the thirst on the rock (all of sixteen tracks for a hot summer day). In our humble opinion, the standouts include Cool Blue Halo (Too Much Kathleen), Universal Honey (Wouldn't Want To Be In Your Shoes), Cinnamon (Another Edit) and the gem of the piece which belongs to that rockin' group of pop hipsters, Clue. Sour Mashslide (Hired Cook), You Will Hear Me and interesting on New Despots (an existential new wave pop experiment) and Minstrels (quaint pop with echoes of baja surfi). A release which is both well executed and important to showcasing the kinds of talent that is currently brewing in our own front doorstep. The release notes for the album called it cool, sweet, simple and pure. That about sums it. Oh, and did we mention it was 100% pure Canadian?\n\nSANDBOX\n- Alternative\nA Murder In The Glee Club\nEMI 857585-F\n\nCool. Here's an album that could be described as that game called Clue... or maybe it would be more intriguing to make the disingenuous association of James Joyce's Ulysses... or maybe it's choose your own adventure. Whatever the true concept of this concept album, the point is that Sandbox have learned a lot about zest, subtlety and strong pop melodies since their last album (1995's Bianco). That album, however, was No. 1, got quiet some promising attention, top ten action on Much, and a slew of nominations from the Junos, CASBY and ECMA's. Despite all that, it's good to hear the band still maintains its independent fervour, something which is evident from a concept album allegorically based on a murder mystery. While the lyrics give us much room to ponder whether Mr. White did it in the red room with a rope, the music stays close to the pop sensibilities that made Curious the wunderhit of yesteryear. Which means that while Murder In The Glee Club might not crown any sleuths over the next month, it will have the tendency to mysteriously appear on radio. The single called Carry and So It Goes will surely follow over at EMI tremendous possibilities for promotion. Of course it has a great chance at success. That's just elementary, my dear Watson.\n\nKEVIN CLOSS\n- Folk 'n Pop\nHomecoming\nTower Bay-1\n\nCarefull Kevin Closs could be catching. After reading the accompanying promotion piece, out of sheer curiosity, his squeaky clean instrumental (acoustic guitar) version of Canada was the first track sampled. The inspiration emerged from a trip to Ireland without saying. Closs is an artist with balls and a unique vocal property to play touch-and-go with not only his own but also the imagination of his listener. His folk roots are pretty obvious. He tailor-fits his word imaging to a warm, almost cuddly projection that creates a message title that fits several moods, all positive. Key here are Homecoming, Pell Mell, Nowhereland, and The Camp Song. But don't overlook Red Dan's Lament. Also Key is Old Voice, written by Ian Tamblyn, who also produced the album and doubles on several instruments, and the Paul Dunn penning of Careful What You Wish For. Recorded at Ottawa's Sound of One Hand and mastered by Bill Kipper at SNB in Montreal.\n\n11:11 - Newfoundland Classics\nNewfoundland Women Sing\nSongs by Ron and Connie Hynes\nTMP-1111\n\nThere's nothing more that captures the very essence of The Rock and its lush heritage than the works of Newfoundland's Ron and Connie Hynes. Add to that the individual vocal charm and a no-kidding delivery by 11 of the island's best known female vocalists, and you have an entertainment package that underscores not only the importance of being a Newfoundland but a female to boot. Needless to say, this has been a two-year labour of love by Ron and Connie and producer Declan O'Doherty, not to mention the support of TMP The Music Producer. All tracks are key, and whether by accident or design, the music and lyrics fit perfectly, the personality of each of the vocalists. Ants In The House (Met At A Bar), Dammit Doyle (He's Not Wild About You), Liz Picard (Picture To Remember), Kim Stockwood (Leave Or Be The One), Colleen Power (Mary Got A Baby), Vicki Hynes (If You Let Me Go I'll Fall), Mary Barry (April Fools), Shirley Montague (Only Lonely Sometimes), Shirley Dalton (I've Got Thin Lines), Pamela Morgan (May I Shiver Here?), and Kathy Phippard (Heart Of A Man). Recorded at The Junction Sound Studios in Toronto and mastered by Ted Carson at MusicLane Inc. in Markham, Ontario. Available through TMP The Music Producer 416-986-7788. Distributed on the east coast by Tidemark.\n\nOLIVE\nExtra Virgin\nRCA 67507-N\n\nSure, BMG staffers Dale I Wish I Was Dick Assman' Peters and Cameron Carpenter bagged the every RPM staff with boozoo, turkey subs and olives when they dropped off this release, but that's not why you are currently reading this review. Olive pricked our ears because we heard in it what 500,000 Britons heard when they rushed out to buy the first single from the exploding UK phenom. The song was You're Not Alone and is, of course, included here in the trio's third North American release called Extra Virgin. The sound harkens to something we've heard before, notably Everything But The Girl, though Olive aims to throw a tasty splash of R&B into the techno-tinged trip hop mix that give their particular potion the taste of heaven. Something about the new Extra Virgin plays itself out, suggesting us that there's a huge crossover market for this music, including CHR, A/C and alternative. The fluid, soulful ebbs and flows reach crescendoes with Miracle, Safer Hands and, of course, You're Not Alone. Understandably, there is big anticipation for a North American invasion and the possibility seems glaringly tangible after a cursory listen to the album. Like their natural counterpart, Olive may be a matter of taste, but whatever you do, don't fail to give it a listen. You might be missing out on one of the main events of the year.\n\nTHE LAST TIME I COMMITTED SUICIDE\nSoundtrack - Various Artists\nBlue Note-36736-F\n\nThe music is good, the lyrics are interesting, but the album is not really all that. It's a bit too long and the songs are a bit too similar to each other. The vocals are also a bit too high-pitched for my taste.\n\nCOLUMBIA PICTURES WILL RELEASE KIRKLAND'S FAVORITE MOVIE SOUNDTRACK ON OCTOBER 21. THE LAST TIME I COMMITTED SUICIDE IS A COLLECTIVE OF MUSIC FROM THE FILM OF THE SAME NAME. THE ALBUM FEATURES A VARIETY OF GENRES, INCLUDING ROCK, POP, AND JAZZ. THE SONGS ARE ALL ORIGINAL COMPOSITIONS BY VARIOUS ARTISTS, INCLUDING BRIAN ENO, ROGER DALTREY, AND RICHARD HAMILTON. THE ALBUM IS AVAILABLE AT MOST RECORD STORES AND ONLINE.\n\n| TW | LW | WO | Artist/Title | Label | Catalog |\n|----|----|----|--------------|-------|---------|\n| 1 | 1 | 5 | AQUA | Aquarium (MCA) 895020 |\n| 2 | NEW| | JANET JACKSON | Velvet Rope (Virgin) 47692 |\n| 3 | 3 | 2 | LOREENA McKENNITT | The Book Of Secrets (WEA) 19404 |\n| 4 | 7 | 4 | JEWEL | Pieces Of You (Atlantic) 82700 |\n| 5 | 6 | 9 | BACKSTREET BOYS | Backstreet's Back (Jive) 41617 |\n| 6 | 4 | 13 | SARAH McLACHLAN | Surfacing (Nettwerk) 30116 |\n| 7 | 2 | 2 | THE ROLLING STONES | Bridges To Babylon (Virgin) 44712 |\n| 8 | 8 | 12 | PUFF DADDY & THE FAMILY | No Way Out (Bad Boy) 3072 |\n| 9 | 10 | 4 | MARIAH CAREY | Butterfly (Columbia) 67835 |\n| 10 | 14 | 15 | ANDREA BOCELLI | Romantica (Philips) 56456 |\n| 11 | 9 | 3 | BOYZ II MEN | Evolution (Motown) 30818 |\n| 12 | 12 | 7 | TRISHA YEARWOOD | Songbook (Universal) 70001 |\n| 13 | 11 | 13 | JANIN ARDEN | Happy? (Asm) 40789 |\n| 14 | 13 | 4 | SOULFOOD O.C.S.| Various Artists (Arista) 26041 |\n| 15 | 15 | 38 | OUR LADY PEACE | Cuntry (Columbia) 80242 |\n| 16 | 5 | 2 | PORTISHEAD | Portishead (London) 539189 |\n| 17 | 17 | 15 | PRODIGY | The Fat Of The Land (XL Recordings/Koch) 40121 |\n| 18 | 19 | 12 | SUGAR RAY | Flavors (Atlantic) 83006 |\n| 19 | 18 | 44 | SPICE GIRLS | Spice (Virgin) 42174 |\n| 20 | 16 | 3 | ELTON JOHN | The Big Picture (Mercury) 538286 |\n| 21 | 20 | 7 | OASIS | Be Here Now (Epic) 68530 |\n| 22 | 33 | 4 | CHUMBAWUMBA | Tubthumper (MCA) 53059 |\n| 23 | 22 | 4 | BROOKS & DUNN | Greatest Hits Collection (Arista) 18852 |\n| 24 | 25 | 29 | MATCHBOX 20 | Yourself Or Someone Like You (Lava) 92721 |\n| 25 | 24 | 3 | DANCE HITS ALL STARS | Various Artists (Pipper) 80150 |\n| 26 | NEW| | FRANCOIS PERUSSE | L'Album Du Peu (Zol) 90009 |\n| 27 | 23 | 24 | NOW! 2 | Various Artists (WEA) 35296 |\n| 28 | 21 | 5 | LEANN RIMES | You Light Up My Life (Curb) 77895 |\n| 29 | 23 | 8 | HANSON | Middle Of Nowhere (Mercury) 34615 |\n| 30 | 52 | 13 | HELMUT LOTTI | Various Artists (Masc) 1884 |\n| 31 | 29 | 45 | WALLFLOWERS | Bringing Down The... (MCA) 90055 |\n| 32 | 31 | 54 | AMANDA MARSHALL | Amanda Marshall (Columbia) 80229 |\n| 33 | 39 | 8 | SMASH MOUTH | Fush-Ya Mang (Interscope) 90142 |\n| 34 | 34 | 30 | DAFT PUNK | Homework (Virgin) 42609 |\n| 35 | 36 | 3 | PURE DANCE | Various Artists (PolyTel) 40106 |\n| 36 | 42 | 53 | BACKSTREET BOYS | Backstreet Boys (Jive/Zomba) 15981 |\n| 37 | 26 | 3 | BJORK | Homogenic (Elektra) 62061 |\n| 38 | 44 | 4 | MC MARIO DANCE | Various Artists (Sony) 24028 |\n| 39 | 35 | 4 | BUSTA RHYMES | When Disaster Strikes (Elektra) 62064 |\n| 40 | 32 | 15 | MEN IN BLACK O.S.T. | Various Artists (Columbia) 68189 |\n| 41 | 30 | 2 | THE VERVE | Urban Hymns (Virgin) 44913 |\n| 42 | 45 | 21 | FOO FIGHTERS | Colour And The Shape (EMI) 55632 |\n| 43 | 38 | 29 | NOTORIOUS B.I.G.| Lite After Death (Blues Boy) 073011 |\n| 44 | 47 | 21 | GREAT BIG SEA | Play (Warner Bros.) 18592 |\n| 45 | 43 | 34 | LIVE | Secret Sumachi (Radioactive) 11590 |\n| 46 | 27 | 2 | BOB DYLAN | Time Out Of Mind (Columbia) 68556 |\n| 47 | 40 | 16 | THE TEA PARTY | Transmission (EMI) 55358 |\n| 48 | 41 | 26 | SAVAGE GARDEN | Savage Garden (Columbia) 67954 |\n| 49 | NEW| | EVERCLEAR | So Much For The After Glow (EMI) 36503 |\n| 50 | 37 | 17 | RADIOHEAD | OK Computer (EMI) 55229 |\n| 51 | NEW| | DIANA PRINCESS OF WALES 1961-1997 | Various Artists (London) 480000 |\n| 52 | NEW| | HOLLY COLE | Dark Dear Heart (Alert) 81034 |\n| 53 | 50 | 3 | USHER | My Way (Arista) 28043 |\n| 54 | 55 | 16 | ROBYN | Robyn Is Here (RCA) 67477 |\n| 55 | 99 | 2 | SWEET P MORIFOD | 20 Ans Depa... (Dorr) 79345 |\n| 56 | 59 | 54 | CELINE DION | Falling Into You (Columbia) 33068 |\n| 57 | 53 | 8 | FLEETWOOD MAC | The Dance (Reprise) 46702 |\n| 58 | 46 | 9 | 98 DEGREES | 98 Degrees (Motown) 530796 |\n| 59 | 49 | 50 | JAMIROUQAI | Traveling Without Moving (Columbia) 91109 |\n| 60 | 51 | 54 | ELTON JOHN | Love Songs (MCA) 11481 |\n| 61 | 58 | 6 | CMT COLLECTION | Various Artists (EMI/BMG) 1253 |\n| 62 | 57 | 8 | ESCAPES Vol. 2 | Various Artists (Warner Bros.) 35691 |\n| 63 | 48 | 4 | SOUL GROOVE | Various Artists (Universal) 81058 |\n| 64 | 68 | 16 | WYCLEF JEAN | Presents...The Carnival (Columbia) 67974 |\n| 65 | 54 | 8 | BRUNO PELLETIER | Miraire (Born) 30116 |\n| 66 | 62 | 21 | MEREDITH BROOKS | Blurring The Edges (EMI) 36919 |\n| 67 | 60 | 22 | TONIC | Lemon Parade (PolyGram) /1042 |\n| 68 | 56 | 4 | ADAM SANDLER | What's Your Name? (Warner Bros.) 46738 |\n| 69 | 61 | 19 | TIM McGRAW | Everywhere (Curb) 77888 |\n| 70 | NEW| | THE PHILOSOPHER KINGS | Famous, Rich And Beautiful (Columbia) 80291 |\n| 71 | 63 | 21 | TRAGICALLY HIP | Live Between Us (Universal) 81055 |\n| 72 | 67 | 54 | NO DOUBT | Tragic Kingdom (Interscope) 90003 |\n| 73 | 64 | 22 | THIRD EYE BLIND | Third Eye Blind (Elektra) 62012 |\n| 74 | 75 | 4 | MACK 10 | Based On A True Story (Virgin) 50675 |\n| 75 | 81 | 4 | BRIGHTMAN/CURA | Time to Say Go (A&M) 58311 |\n| 76 | 70 | 30 | AEROSMITH | Nine Lives (Columbia) 67547 |\n| 77 | 66 | 9 | SVW | Release Some Tension (RCA) 67525 |\n| 78 | 93 | 19 | DUBMETIQUE | The Force de Compre... (Select) 43022 |\n| 79 | 80 | 16 | BRAN VAN 3000 | Gee (Select) 77105 |\n| 80 | 77 | 16 | MY BEST FRIEND'S WEDDING O.S.T. | Various Artists (Epic) 68168 |\n| 81 | 65 | 4 | PAUL BRANDT | Outside The Frame (WEA) 46635 |\n| 82 | 71 | 11 | SPAWN O.S.T. | Various Artists (Epic) 69494 |\n| 83 | 76 | 34 | BLUR | Blur (EMI) 55582 |\n| 84 | 82 | 54 | TONI BRAXTON | Secrets (Ja Face) 26020 |\n| 85 | 84 | 21 | NEW COUNTRY 4 | Various Artists (Warner) 35328 |\n| 86 | 79 | 7 | DIANA KRALL | Low Scenes (Impulse/Universal) 50234 |\n| 87 | 73 | 16 | HOLLY McNARLAND | Stuff (Universal) 53075 |\n| 88 | 68 | 8 | BOB DYLAN | The Best Of Bob Dylan (Sony) 24037 |\n| 89 | 72 | 50 | DEANA CARTER | Did I Shave My Legs (EMI) 96080 |\n| 90 | 78 | 54 | LEANN RIMES | Blue (Curb) 77821 |\n| 91 | 83 | 6 | MONEY TALKS O.S.T. | Various Artists (Arista) 18875 |\n| 92 | NEW| | JIMI HENDRIX | South Saturn Delta (MCA) 11684 |\n| 93 | 85 | 25 | VERVE PIPE | Villains (BMG) 88809 |\n| 94 | 74 | 19 | WU-TANG CLAN | Wu-Tang Forever (BMG) 69805 |\n| 95 | 89 | 3 | EPMD | Back In Business (DefJam) 536389 |\n| 96 | 91 | 54 | BECK | Odelay (Geffen) 24623 |\n| 97 | 92 | 14 | BLUE RODEO | Tremolo (WEA) 19253 |\n| 98 | 88 | 7 | COOLIO | Coolia My Soul (Tommy Boy) 1180 |\n| 100| 95 | 54 | SHERYL CROW | Sheryl Crow (A&M) 314540 587 |\n\nGary Fjellgaard has been selected to perform at the 9th annual Western Music Festival which will be held in Calgary, Alberta from October 24-26. The festival is a showcase for Western music and features performances by some of the best artists in the genre.\n\nChely Wright is on the same edition where she will talk about her new single \"Shut Up And Drive.\" The song is from her upcoming album \"The Other Side,\" which is set to be released later this year. Chely has been making waves in the country music scene with her powerful vocals and unique style.\n\nannounced plans for a 14-city tour of Germany as well as a 20-city tour of the U.S. in November and December.\n\n### RPM Adult Contemporary Tracks\n\n**Record Distributor Codes:**\n- BMG - N\n- EMI - F\n- Universal - J M Quality\n- Polygram - Q\n- Sony - H\n- Warner - P\n- Koch - K\n\n#### October 20, 1997\n\n| TW | LW | WD |\n|----|----|----|\n| 1 | 1 | 6 |\n| 2 | 12 | 12 |\n| 3 | 3 | 12 |\n| 4 | 7 | 7 |\n| 5 | 6 | 7 |\n| 6 | 7 | 10 |\n| 7 | 5 | 17 |\n| 8 | 10 | 11 |\n| 9 | 9 | 9 |\n| 10 | 11 | 14 |\n| 11 | 8 | 12 |\n| 12 | 13 | 11 |\n| 13 | 16 | 12 |\n| 14 | 14 | 13 |\n| 15 | 17 | 31 |\n| 16 | 12 | 31 |\n| 17 | 18 | 15 |\n| 18 | 15 | 18 |\n| 19 | 20 | 8 |\n| 20 | 21 | 15 |\n\n#### CANDLE IN THE WIND '97\nElton John - CD single\nRocket (supplied by Digital Counter)\n\n#### TAKES A LITTLE TIME\nAmy Grant - From The Eyes\nCapitol-1464 (pro single)-F\n\n#### THE SOUND OF\nJohn Alden - Heartbeat\nAtlantic-19703 (pro single)-Q\n\n#### SOMETHING ABOUT THE WAY YOU LOOK\nElton John - Title track\nRocket-316-574-8912 (pro single)-Q\n\n#### 2 BECOME 1\nSheryl Crow - Space\nVirgin-2174 (pro single)-F\n\n#### BUILDING A MYSTERY\nAmy Grant - The Eyes\nNetswtrks-30116 (pro single)-F\n\n#### IF MY HEART HAD WINGS\nAmy Sky - Cool Rain\nWarner-31085 (CD track)-N\n\n#### HONEY\nMiriam Carey - Butterfly\nColumbia-67835 (CD single)-H\n\n#### SHED A LIGHT\nAmy Grant - Kissing Rain\nR.V International/3M-43978 (pro single)-N\n\n#### IT COULD HAPPEN TO YOU\nAmy Grant - The Eyes\nWFA-19253 (comp 327)-P\n\n#### FOOLISH GAMES\nJames - Pieces Of Your Soul\nAtlantic-19703 (CD single)-P\n\n#### GOOD MAN, FEELING BAD\nTim Crochere - Songs Of A Circling Spirit\nEMI-44688 (pro single)-Q\n\n#### WHERE'S THE LOVE\nHanson - Middle Of Nowhere\nMercury-314-534-6152 (comp 509)-Q\n\n#### I DON'T WANT TO WAIT\nTrisha Yearwood - Greatest Hits\nMCA-79079 (CD track)-U\n\n#### SEMI-CHARMED LIFE\nLyle Lovett - Self-titled\nElektra-82012 (CD track)-P\n\n#### TO THE MOON AND BACK\nSavage Garden - Self-titled\nColumbia-67834 (comp 058)-H\n\n#### DO WHAT YOU DO\nCarolyn Arezzo - Feel Free\nPhilips-4466466 (comp 30306-2) (CD track)\n\n#### SILVER SPARKS\nFlawed Mic - The Dance\nReprise-46702 (comp 331)-P\n\n#### ANYBODY SEEN MY BABY\nThe B-52's - The Eyes Of Babylon\nVirgin-44712 (pro single)-E\n\n#### SUNNY CAME HOME\nShawn Colvin - New Small Repairs\nColombia-67834 (comp 19704)-H\n\n#### FOR YOU I WILL\nMonica - Space Jam OST\nAtlantic-19703 (CD single)-P\n\n#### A SMILE LIKE YOURS\nNatalie Cole - Title track OST\nWarner Bros-62093 (comp 328)-H\n\n#### HOW DO I LIVE\nLeAnn Rimes - Light Up My Life\nCurb-77885 (pro single)\n\n#### HEALING WATERS - FOR DIANA\nCynthia - Self-titled\nColumbia (CD single env)\n\n#### HOW DO I LIVE\nTrisha Yearwood - Greatest Hits\nMCA-79079 (CD track)-U\n\n#### MORE THAN THIS\n10,000 Maniacs - Love Among The Ruins\nGeffen-25000 (comp 10)-H\n\n#### SITTING ON TOP OF THE WORLD\nAerosmith - Love Song\nEpic-80229 (comp 061)-H\n\n#### I'VE JUST SEEN A FACE\nTina Turner - Private Part\nA&M-615-201-024 (pro single)-Q\n\n#### DO YOU KNOW WHAT IT TAKES\nRobyn - Robin In Her Eyes\nRCA-44688 (pro single)-Q\n\n#### GO THE DISTANCE\nMichael Bolton - Disney's Hercules OST\nColumbia-98938 (pro single)-H\n\n#### ALL FOR YOU\nRoger Hanin - Somewhere More Familiar\nUniversal-53030 (pro single)-J\n\n#### INVISIBLE MAN\nThe Black Crowes - Self-titled\nMotown-316-530-796 (comp 6)-Q\n\n#### THE DIFFERENCE\nThe Wallflowers - Bringing Down The Horse\nInterscope-30268 (CD track)-J\n\n#### DO WHAT I CAN\nSara Jordan - Present\nAquarius-80229 (pro single)-F\n\n#### WHEN I'M UP (I Can't Get Down)\nGreat Big Sea - Play\nWEA-18592 (comp 323)-P\n\n#### MY NEW JUDGMENT\nDiana Marroquin - Vigo-1\nEMI-56635 (CD track)-F\n\n#### TIME TO SAY GOODBYE\nBarbara Streisand - Romanza\nPhilips-566466 (CD track)-U\n\n#### NO TENGO DINERO\nLos Urrutelos - Red Hot Latin Hits\nEMI-77393 (comp 328)-H\n\n#### YOU SHOULD BE HAVING FUN\nBarenaked Ladies - Legendary Hearts - Til Tomorrow\nColumbia-80252 (comp 064)-H\n\n#### DO YOU LOVE ME THAT MUCH\nThe Beach Boys - Self-titled\nRiver North-768-74-2313 (CD track)-Q\n\n#### A CHANGE WOULD DO YOU GOOD\nSteryl Crow - Self-titled\nA&M-615-201-024 (comp 3)-Q\n\n#### YOUNG BOY\nPaul McCartney - Flaming Pie\nCapitol-50000 (CD single)-F\n\n#### SOLDIER'S BOY\nSpirit Of The West - Weights & Measures\nWEA-19716 (comp 334)-P\n\n#### IF I WAIT THERE FOR YOU\nThe Beach Boys - Self-titled\nNar/Popne-001 (CD track)\n\n#### SO BEAUTIFUL\nChris de Burgh - Greatest Songs\nArista-615-040-734 (comp 7)-H\n\n#### TO MAKE YOU FEEL MY LOVE\nBilly Joel - Greatest Hits Vol. III\nColumbia-67834 (comp 19704)-H\n\n#### IT'S OKAY, I UNDERSTAND\nGavin Hone - No album\nPopular (pro single)-P\n\n#### PUSH\nMarching 20 - Yourself With Someone\nLava-92721 (CD single)-J\n\n#### COME BACK\nThe Black Crowes - Self-titled\nTV-1 (CD track)\n\n#### GOOD ENOUGH\nDana - Good Enough\nAsm-514-540-573 (comp 3)-O\n\n#### I DON'T WANT TO\nToni Braxton - Secrets\nLaFace-80229 (CD single)-N\n\n#### STILL WATERS RUN DEEP\nThe Black Crowes - Self-titled\nPolydor-31453-7302 (comp 520)-O\n\n#### SO HELP ME GIRL\nGary Clark - Self-titled\nArista-07822-18549 (comp 241)-N\n\n#### FLY\nScott Ray - Hooray\nAtlantic-43008 (CD single)-P\n\n#### ON MY OWN\nPeachy King - Audeoptron\nMCA-79079 (CD track)-U\n\n#### SEE THE PEOPLE\nSoul Attitudes - Self-titled\nEpic-80234 (comp 058)-H\n\n#### SAY A LITTLE PRAYER\nDonna King\nSony-H\n\n#### CAN YOU KEEP A SECRET\nFirst Base\nArista-N\n\n#### YOUR NOT ALONE\nDana\nBMG-N\n\n#### MARIA\nRobert Maran\nColumbia-H\n\n#### GET UP GO INSANE\nStretch N Vern\nPolydor-Q\n\n#### FIX\nBlacstreet\nUniversal-J\n\n#### SONG FOR MY BROTHER\nKenny Rankson - That's Right\nUniversal\n\n#### CAN YOU FEEL IT\nThe Party\nA&M-D\n\n#### PUT YOUR HANDS WHERE MY...\nBusta Rhymes\nVerve\n\n#### ONE DAY OF KISSES\nCarol Medina\nPopular-P\n\n### RPM Dance\n\n**Record Distributor Codes:**\n- BMG - N\n- EMI - F\n- Universal - J M Quality\n- Polygram - Q\n- Sony - H\n- Warner - P\n- Koch - K\n\n#### October 20, 1997\n\n| TW | LW | WD |\n|----|----|----|\n| 1 | 2 | 2 |\n| 2 | 1 | 7 |\n| 3 | NEW | 1 |\n| 4 | 8 | 4 |\n| 5 | 3 | 9 |\n| 6 | 22 | 9 |\n| 7 | 13 | 2 |\n| 8 | 18 | 8 |\n| 9 | 11 | 2 |\n| 10 | 4 | 8 |\n\n#### HONEY (REMIX)\nMiriam Carey\nColumbia-67835-F\n\n#### BABIE GIRL\nKylie\nUniversal - J\n\n#### FEEL SO GOOD\nKylie\nRCA-N\n\n#### BEEN AROUND THE WORLD\nPuff Daddy\nCapitol-N\n\n#### GET READY TO BOUNCE\nBrooklyn Bounce\nA&M\n\n#### NOT TONIGHT\nU2\nKing\nWarner - P\n\n#### ANGUS\nNathan Camp\nBMG-N\n\n#### EVERYBODY\nBackstreet Boys\nBMG-N\n\n#### SOMEONE\nSWV/Puff Daddy\nRCA-N\n\n#### RIPGROOVE\nDouble 98\nIce Cream-N\n\n#### EXTASY\nElite\nQuicks-M\n\n#### C-LIME WOMAN\nThe People Movers\nPopular-P\n\n#### FREE\nUltra Nate\nQuality - M\n\n#### MO MONEY MO PROBLEMS\nNotorious B.I.G.\nBMG-N\n\n#### HOLD YOUR HEAD UP HIGH\nBono Dugosh P, Booom\nSPRM\n\n#### DO IT TO IT\nMichelle\nSolid\n\n#### MOVE YA FEET\nPJ\nStickman\n\n#### GOT TIL' IT'S GONE\nJanelle Monae\nFatl-Virgin\n\n#### I'LL BE MISSING YOU\nPuff Daddy\nRox Records\n\n#### PIECE OF MY HEART\nShaggy\nVirgin-F\n\n#### SAY A LITTLE PRAYER\nDonna King\nSony-H\n\n#### CAN YOU KEEP A SECRET\nFirst Base\nArista-N\n\n#### YOUR NOT ALONE\nDana\nBMG-N\n\n#### MARIA\nRobert Maran\nColumbia-H\n\n#### GET UP GO INSANE\nStretch N Vern\nPolydor-Q\n\n#### FIX\nBlacstreet\nUniversal-J\n\n#### SONG FOR MY BROTHER\nKenny Rankson - That's Right\nUniversal\n\n#### CAN YOU FEEL IT\nThe Party\nA&M-D\n\n#### PUT YOUR HANDS WHERE MY...\nBusta Rhymes\nVerve\n\n#### ONE DAY OF KISSES\nCarol Medina\nPopular-P\n\nCLASSIFIEDS\n\nAPPLICATIONS BEING ACCEPTED TO UPDATE FILES\n\nYou are Invited\n\nTo The Second Annual Music Industry Holiday Luncheon\n\nTo Benefit The Canadian Music Therapy Trust Fund\n\nAt The Toronto Ballroom in the Metropolitan Hotel 108 Chestnut Street, Toronto\n\nOn Friday, December 5th, 1997\n\nCocktails 12:00 PM Luncheon 12:30 - 3:00 PM Includes Auction\n\nTickets $125 per person\n\nFor Reservations Please Call (416) 488-6363\n\nMusic Therapy is a method of treatment which uses music to help people cope more effectively with their lives and with their difficulties. The goal of music therapy is to develop the potential of each person involved, not to promote musical ability.\n\nThe Music Therapy Trust Fund is a charitable non-profit organization, supported by volunteers, which raises funds for music therapy projects in Canada. In this past year, with help of the Canadian Music Industry, the Canadian Music Therapy Trust Fund has been able to give assistance to 32 such projects. These range from hospices for terminally ill persons with cancer or AIDS, centres for the aged, schools for children who are autistic, physically or mentally challenged, and for street kids.\n\nCanadian Music Therapy Trust Fund Advisory Board\n\nLaura Bartlett HMV, Rodney Bowes Rodney Bowes Design, Sarah Crawford MuchMusic, Joni Daniels Joni Daniels Management, Fran Herman Chairperson, Carl Herman CMTTF, Steve Kane Virgin, Christine Liber Universal Concerts, John Marshall The NewMusic, Garry Newman Warner, Don Oates Sony, Keith Porteus BMG, John Reid Polygram, Jeff Rogers handsome boy/Swell, Don Simpson Universal Concerts, Steve Tennant Universal Records, Robyn Walters EMI"}}}],"truncated":false,"partial":true},"paginationData":{"pageIndex":2044,"numItemsPerPage":100,"numTotalItems":208496,"offset":204400,"length":100}},"jwt":"eyJhbGciOiJFZERTQSJ9.eyJyZWFkIjp0cnVlLCJwZXJtaXNzaW9ucyI6eyJyZXBvLmNvbnRlbnQucmVhZCI6dHJ1ZX0sImlhdCI6MTc3ODk4MTQyNCwic3ViIjoiL2RhdGFzZXRzL1RlbGVBSS1BSS1GbG93L0luZm9ybWF0aW9uQ2FwYWNpdHkiLCJleHAiOjE3Nzg5ODUwMjQsImlzcyI6Imh0dHBzOi8vaHVnZ2luZ2ZhY2UuY28ifQ.wHPvVoSjKJx2TIBA5I_kUXoSPLmh3dZ8mBUfOa0W_sJJwRupNd-Xwy1kWYeEL6K42RsF3A7YxQDjPU-NWHfSAw","displayUrls":true,"splitSizeSummaries":[{"config":"default","split":"train","numRows":208496,"numBytesParquet":2762384337}]},"discussionsStats":{"closed":1,"open":0,"total":1},"fullWidth":true,"hasGatedAccess":true,"hasFullAccess":true,"isEmbedded":false,"savedQueries":{"community":[],"user":[]}}">
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INTRODUCTION
Defendant Kenosha Education Association (“KEA”) opposes Plaintiffs’ Motion for Summary Judgment. Plaintiffs seek a declaration that all collective bargaining agreements between KEA and other labor union Defendants (collectively referred to as “Defendants”) and the Kenosha Unified School District (“KUSD”) ... |
Teaching Social Justice Through Legal Writing
Pamela Edwards
*CUNY School of Law*
Sheilah Vance
*Cheyney University*
TEACHING SOCIAL JUSTICE THROUGH LEGAL WRITING
Pamela Edwards\(^1\) and Sheilah Vance\(^2\)
INTRODUCTION
Because the topic of social justice is important to both of the authors, we were pleased ... |
100 years of seismic research on the Moho
Claus Prodehl\textsuperscript{a}, Brian Kennett\textsuperscript{b}, Irina M. Artemieva\textsuperscript{c}, Hans Thybo\textsuperscript{c,*}
\textsuperscript{a} Geophysical Institute, University of Karlsruhe, Karlsruhe Institute for Technology, Hertzstr. 16, D76167 Karlsruhe, G... |
Reproductive biology of blacktip grouper, *Epinephelus fasciatus*, in Sulu Sea, Philippines
Hiroaki MISHINA\textsuperscript{1,3}, Benjamin GONZALES\textsuperscript{2}, Honorio PAGALIAWAN\textsuperscript{2}, Masato MOTEKI\textsuperscript{1*} and Hiroshi KOHNO\textsuperscript{1}
**Abstract**: The maturation size, spawn... |
Science-based ecosystem restoration for the 2020s and beyond
Science Task Force for the UN Decade on Ecosystem Restoration
Science-based ecosystem restoration for the 2020s and beyond
Science Task Force for the UN Decade on Ecosystem Restoration
The designation of geographical entities in this publication, and the ... |
Double-stranded oligonucleotides
Antisense sequences, including duplex RNAi compositions, which possess improved properties over those taught in the prior art are disclosed. The invention provides optimized antisense oligomer compositions and method for making and using the both in *in vitro* systems and therapeutical... |
Mind the Gap: Two Dissociable Mechanisms of Temporal Processing in the Auditory System
Lucy A. Anderson\textsuperscript{1} and Jennifer F. Linden\textsuperscript{1,2}
\textsuperscript{1}Ear Institute, University College London, London, WC1X 8EE, United Kingdom, and \textsuperscript{2}Department of Neuroscience, Physio... |
Let's Talk Plants!
Newsletter of the San Diego Horticultural Society
February 2014, Number 233
The Wild World of Succulents
SEE PAGE 1
SEXY AVOCADOS
PAGE 5
SAY IT WITH FLOWERS
PAGE 6
SPRING HOME/GARDEN SHOW
PAGE 8
SPRING GARDEN TOUR
PAGE 10
On the Cover: Endangered Baobab trees in Madagascar
SDHS OUR 20TH YEAR!... |
St. Mary Roman Catholic Church
32 Pearl Street, Claremont, NH 03743
Phone: (603) 542-9518 / Fax: (603) 542-9614
Website: www.stmaryparishnh.org
Email: email@example.com
Pastor
Rev. Maria Sebastian Susairaj, HGN
Administrative Assistant
Mary K. Keating
Music Director
Joe Labrecque
Interim Faith Formation Director
K... |
Persistent *Ascaris* Transmission Is Possible in Urban Areas Even Where Sanitation Coverage Is High
Drew Capone, Troy Barker, Oliver Cumming, Abeoseh Flemister, Riley Geason, Elizabeth Kim, Jackie Knee, Yarrow Linden, Musa Manga, Mackenzie Meldrum, Rassul Nala, Simrill Smith, and Joe Brown*
**ABSTRACT:** In low-incom... |
COLLISIONS BETWEEN ELECTRONS AND NUCLEI.
By B. Touschek.
All rights reserved
INFORMATION TO ALL USERS
The quality of this reproduction is dependent upon the quality of the copy submitted.
In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also,... |
Local and Global Changes in Brain Metabolism during Deep Brain Stimulation for Obsessive-Compulsive Disorder
Juan Carlos Baldermann 1,*, Karl Peter Bohn 2, Jochen Hammes 2, Canan Beate Schüller 1, Veerle Visser-Vandewalle 3, Alexander Drzezga 2 and Jens Kuhn 1,4
1 Department of Psychiatry and Psychotherapy, Universit... |
Primary sensory cortices contain distinguishable spatial patterns of activity for each sense
M. Liang\textsuperscript{1}, A. Mouraux\textsuperscript{2}, L. Hu\textsuperscript{3} & G.D. Iannetti\textsuperscript{1}
Whether primary sensory cortices are essentially multisensory or whether they respond to only one sense i... |
van Uitert, E, Joachimi, B, Joudaki, S, Amon, A, Heymans, C, Köhlinger, F, Asgari, M, Blake, C, Choi, A, Erben, T, Farrow, DJ, Harnois-Déraps, J, Hildebrandt, H, Hoekstra, H, Kitching, TD, Klaes, D, Kuijken, K, Merten, J, Miller, L, Nakajima, R, Schneider, P, Valentijn, E and Viola, M
KiDS+GAMA: cosmology constraints ... |
AGENDA
MARINA DEL REY DESIGN CONTROL BOARD
Thursday, November 19, 2009, 2:00 p.m.
Burton W. Chace Park Community Building
13650 Mindanao Way ~ Marina del Rey, CA 90292
Design Control Board Members
Peter Phimney, AIA – Chair - Fourth District
Simon Pastueha – Vice Chair - Third District
Helena Jubany – Member - Fi... |
STATE OF WISCONSIN
CIRCUIT COURT
KENOSHA COUNTY
Kristi Lacroix and
CarrieAnn Glembocki,
Plaintiffs,
v.
Case No. 13-CV-1899
Kenosha Unified School District Board of Education,
Kenosha Unified School District, and
Kenosha Education Association Building Corporation,
d/b/a Kenosha Education Association,
Defendants.... |
This is a repository copy of Effect of alkali treatment of lower concentrations on the structure and tensile properties of Pakistan's coarse cotton fibre.
White Rose Research Online URL for this paper:
http://eprints.whiterose.ac.uk/146530/
Version: Accepted Version
Article:
Azeem, F, Mao, N orcid.org/0000-0003-1203... |
Message from the WGO President
WGO 2005–2009—some thoughts
It has been my great privilege and honor to have served as President of the World Gastroenterology Organisation over the past 4 years and to have attempted to follow in the footsteps of my eminent predecessors and mentors, Guido Tytgat and Meinhard Classen. T... |
Performance of a Magnesium-Rich Primer on Pretreated AA2024-T351 in Full Immersion: a Galvanic Throwing Power Investigation Using a Scanning Vibrating Electrode Technique.
Kannan, B., Glover, C., McMurray, H., Williams, G. & Scully, J. (2018). *Journal of The Electrochemical Society*, 165(2), C27-C41.
http://dx.doi.o... |
Imaging Breast Adipose and Fibroglandular Tissue Molecular Signatures by Using Hybrid MRI-Guided Near-Infrared Spectral Tomography
Ben Brooksby
*Dartmouth College*
Brian W. Pogue
*Dartmouth College*
Shudong Jiang
*Dartmouth College*
Hamid Dehghani
*Dartmouth College*
Subhadra Srinivasan
*Dartmouth Colleg... |
We are delighted to present the annual report of Maris Stella College for the academic year 2022-23. This report offers a comprehensive overview of the accomplishments, challenges, and progress made during the past year. Higher education plays a pivotal role in shaping the future of our society, making it crucial to mo... |
Dear Sir or Madam,
I beg to enclose you a copy of the statement re The League of Nations and Slavery which I have been impelled to prepare through studying Lady John Simon's terrible exposure of Slavery, as still carried on in many parts of the world, and the reports of the League of Nations re the Slavery Conventions... |
Negative Baryon density and the Folding structure of the $B=3$ Skyrmion
David Foster† and Steffen Krusch§
School of Mathematics, Statistics and Actuarial Science,
University of Kent, Canterbury CT2 7NF, United Kingdom
Abstract. The Skyrme model is a non-linear field theory whose solitonic solutions, once quantised, d... |
Gene sharing networks to automate genome-based prokaryotic viral taxonomy
Ho Bin Jang\textsuperscript{1*}, Benjamin Bolduc\textsuperscript{1*}, Olivier Zablocki\textsuperscript{1}, Jens H. Kuhn\textsuperscript{2}, Simon Roux\textsuperscript{3}, Evelien M. Adriaenssens\textsuperscript{4}, J. Rodney Brister\textsuperscr... |
Wallaceward the American Literature Survey Course Takes Its Way
Ralph Clare
Boise State University, firstname.lastname@example.org
Follow this and additional works at: https://scholarworks.boisestate.edu/english_facpubs
Part of the American Literature Commons, and the Literature in English, North America Commons
Pu... |
20 • Piper Flyer May 2020
The difficult task of seat sewing is within the capability of most owners, but it’s important to test-fit, measure correctly, and have the right tools on hand to complete the job. By Dennis Wolter
In the process of writing these articles, I’ve come to realize that some readers may wonder why... |
Chapter 400 Representative of Inventor or Owner
401 Patent Office Cannot Aid in Selection of Attorney
Rule 31. Applicants May Be Represented by Attorney or Agent. An applicant for patent may file and prosecute his own case, or he may be represented by an attorney or agent authorized to practice before the Patent Off... |
This is a repository copy of Blast furnace slag-Mg(OH)(2) cements activated by sodium carbonate.
White Rose Research Online URL for this paper:
http://eprints.whiterose.ac.uk/135348/
Version: Published Version
Article:
Walling, S.A., Bernal, S.A., Gardner, L.J. orcid.org/0000-0003-3126-2583 et al. (2 more authors) (... |
Troop Leadership Training
BOY SCOUTS OF AMERICA®
Leadership is a vital part of the Scouting program. Scouts in positions of leadership run their patrols and the troop. They take care of the many tasks necessary for troop meetings and activities to run smoothly and well. By accepting the responsibilities of troop and ... |
DISTANCE LEARNING MASTER’S PROGRAM IN ECUMENICAL STUDIES
UKRAINIAN CATHOLIC UNIVERSITY
DISTANCE LEARNING MASTER’S PROGRAM
Dear Prospective Student,
The DLPES is a cooperation between the committed and innovative staff of the Institute of Ecumenical Studies, an accomplished, multi-confessional and international facu... |
Nematode response to nitrogen and phosphorus in grasslands, assessed by microscopy and molecular methods
Xiaoyun Chen
National University of Ireland, Galway
Ph.D 2012
Nematode response to nitrogen and phosphorus in grasslands, assessed by microscopy and molecular methods
A thesis presented for the degree of
Docto... |
JURIST 1988
THE JURIST
Volume VI, nineteen hundred eighty-eight
Texas Tech University
School of Law
Lubbock, Texas
TABLE OF CONTENTS
Dedication ........................................... 2
Comments ............................................ 3
Student Body ......................................... 6
Faculty and St... |
ARANI
VOL. 6 - FALL EDITION
OCTOBER 2018
An Expression of Srishti
Bengali Cultural Association of Charlotte, North Carolina
INDIA GROCERS
Providing the highest quality, ethnic grocery and spice products
Where Quality Meets Value, Low Prices Every Day!
Wishing all a very Happy Dussehera
WE CARRY ASLI, DEEP, LAXMI &... |
Dear Councilmembers,
Thanks to several of you for attending the community listening session I held last week relating to draft changes of hazard sheltering and homelessness policy within the Spokane Municipal Code (SMC). As you know, I believe policy changes should be passed with enough time for thoughtful input and c... |
Mortensen, M. and Iqbal, F. and Pandurangan, Arun and Hannan, S. and Huckvale, R. and Topf, Maya and Baker, J.R. and Smart, T.G. (2014) Photo-antagonism of the GABAA receptor. Nature Communications 5 , ISSN 2041-1723.
Downloaded from: https://eprints.bbk.ac.uk/id/eprint/10293/
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ABSTRACT
Systems and methods presented herein provide for real time communications between service provider subscribers. In one embodiment, a web server is operable to provide a network-to-network interface (NNI) with a plurality of service providers, to communicate with the service providers through WebRTC links, and... |
TESTIMONY OF
L. WILLIAM SEIDMAN
CHAIRMAN
FEDERAL DEPOSIT INSURANCE CORPORATION
ON
THE FINANCIAL INSTITUTIONS REFORM, RECOVERY AND ENFORCEMENT ACT OF 1989
BEFORE THE
SUBCOMMITTEE ON FINANCIAL INSTITUTIONS SUPERVISION, REGULATION AND INSURANCE COMMITTEE ON BANKING, FINANCE AND URBAN AFFAIRS UNITED STATES HOUSE OF RE... |
Theses Digitisation:
https://www.gla.ac.uk/myglasgow/research/enlighten/theses/digitisation/
This is a digitised version of the original print thesis.
Copyright and moral rights for this work are retained by the author
A copy can be downloaded for personal non-commercial research or study, without prior permission ... |
TRACING ALIENS: IDENTIFICATION OF INTRODUCED WATER FROGS IN BRITAIN BY MALE ADVERTISEMENT CALL CHARACTERISTICS
JULIA WYCHERLEY\(^1\), SIMON DORAN\(^2\) AND TREVOR J. C. BEEBEE\(^1\)
\(^1\)School of Biological Sciences, University of Sussex, Falmer, Brighton BN1 9QG, UK
\(^2\)Department of Physics, University of Surr... |
Rothamsted Research
Annual Report 2002-2003
Enquiries about this report should be addressed to:
Dr Susannah Bolton
Head of International Liaison and PR
Tel: +44 (0)1582 763133
Fax: +44 (0)1582 760981
e-mail: firstname.lastname@example.org
Further information is available on the internet at:
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Let us start with your initial academic path. Your first university degree is in Mathematics and then you did your third cycle thesis\textsuperscript{1} on automata, more precisely on Černý’s Conjecture, a conjecture that is still unsolved...
I did not start working on automata, it happened by chance. I started by att... |
Scalar Verb Classes
Scalarity, Thematic Roles, and Arguments in the Estonian Aspectual Lexicon
Anne Tamm
BIBLIOTECA DI STUDI DI FILOLOGIA MODERNA
– 14 –
BIBLIOTECA DI STUDI DI FILOLOGIA MODERNA
Aree Anglofona, Francofona, di Germanistica,
Sezione di Comparatistica, Filologie e Studi Linguistici,
e Sezioni di Iberi... |
Safety Training for Workers in the Onsite Industry
We are seeing a change in the liability exposure to small business owners in our industry? Do you have a safety program? Is it doing what you think it is? Companies are being hit with fines from OSHA and State Labor and Industry programs, but recent state supreme cour... |
THE ERYTHROCYTE SEDIMENTATION RATE
Choice of Technique for Sanatorium Use.
A Thesis for the Degree of M.D. Presented by Andrew Clark Penman M.B., Ch.B.
ProQuest Number: 13849827
All rights reserved
INFORMATION TO ALL USERS
The quality of this reproduction is dependent upon the quality of the copy submitted.
In th... |
Parole Interview Transcript/Decision - FUSL000017 (2002-01-09)
Follow this and additional works at: https://ir.lawnet.fordham.edu/trans
Recommended Citation
"Parole Interview Transcript/Decision - FUSL000017 (2002-01-09)" (2019). Parole Information Project. https://ir.lawnet.fordham.edu/trans/42
This Parole Document... |
What does survivorship mean?
Let us explain it to you.
ESMO Patient Guide Series
based on the ESMO Clinical Practice Guidelines
esmo.org
Survivorship is a unique and ongoing experience, which is different for each person and those close to them. A key to survivorship is to regain, as far as possible, the important ... |
MONTHLY REVIEW
JULY 1976
Contents
The Business Situation .................................................. 179
The Money and Bond Markets in June ......................... 183
A Probabilistic Approach to Early Warning of Changes in Bank Financial Condition ............... 187
The Business Situation
The latest rea... |
Roma rights
Discrimination, paths of redress and how the law can improve the situation of Roma
Roma rights
Discrimination, paths of redress and how the law can improve the situation of Roma
Swedish Equality Ombudsman (Diskrimineringsombudsmannen, DO)
R2 ENG 2011
Printed by DanagardLITHO, Ödeshög, 2011
ISBN 978-91-... |
Juvenile Law--A Potential for California Change
Glendalee Garfield
University of the Pacific; McGeorge School of Law
Follow this and additional works at: https://scholarlycommons.pacific.edu/mlr
Part of the Juvenile Law Commons
Recommended Citation
Glendalee Garfield, *Juvenile Law--A Potential for California Change... |
PARISH MISSION STATEMENT
St. Julie Billiart is a welcoming Roman Catholic community that deepens our personal relationship with Jesus Christ by worshiping together, reaching out to others and building up the Kingdom of God.
THE ASSUMPTION OF THE BLESSED VIRGIN MARY
August 15, 2021
PASTOR: Rev. George A. Vrabel
Deac... |
CO-STAR: Conceptualisation of Stereotypes for Analysis and Reasoning
Author:
John Kwon
Supervisor:
Dr Anandha Gopalan
Submitted in partial fulfilment of the requirements for the MSc degree in Computing of Imperial College London
September 2021
Disclaimer
This report contains content which may be offensive or upse... |
Holland City News, Volume 67, Number 50: December 15, 1938
Follow this and additional works at: https://digitalcommons.hope.edu/hcn_1938
Part of the Archival Science Commons
Recommended Citation
Holland City News, "Holland City News, Volume 67, Number 50: December 15, 1938" (1938). Holland City News: 1938. 50. https... |
"FASTEST GUITAR ALIVE" PACKS EMBASSY
There's a saying going 'round Toronto these days that "The Embassy must be doing something right". They haven't had a turkey since Claude Gilbert took over the management of the Palm Grove Lounge. What he's doing right is bringing in the attractions that the just twenty-ones rememb... |
Fine Structural Morphology of Identified X- and Y-Cells in the Cat's Lateral Geniculate Nucleus
Author(s): J. R. Wilson, M. J. Friedlander and S. M. Sherman
Source: *Proceedings of the Royal Society of London. Series B, Biological Sciences*, Vol. 221, No. 1225 (Jun. 22, 1984), pp. 411-436
Published by: Royal Society... |
Osteoporosis and fragility fractures
A policy toolkit
The Health Policy Partnership
This toolkit was initiated and funded by Amgen (Europe) GmbH. See back cover for full details.
About this toolkit
Research, coordination and drafting of *Osteoporosis and fragility fractures: a policy toolkit* were led by Kirsten Bu... |
Graphic Design encompasses a wide range of activities from the design of traditional print media (e.g. books and posters) to site specific (e.g. signage systems) and electronic media (e.g. interfaces). Its practice always explores the new possibilities of information and communication technologies. Therefore, interacti... |
Specify
In 2000, the curators of the Angelo State Natural History Collections, with financial support from the National Science Foundation and the Texas Higher Education Coordinating Board Advanced Research Program (herbarium), began the formidable task of developing a computerized database of specimen records for eac... |
Smart Metering Implementation Programme: Consultation on the second version of the Smart Metering Equipment Technical Specifications
EDF Energy is one of the UK’s largest energy companies with activities throughout the energy chain. Our interests include nuclear, coal and gas-fired electricity generation, renewables, ... |
The Genie and the Bottle: Collateral Sources under the September 11th Victim Compensation Fund
Kenneth S. Abraham
Kyle D. Logue
Follow this and additional works at: https://via.library.depaul.edu/law-review
Recommended Citation
Kenneth S. Abraham & Kyle D. Logue, The Genie and the Bottle: Collateral Sources under th... |
DRAFT
A Vision for Sherman Oaks
OPPORTUNITIES/ GATEWAYS/ ELEMENTS THAT WILL ENRICH SHERMAN OAKS
JUNE 2014
SHERMAN OAKS NEIGHBORHOOD COUNCIL
INTRODUCTION
• A Vision for Sherman Oaks grew out of a need to understand the growth potential of our community and what benefits would enhance the lives of those of us who l... |
In this issue:
4. **Real-Time Visual Analytics: An Experiential Learning Activity for Undergraduates**
Paul Stephens, Bradley University
Jacob Young, Bradley University
13. **eXtensible Computing Curriculum Reporting Language (XCCRL)**
Jeffry Babb, West Texas A&M University
Jason Sharp, Tarleton State U... |
BIG COUNTRY
In a big feature
MICHAEL JACKSON and DAVID BOWIE
In the flesh in colour
Songs by Irene Cara, Kissing The Pink, Booker Newberry III and loads more
STARTS THIS WEEK
THE SPANDAU BALLET
No. 1 Martin Kemp INTERVIEWS
No helicopters in this week’s video spread. Instead, we talk to two musical fine artists – Ro... |
WEDNESDAY, MAY 20 - DINNER MEETING
"Now that you've cut city budgets, how do you pay for growth?"
The Good Table Restaurant
2600 Bancroft Way
Berkeley
(415) 548-4871
(r.s.v.p. to Joan Lamphier or call her for information at (415) 451-8046, leave message)
...wherein we will discuss the Planning Roundtable's first ma... |
Garth Brooks
1992 CCMA
Robertson and Berman to talk about NAFTA
Things are definitely heating up in regard to the exemption granted to Canadian cultural industries under the North American Free Trade Agreement (NAFTA).
Jay Berman, the president of the Recording Industry Association of America (RIAA) who recently ca... |
Reviews
"Oliver has done an exceptional job of highlighting the flawed logic in use in religious arguments today on all sides of the issue of faith."
"In this slim, well-written volume, Oliver presents an Islamist view of the world that should be read widely by people of all faiths for a greater understanding of Isla... |
DELTA$^2$ guidance on choosing the target difference and undertaking and reporting the sample size calculation for a randomised controlled trial
Jonathan A. Cook$^{1*}$, Steven A. Julious$^2$, William Sones$^1$, Lisa V. Hampson$^{3,4}$, Catherine Hewitt$^5$, Jesse A. Berlin$^6$, Deborah Ashby$^7$, Richard Emsley$^8$, ... |
IN THE CONSTITUTIONAL COURT OF SOUTH AFRICA
Case no:
SCA case no: 485/2012
NGHC case no: 77150/2009
In the matter between:
NATIONAL COMMISSIONER OF THE SOUTH AFRICAN POLICE SERVICE Applicant
and
SOUTHERN AFRICAN HUMAN RIGHTS LITIGATION CENTRE First respondent
ZIMBABWE EXILES FORUM Second respondent
FOUNDING AFFI... |
Transglutaminase in the Life and Death of the Pancreatic β-cell
Shakthi Dookie
Thesis submitted in partial fulfillment with the requirements of Nottingham Trent University for the degree of Doctor of Philosophy
June 2010
Tissue transglutaminase (TG2) is a ubiquitous enzyme that catalyses both the Ca$^{2+}$-dependen... |
DPM
MuchMoreMusic
The New Collection
disc one
Annie Lennox Why
Eric Clapton My Father's Eyes
Sting You Still Touch Me
Natalie Merchant Carnival
Seal Kiss From A Rose
Jann Arden The Sound Of
Amanda Marshall Dark Horse
Boyz II Men A Song For Mama
Vanessa Williams Save The Best For Last
Celine Dion It's All Coming Back ... |
MORPHOLOGY OF PHYSIOLOGICALLY IDENTIFIED W-CELLS IN THE C LAMINAE OF THE CAT'S LATERAL GENICULATE NUCLEUS
L. R. STANFORD, MICHAEL J. FRIEDLANDER,2 AND S. MURRAY SHERMAN3
Department of Neurobiology and Behavior, State University of New York at Stony Brook, Long Island, New York 11794
Abstract
The projections from th... |
Multipatch Unbiased Distance Non-Local Adaptive Means With Wavelet Shrinkage
Xiaoyao Li, Yicong Zhou\textsuperscript{✉}, Senior Member, IEEE, Jing Zhang, and Lianhong Wang
Abstract—Many existing non-local means (NLM) methods either use Euclidean distance to measure the similarity between patches, or compute weight $\... |
Sunflower County Consolidated School District
Miskia Davis, Superintendent
“United for Excellence”
APPROVED
SEP 14 2021
Sunflower Co Cons. School District
Board of Trustees
Instructional Management Plan
Office of Curriculum and Instruction
# Table of Contents
| Section ... |
Contribution à la robustesse des traitements fongiques et enzymatiques de contaminants organiques persistants dans des matrices environnementales complexes
Thèse de doctorat
Spécialité : Génie civil
Arielle Farida ARISTE
Sherbrooke (Québec) Canada
Novembre 2020
MEMBRES DU JURY
Professeur
Hubert CABANA
Directeur de... |
of our concept, next to the Japanese American National Museum and because they have an entrance and exit as well.
So far, our design meets the standards, the typical standards, but definitely we have to go through the process of working with everybody during this EIR, the draft of the report. And in addition to that, ... |
Batch-to-batch model improvement for cooling crystallization
Marco Forgione\textsuperscript{a,*}, Georgios Birpoutsoukis\textsuperscript{e}, Xavier Bombois\textsuperscript{a}, Ali Mesbah\textsuperscript{b}, Peter J. Daudey\textsuperscript{c}, Paul M.J. Van den Hof\textsuperscript{d}
\textsuperscript{a} Laboratoire Am... |
WORLD TOURISM DAY 2011
Tourism Linking Cultures
The Banker Awards 2010
The Banker
Bank of the Year 2010
NEPAL
नेपाल इन्वेस्टमेंट बैंक लि.
NEPAL INVESTMENT BANK LTD.
With each award,
We thank the true winners.
Our Clients, Employees, Stakeholders, Partners & Regulators
Winning our 4th Bank of the year award in 7 ... |
Putting Auction Theory to Work:
The Simultaneous Ascending Auction
Paul Milgrom
Stanford University
I review the uses of economic theory in the initial design and later improvement of the “simultaneous ascending auction,” which was developed initially for the sale of radio spectrum licenses in the United States. I an... |
LIQUID CRYSTAL DISPLAY DEVICE VIEWABLE FROM BOTH SURFACES AND PORTABLE APPARATUS USING SAME
VON BEIDEN OBERFLÄCHEN AUS BETRACHTBARE FLÜSSIGKRISTALLANZEIGEEINRICHTUNG UND TRAGBARE VORRICHTUNG DAMIT
DISPOSITIF D'AFFICHAGE A CRISTAUX LIQUIDES VISIBLE A PARTIR DE DEUX SURFACES ET APPAREIL PORTABLE UTILISANT LESDITS DISPO... |
A State of Emergency
- Nepal-China Tourism Agreement
- The Fall of Kabul
- Profile: Father Donnelly
नया Superior Pepsodent
GERMICHECK PLUS FORMULA
FLUORIDE को साथमा
NEW SUPERIOR
Pepsodent
FIGHTS GERMS EVEN HOURS AFTER BRUSHING
GERMICHECK PLUS
आफ्नौ Pepsodent ले दिनको दुई पटक अवश्य ब्रश गर्नुहोस्। दन्त चिकित्सक... |
6th Meeting of the Working Group on Alternative Reference Rates in Mexico (GTTR)
October 2022
Introduction
- At the previous meeting of the Working Group on Alternative Reference Rates in Mexico (GTTR) on July 5th, the proposed timeline and methodologies regarding the transition of TIIE rates with tenors greater than... |
THANK HEAVENS FOR PERCH
TARGETING BIG CHUB
QUEST FOR SPRING BREAM
BILL & VIRGINIA’S COMMERCIAL BREAKS
AT THE SHARP END! FIND THE PERFECT HOOK
CATCH YOUR FIRST ZANDER
Having recently ‘discovered’ the zander, Duncan Charman (who hasn’t changed his name to Cushelle) wants to spread the word.
Amazingly, with over fo... |
2021 SENTINEL LANDSCAPES ACCOMPLISHMENTS REPORT
SENTINELANDSCAPES.ORG
Cover photo credits: (clockwise)
U.S. Air Force F-15E Strike Eagles, U.S. Air Force photo by Staff Sgt. Eric Harris/Released; Fort Huachuca, Pacheco Conservation Easement photo by Arizona Land and Water Trust; Black duck at Blackwater National Wil... |
This is a repository copy of *Measurements of the $yvp \rightarrow p'\pi^+\pi^-$ cross section with the CLAS detector for 0.4 GeV$^2 < Q^2 < 1.0$ GeV$^2$ and 1.3 GeV$<W<1.825$ GeV*.
White Rose Research Online URL for this paper:
https://eprints.whiterose.ac.uk/135799/
Version: Published Version
**Article:**
Fedotov,... |
Beyond a One-Dimensional State: An Emerging Right to Autonomy?
Edited by Zelim A. Skurbaty
Martinus Nijhoff Publishers
## TABLE OF CONTENTS
### Autonomy and Cultural Rights
*The Argument of Cultural Disadvantage*
**Juha Räikkä** ........................................................................................ |
Highway Boondoggles
Wasted Money and America’s Transportation Future
WISPIRG Foundation
Highway Boondoggles
Wasted Money and America’s Transportation Future
WISPIRG Foundation
Jeff Inglis,
Frontier Group
Phineas Baxandall, Ph.D.,
U.S. PIRG Education Fund
September 2014
Acknowledgments
The authors wish to thank K... |
AN ORDINANCE TO AMEND CHAPTERS 4, 5, AND 28 OF THE TOWN OF CHEVY CHASE MUNICIPAL CODE TO CLARIFY APPLICABILITY.
WHEREAS, Maryland Code, Local Government Article, Section 5-202, as amended, authorizes the legislative body of each municipal corporation in the State of Maryland to pass ordinances that such legislative bo... |
Polar rotation angle identifies elliptic islands in unsteady dynamical systems
Mohammad Farazmand\textsuperscript{a,}\textsuperscript{*}, George Haller\textsuperscript{b}
\textsuperscript{a} Center for Nonlinear Science, School of Physics, Georgia Institute of Technology, 837 State Street, Atlanta GA 30332, USA
\text... |
BELL LABORATORIES RECORD
INDEX
VOLUME 26
January 1948 to December 1948
Bell Laboratories Record
Editor
PAUL B. FINDLEY
Science Editor
PHILIP C. JONES
Associate Editor
R. LINSLEY SHEPHERD
Assistant Editor
HELEN McLoughlin
Circulation
LEAH E. SMITH
BELL TELEPHONE LABORATORIES, INCORPORATED
463 West Street, New Y... |
Language and social power
Karodia, Ahmed Said
How to cite:
Karodia, Ahmed Said (1989) Language and social power. Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/6540/
Use policy
The full-text may be used and/or reproduced, and given to third parties in any format or ... |
Appendix I
*Phrynopus barthlmai*: Peru: Departamento Huánuco: about 15km southeast of Maraypata near Laguna Gwengu, 09°08'S, 76°05.60'W, 3680m elevation; MHNSM 20603–06, MHNSM 20448–50, MTD 4434–36, SMF 80465–47, SMF 80467–21.
*Phrynopus dagmarae*: Peru: Departamento Huánuco, Provincia Pachitea: Palma Pampa (09°53'12... |
CONTENTS
Provisional agenda (S/Agenda/2200) ........................................ 1
Adoption of the agenda ......................................................... 1
The situation in the occupied Arab territories:
(a) Letter dated 15 February 1980 from the Permanent Representative of Jordan to the United Nations... |
AGENDA
This meeting will be held in person and the public is welcome to attend.
Storey County Board of County Commissioners are hosting a teleconference meeting this month. Members of the public who wish to attend the meeting remotely, may do so by accessing the following meeting on Zoom.com. Public comment may be ma... |
A Climatology of Wintertime Barrier Winds off Southeast Greenland
B. E. Harden and I. A. Renfrew
University of East Anglia, Norwich, United Kingdom
G. N. Petersen
Icelandic Met Office, Reykjavik, Iceland
(Manuscript received 6 October 2010, in final form 23 February 2011)
ABSTRACT
A climatology of barrier wind... |
Holland City News, Volume 97, Number 38: September 19, 1968
Follow this and additional works at: https://digitalcommons.hope.edu/hcn_1968
Part of the Archival Science Commons
Recommended Citation
Holland City News, "Holland City News, Volume 97, Number 38: September 19, 1968" (1968). Holland City News: 1968. 38. htt... |
Estimating the Opportunity Costs of REDD+
A training manual
Version 1.3
March 2011
Estimating the opportunity costs of REDD+
A training manual
Version 1.3
March 2011
The findings, interpretations and conclusions herein are those of the author(s) and do not necessarily reflect the views of the International Bank fo... |
Effects of test administrations on general, test, and computer anxiety, and efficacy measures
Susan Kiskis
Follow this and additional works at: https://scholarworks.lib.csusb.edu/etd-project
Part of the Educational Psychology Commons
Recommended Citation
Kiskis, Susan, "Effects of test administrations on general, t... |
Dosing methods in ECT
Should the Scandinavian time-titration method be resumed?
NACT 16th Nordic Experience Meeting | Tallinn, May 25-27, 2022
Per Bergsholm, M.D., dr. med.
Psychiatrist, District General Hospital of Førde, Norway
One day in 2018, I sat in my home in Førde, Western Norway, screening PubMed on electro... |
About the Sweetwater County Adult Protection Team
The Sweetwater County Adult Protection Team is a multi-disciplinary team formed in 1996. The Team obtains its legal authority from statutes in compliance with Wyoming Statute 35-20-102 through 108 and the Adult Protection Rules of the Wyoming Department of Family Servi... |
This thesis is made available online and is protected by original copyright.
Please scroll down to view the document itself.
Please refer to the repository record for this item for information to help you to cite it. Our policy information is available from the repository home page.
Synthesis of Oligomers / Polymers... |
REM
have rivalled for years. The club was launched two years ago, attracting 800,000 members which immediately caused a drop in pricing of club CDs as a direct result of the newly created competitive arena.
"The only conclusion one can make on Warner's renegeing on its initial agreement to supply BMG with product is ... |
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