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Copolymerization of lactones and bioaromatics via concurrent ring-opening polymerization/polycondensation

Profile image of Pengxu QiPengxu Qi

2017, Green Chemistry

https://doi.org/10.1039/C6GC03238A
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198 pages

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Abstract

Concurrent ring-opening polymerization/polycondensation of lactones and bioaromatic hydroxy-acids yields random copolymers with improved and controlled thermal properties.

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2-Chloroethanol was purchased from Acros Organics. Syringic acid was purchased from AK Scientific and vanillic acid was purchased from ICC Indofine. «¢- Caprolactone was purchased from Acros Organics and distilled before use. L-lactide (PURASORB®) was purified by sublimation and stored in the glovebox before use. These were all utilized without further purification. NMR solvents, including deuterated 1,1,2,2- tetrachloroethane (TCE-d,) deuterated chloroform (CDCI,), deuterated dimethyl sulfoxide (DMSO-d,), and deuterated trifluoroacetic acid (TFA-d) were purchased from Cambridge Isotope Laboratories. All other chemicals, unless expressly mentioned, were utilized as received. Via alibaba.com, ferulic acid (99%) was purchased from Xian Erica Botanical Products Co. or from Nanjing Zelang Medical Technology Co. and p-coumaric acid (99%) was purchased from Nanjing Zelang Medical Technology Co.
2-Chloroethanol was purchased from Acros Organics. Syringic acid was purchased from AK Scientific and vanillic acid was purchased from ICC Indofine. «¢- Caprolactone was purchased from Acros Organics and distilled before use. L-lactide (PURASORB®) was purified by sublimation and stored in the glovebox before use. These were all utilized without further purification. NMR solvents, including deuterated 1,1,2,2- tetrachloroethane (TCE-d,) deuterated chloroform (CDCI,), deuterated dimethyl sulfoxide (DMSO-d,), and deuterated trifluoroacetic acid (TFA-d) were purchased from Cambridge Isotope Laboratories. All other chemicals, unless expressly mentioned, were utilized as received. Via alibaba.com, ferulic acid (99%) was purchased from Xian Erica Botanical Products Co. or from Nanjing Zelang Medical Technology Co. and p-coumaric acid (99%) was purchased from Nanjing Zelang Medical Technology Co.
The polymerizations were typically conducted in a rounc bottom flask, connected to a rotary evaporation bumr trap, connected to a vacuum line. With this apparatus, t by-product of condensation could be collected and seen the bump trap. At the same time, all volatiles could removed without changing the initial glassware configuration. Polymerizations were performed und ambient light, except the copolymer series witt hydroxyethylferulic acid and hydroxyethylcoumaric acid. which were conducted in the dark by covering t apparatus in aluminum foil. See below. he ir be el ne The copolymers of hydroxyethylsyringic acid and e- caprolactone were dissolved in 6 mL tetrachloroethane. These polymers were precipitated by pouring the polymer solution into 150 mL of cold methanol and cooling in the freezer overnight. These polymers were isolated by filtration and washed with methanol. The polymers were then dried under vacuum overnight. All other polymers were melted to remove them from the flask and used without further purification.
The polymerizations were typically conducted in a rounc bottom flask, connected to a rotary evaporation bumr trap, connected to a vacuum line. With this apparatus, t by-product of condensation could be collected and seen the bump trap. At the same time, all volatiles could removed without changing the initial glassware configuration. Polymerizations were performed und ambient light, except the copolymer series witt hydroxyethylferulic acid and hydroxyethylcoumaric acid. which were conducted in the dark by covering t apparatus in aluminum foil. See below. he ir be el ne The copolymers of hydroxyethylsyringic acid and e- caprolactone were dissolved in 6 mL tetrachloroethane. These polymers were precipitated by pouring the polymer solution into 150 mL of cold methanol and cooling in the freezer overnight. These polymers were isolated by filtration and washed with methanol. The polymers were then dried under vacuum overnight. All other polymers were melted to remove them from the flask and used without further purification.
“1 mol% catalyst except 0.5 mol% hydrotalcite; TBD = triazabicyclodecene; melted under argon for 5 hours with a temperature ramp from 150 to 200 °C; 8 hours dynamic vacuum at 200 °C. °GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. ‘Determined by DSC. “4 hours dynamic vacuum at 200 °C then 4 hours at 220 °C. “Bump trap charged with 1.5 equivalents of P2Os. Table S1. ROP polycondensation optimization conditions for the copolymer of ¢-caprolactone and hydroxyethylsyringic acid prepared with < 20:80 ratio of monomers. respectively.”
“1 mol% catalyst except 0.5 mol% hydrotalcite; TBD = triazabicyclodecene; melted under argon for 5 hours with a temperature ramp from 150 to 200 °C; 8 hours dynamic vacuum at 200 °C. °GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. ‘Determined by DSC. “4 hours dynamic vacuum at 200 °C then 4 hours at 220 °C. “Bump trap charged with 1.5 equivalents of P2Os. Table S1. ROP polycondensation optimization conditions for the copolymer of ¢-caprolactone and hydroxyethylsyringic acid prepared with < 20:80 ratio of monomers. respectively.”
Table S2. Polymerization results and characterization of copolymers prepared from a-caprolactone and bioaromatics HESA, HEVA, HEFA, and HECA.“ “1 mol% Sb2O3. °1.5 eq. of P2Os; melted under argon for 5 hours with a temperature ramp from 150 to 200 °C; 8 hours dynamic vacuum at 200 °C. °3.0 eq. of MgSO,; melted under argon for 22 hours with a temperature ramp from 175 to 240 °C; 8 hours dynamic vacuum at 240 °C. “No drying agent; melted under argon for 20 hours with a temperature ramp from 165 to 240 °C; 6 hours dynamic vacuum at 240 °C. “Comonomer incorporation determined by 'H NMR. ‘GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. Determined by DSC. “Determined by TGA; temperature at which 5% mass loss is observed under nitrogen. ‘Insolubility of the polymers prevented GPC analysis.
Table S2. Polymerization results and characterization of copolymers prepared from a-caprolactone and bioaromatics HESA, HEVA, HEFA, and HECA.“ “1 mol% Sb2O3. °1.5 eq. of P2Os; melted under argon for 5 hours with a temperature ramp from 150 to 200 °C; 8 hours dynamic vacuum at 200 °C. °3.0 eq. of MgSO,; melted under argon for 22 hours with a temperature ramp from 175 to 240 °C; 8 hours dynamic vacuum at 240 °C. “No drying agent; melted under argon for 20 hours with a temperature ramp from 165 to 240 °C; 6 hours dynamic vacuum at 240 °C. “Comonomer incorporation determined by 'H NMR. ‘GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. Determined by DSC. “Determined by TGA; temperature at which 5% mass loss is observed under nitrogen. ‘Insolubility of the polymers prevented GPC analysis.
“1 mol% Sb203. °3.0 eq. of MgSO4; melted under argon for 40 hours with a temperature ramp from 160 to 180 °C; 8 hours dynamic vacuum at 180 °C. °3.0 eq. of MgSO,; melted under argon for 40 hours with a temperature ramp from 160 to 200 °C; 8 hours dynamic vacuum at 200 °C. “No drying agent; melted under argon for 40 hours with a temperature ramp from 160 to 220 °C; 8 hours dynamic vacuum at 220 °C. ‘Comonomer incorporation determined by 'H NMR. /GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. ‘Determined by DSC. "Determined by TGA; temperature at which 5% mass loss is observed under nitrogen. ‘Insolubility of the polymers prevented GPC analysis. Table $3. Polymerization results and characterization of copolymers prepared from L-lactide and bioaromatics HESA, HEVA, HEFA, and HECA.“
“1 mol% Sb203. °3.0 eq. of MgSO4; melted under argon for 40 hours with a temperature ramp from 160 to 180 °C; 8 hours dynamic vacuum at 180 °C. °3.0 eq. of MgSO,; melted under argon for 40 hours with a temperature ramp from 160 to 200 °C; 8 hours dynamic vacuum at 200 °C. “No drying agent; melted under argon for 40 hours with a temperature ramp from 160 to 220 °C; 8 hours dynamic vacuum at 220 °C. ‘Comonomer incorporation determined by 'H NMR. /GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. ‘Determined by DSC. "Determined by TGA; temperature at which 5% mass loss is observed under nitrogen. ‘Insolubility of the polymers prevented GPC analysis. Table $3. Polymerization results and characterization of copolymers prepared from L-lactide and bioaromatics HESA, HEVA, HEFA, and HECA.“
Figure S1. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 1).
Figure S1. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 1).
Figure 82. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 2).
Figure 82. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 2).
Figure S3. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 3).
Figure S3. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 3).
Figure S4. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 4).
Figure S4. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 4).
Figure S5. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 5).
Figure S5. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 5).
Figure S6. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 6).
Figure S6. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 6).
Figure $7. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 7).
Figure $7. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 7).
Figure S8. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 8).
Figure S8. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 8).
Figure S9. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 8 and Table S2 entry 9).
Figure S9. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 8 and Table S2 entry 9).
Figure $10. GPC Chromatogram of polycaprolactone (Table S2, entry 1).
Figure $10. GPC Chromatogram of polycaprolactone (Table S2, entry 1).
Figure S11. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2)
Figure S11. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2)
Figure S12. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3).
Figure S12. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3).
Figure S13. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table S2, entry 4)
Figure S13. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table S2, entry 4)
Figure § S14. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure § S14. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure $15. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6)
Figure $15. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6)
Figure S16. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7)
Figure S16. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7)
Figure S17. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure S17. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure $18. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure $18. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure $20. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [90:10] (Table S2, entry 12). Figure S19. GPC Chromatogram of polyethylene syringate (Table S2, entry 21).
Figure $20. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [90:10] (Table S2, entry 12). Figure S19. GPC Chromatogram of polyethylene syringate (Table S2, entry 21).
Figure | $21. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [80:20] (Table S2, entry 13)
Figure | $21. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [80:20] (Table S2, entry 13)
Figure $22. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [70:30] (Table 2, entry 14).
Figure $22. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [70:30] (Table 2, entry 14).
Figure $23. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [60:40] (Table S2, entry 15).
Figure $23. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [60:40] (Table S2, entry 15).
Figure $25. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [40:60] (Table S2, entry 17).
Figure $25. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [40:60] (Table S2, entry 17).
Figure | $26. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [30:70] (Table S2, entry 18).
Figure | $26. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [30:70] (Table S2, entry 18).
Figure S27. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [20:80] (Table S2, entry 19
Figure S27. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [20:80] (Table S2, entry 19
Figure $28. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [10:90] (Table S2, entry 20).
Figure $28. GPC Chromatogram of copoly(caprolactone/ hydroxyethylvanilic acid) [10:90] (Table S2, entry 20).
Figure S29. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table S2, entry 22).
Figure S29. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table S2, entry 22).
Figure | $31. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure | $31. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $32. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure $32. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure | $33. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26)
Figure | $33. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26)
Figure S34. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27).
Figure S34. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27).
Figure $35. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28)
Figure $35. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28)
Figure $36. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29).
Figure $36. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29).
Figure | S837. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure | S837. GPC Chromatogram of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure S39. GPC Chromatogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32)
Figure S39. GPC Chromatogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32)
Figure S41. GPC Chromatogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34)
Figure S41. GPC Chromatogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34)
Figure $43. GPC Chromatogram of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table S3, entry 2).
Figure $43. GPC Chromatogram of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table S3, entry 2).
Figure S45. GPC Chromatogram of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table S3, entry 4).
Figure S45. GPC Chromatogram of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table S3, entry 4).
Figure S46. GPC Chromatogram of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table S3, entry 5).
Figure S46. GPC Chromatogram of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table S3, entry 5).
Figure S47. GPC Chromatogram of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table S3, entry 7).
Figure S47. GPC Chromatogram of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table S3, entry 7).
Figure S49. GPC Chromatogram of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table S3, entry 9).
Figure S49. GPC Chromatogram of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table S3, entry 9).
Figure S51. GPC Chromatogram of copoly(L-lactide/ hydroxyethylferulic acid) [90:10] (Table S3, entry 12).
Figure S51. GPC Chromatogram of copoly(L-lactide/ hydroxyethylferulic acid) [90:10] (Table S3, entry 12).
Figure S53. GPC Chromatogram of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table S3, entry 14).
Figure S53. GPC Chromatogram of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table S3, entry 14).
Figure S56. GPC Chromatogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table S3, entry 18) Figure S55. GPC Chromatogram of copoly(L-lactide/ hydroxyethylferulic acid) [20:80] (Table S3, entry 16).
Figure S56. GPC Chromatogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table S3, entry 18) Figure S55. GPC Chromatogram of copoly(L-lactide/ hydroxyethylferulic acid) [20:80] (Table S3, entry 16).
Figure S58. GPC Chromatogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure S58. GPC Chromatogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure S59. GPC Chromatogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
Figure S59. GPC Chromatogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
‘igure $61. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
‘igure $61. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure S62. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure S62. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
‘igure. $63. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
‘igure. $63. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure S64. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4)
Figure S64. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4)
Figure S65. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entr 5).
Figure S65. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entr 5).
Figure S66. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6).
Figure S66. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6).
Figure S67. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure S67. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure | S68. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure | S68. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure S69. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9).
Figure S69. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9).
Figure S71. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entr 11).
Figure S71. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entr 11).
Figure $72. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure $72. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure S73. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13
Figure S73. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13
Figure S74. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure S74. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
‘igure S75. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
‘igure S75. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Figure S76. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16)
Figure S76. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16)
Figure S77 . GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure S77 . GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure $78. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table S4, entr 18).
Figure $78. GPC Chromatogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table S4, entr 18).
Figure S79. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 1).
Figure S79. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 1).
Figure S81. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 3).
Figure S81. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 3).
Figure S82. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 5).
Figure S82. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 5).
Figure S84. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 7). Figure S83. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 6).
Figure S84. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 7). Figure S83. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 6).
Figure S85. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 8).
Figure S85. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 8).
Figure S86. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 9 and Table S2. entry 9).
Figure S86. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S1, entry 9 and Table S2. entry 9).
Figure S88. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure S88. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure S90. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table S2, entry 4).
Figure S90. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table S2, entry 4).
Figure S92. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure S92. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure $93. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7).
Figure $93. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7).
Figure S94. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure S94. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure S95. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure S95. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure S97. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S2, entry 12).
Figure S97. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S2, entry 12).
Figure S98. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure S98. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure S99. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure S99. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure $101. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [50:50] (Table S2, entry 16).
Figure $101. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [50:50] (Table S2, entry 16).
Figure $102. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $102. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $103. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18).
Figure $103. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18).
Figure $104. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [20:80] (Table S2, entry 19).
Figure $104. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [20:80] (Table S2, entry 19).
Figure $105. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [10:90] (Table S2, entry 20).
Figure $105. DSC Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [10:90] (Table S2, entry 20).
Figure $108. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23). Figure $107. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table $2, entry 22).
Figure $108. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23). Figure $107. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table $2, entry 22).
Figure $109. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $109. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $110. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure $110. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure $112. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27). Figure S111. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure $112. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27). Figure S111. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure $114. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29). Figure $113. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure $114. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29). Figure $113. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure $115. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure $115. DSC Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure $118. DSC Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33). Figure $117. DSC Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32).
Figure $118. DSC Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33). Figure $117. DSC Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32).
Figure $119. DSC Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34).
Figure $119. DSC Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34).
Figure $122. DSC Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table S3, entry 2).
Figure $122. DSC Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table S3, entry 2).
Figure $123. DSC Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [60:40] (Table S3, entry 3).
Figure $123. DSC Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [60:40] (Table S3, entry 3).
Figure S125. DSC Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table S3, entry 5).
Figure S125. DSC Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table S3, entry 5).
Figure $126. DSC Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table S3, entry 7).
Figure $126. DSC Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table S3, entry 7).
Figure $127. DSC Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table $3, entry 8).
Figure $127. DSC Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table $3, entry 8).
Figure $129. DSC Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [20:80] (Table S3, entry 9).
Figure $129. DSC Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [20:80] (Table S3, entry 9).
Figure $132. DSC Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table S3, entry 14). Figure $131. DSC Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table S3, entry 13).
Figure $132. DSC Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table S3, entry 14). Figure $131. DSC Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table S3, entry 13).
Figure $133. DSC Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table S3, entry 15).
Figure $133. DSC Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table S3, entry 15).
Figure $136. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [80:20] (Table S3, entry 19). Figure $135. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table $3, entry 18).
Figure $136. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [80:20] (Table S3, entry 19). Figure $135. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table $3, entry 18).
Figure $137. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure $137. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure $138. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
Figure $138. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
Figure $140. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1). Figure S139. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [20:80] (Table S3, entry 22).
Figure $140. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1). Figure S139. DSC Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [20:80] (Table S3, entry 22).
Figure $141. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure $141. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure $8142. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure $8142. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure $143. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4).
Figure $143. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4).
Figure $144. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entr 5).
Figure $144. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entr 5).
Figure $145. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6).
Figure $145. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6).
Figure S146. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure S146. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure S148. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 0) Figure $147. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure S148. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 0) Figure $147. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
ee ee: eee Figure $149. DSC Thermogram of copoly(caprolactone/ ‘hydroxyethylsyringic acid) [50:50] at 4 hours (Table S4, entry 10).
ee ee: eee Figure $149. DSC Thermogram of copoly(caprolactone/ ‘hydroxyethylsyringic acid) [50:50] at 4 hours (Table S4, entry 10).
Figure $150. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table $4, entry 11).
Figure $150. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table $4, entry 11).
Figure S152. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13). Figure $151. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure S152. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13). Figure $151. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure $153. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure $153. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure $154. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Figure $154. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Re ee Figure $155. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16)
Re ee Figure $155. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16)
Figure $156. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entr 17).
Figure $156. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entr 17).
Figure $157. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table S4, entry 18).
Figure $157. DSC Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table S4, entry 18).
rhermogravimetric Analysis (TGA) Thermograms
rhermogravimetric Analysis (TGA) Thermograms
Figure $159. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure $159. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure S160. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3).
Figure S160. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3).
Figure $162. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure $162. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure S163. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure S163. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure $164. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7).
Figure $164. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7).
Figure $165. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure $165. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure $166. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S2, entry 9).
Figure $166. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S2, entry 9).
Figure S167. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure S167. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure $168. TGA Thermogram of polyethylene synringate (Table S2, entry 11).
Figure $168. TGA Thermogram of polyethylene synringate (Table S2, entry 11).
Figure $169. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S2, entry 12).
Figure $169. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S2, entry 12).
Figure $170. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure $170. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure $171. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure $171. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure $172. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [60:40] (Table S2, entry 15).
Figure $172. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [60:40] (Table S2, entry 15).
Figure $174. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $174. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $175. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18).
Figure $175. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18).
Figure S176. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [20:80] (Table S2, entry 19).
Figure S176. TGA Thermogram of copoly(caprolactone/ hydroxyethylvanillic acid) [20:80] (Table S2, entry 19).
Figure $178. TGA Thermogram of polyethylene vanillate (Table S2, entry 21).
Figure $178. TGA Thermogram of polyethylene vanillate (Table S2, entry 21).
Figure $179. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table S2, entry 22).
Figure $179. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table S2, entry 22).
Figure S180. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23).
Figure S180. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23).
Figure $181. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $181. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $182. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure $182. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure $183. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure $183. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure S184. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S3, entry 37).
Figure S184. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S3, entry 37).
Figure $185. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure $185. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure $186. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29).
Figure $186. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29).
Figure 8187. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure 8187. TGA Thermogram of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure $189. TGA Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32). Figure S188. TGA Thermogram of polyethylene ferulate (Table 82, entry 31).
Figure $189. TGA Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32). Figure S188. TGA Thermogram of polyethylene ferulate (Table 82, entry 31).
Figure 8190. TGA Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33).
Figure 8190. TGA Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33).
Figure $191. TGA Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34).
Figure $191. TGA Thermogram of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34).
remperature (| UY) Figure $193. TGA Thermogram of polylactic acid (Table S3, entry 1). Figure $192. TGA Thermogram of polyethylene coumarate (Table 82, entry 35).
remperature (| UY) Figure $193. TGA Thermogram of polylactic acid (Table S3, entry 1). Figure $192. TGA Thermogram of polyethylene coumarate (Table 82, entry 35).
tigure $194. TGA Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table $3, entry 2).
tigure $194. TGA Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table $3, entry 2).
Figure $196. TGA Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table $3, entry 4).
Figure $196. TGA Thermogram of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table $3, entry 4).
Figure S198. TGA Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table $3, entry 7).
Figure S198. TGA Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table $3, entry 7).
Figure $199. TGA Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table S3, entry 8).
Figure $199. TGA Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table S3, entry 8).
Figure S200. TGA Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table S3, entry 9).
Figure S200. TGA Thermogram of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table S3, entry 9).
Figure $202. TGA Thermogram of copoly(L-lactide/ hydroxyethyl ferulic acid) [90:10] (Table $3, entry 12).
Figure $202. TGA Thermogram of copoly(L-lactide/ hydroxyethyl ferulic acid) [90:10] (Table $3, entry 12).
Figure $203. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table $3, entry 13).
Figure $203. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table $3, entry 13).
Figure $204. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table $3, entry 14).
Figure $204. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table $3, entry 14).
Figure S205. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table S3, entry 15).
Figure S205. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table S3, entry 15).
Figure S206. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [20:80] (Table S3, entry 16).
Figure S206. TGA Thermogram of copoly(L-lactide/ hydroxyethylferulic acid) [20:80] (Table S3, entry 16).
Figure S208. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [80:20] (Table S3, entry 19).
Figure S208. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [80:20] (Table S3, entry 19).
Figure S209. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure S209. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure 8210. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
Figure 8210. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
Figure S211. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [20:80] (Table S3, entry 22).
Figure S211. TGA Thermogram of copoly(L-lactide/ hydroxyethylcoumaric acid) [20:80] (Table S3, entry 22).
Figure $8212. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure $8212. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure 8214. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure 8214. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure S216. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5).
Figure S216. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5).
Figure $218. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure $218. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure $8220. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9).
Figure $8220. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9).
Figure $222. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entry 11).
Figure $222. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entry 11).
Figure $224. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13)
Figure $224. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13)
Figure 8225. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure 8225. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure 8226. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Figure 8226. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Figure 8227. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16).
Figure 8227. TGA Thermogram of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16).
ere wee AES we gay Figure $228. TGA Thermogram of copoly(caprolactone/ ‘hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
ere wee AES we gay Figure $228. TGA Thermogram of copoly(caprolactone/ ‘hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure 8233. 'H NMR spectrum of hydroxyethylvanillic acid.
Figure 8233. 'H NMR spectrum of hydroxyethylvanillic acid.
Figure $234. 'H NMR spectrum of polycaprolactone (Table $2, entry 1).
Figure $234. 'H NMR spectrum of polycaprolactone (Table $2, entry 1).
Figure 8235. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure 8235. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure S236. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3).
Figure S236. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3).
i al i | Figure $237. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table $2, entry 4).
i al i | Figure $237. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table $2, entry 4).
Figure 8238. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure 8238. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure $239. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure $239. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
ee eT a Dee ee SU ee Figure $240. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [40:30] (Table S2, entry 7).
ee eT a Dee ee SU ee Figure $240. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [40:30] (Table S2, entry 7).
ee a we ne ee ee Figure $242. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table 82, entry 9). Figure $241. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
ee a we ne ee ee Figure $242. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table 82, entry 9). Figure $241. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure $243. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure $243. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10).
Figure $244. 'H NMR spectrum of polyethylene syringate (Table 82, entry 11)
Figure $244. 'H NMR spectrum of polyethylene syringate (Table 82, entry 11)
Figure $245. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S2, entry 12). $132
Figure $245. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S2, entry 12). $132
Figure S246. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure S246. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
a ae Figure $247. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
a ae Figure $247. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure $248. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [60:40] (Table S2, entry 15).
Figure $248. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [60:40] (Table S2, entry 15).
Figure S249. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [50:50] (Table S2, entry 16).
Figure S249. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [50:50] (Table S2, entry 16).
Figure $250. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $250. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $251. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18)
Figure $251. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18)
Figure $252. 'd NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [20:80] (Table S2, entry 19).
Figure $252. 'd NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [20:80] (Table S2, entry 19).
Figure $253. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [10:90] (Table S2, entry 20).
Figure $253. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [10:90] (Table S2, entry 20).
Figure $254. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table S2, entry 22).
Figure $254. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [90:10] (Table S2, entry 22).
Figure S255. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23).
Figure S255. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23).
Figure $256. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $256. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
POT ENCSES me OPES Apres Figure $257. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
POT ENCSES me OPES Apres Figure $257. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
‘igure $258. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
‘igure $258. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure $259. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27).
Figure $259. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27).
Figure S260. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure S260. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure $261. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29).
Figure $261. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [20:80] (Table S2, entry 29).
Figure $262. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure $262. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [10:90] (Table S2, entry 30).
Figure 8263. 'H NMR spectrum of polyethylene ferulate (Table S2, entry 31).
Figure 8263. 'H NMR spectrum of polyethylene ferulate (Table S2, entry 31).
Figure $264. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32).
Figure $264. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32).
Figure $265. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33).
Figure $265. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33).
Figure $266. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34).
Figure $266. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [20:80] (Table S2, entry 34).
Figure S267. 'H NMR spectrum of polyethylene coumarate (Table S2, entry 35) Figure S268. 'H NMR spectrum of polylactic acid (Table $3, entry 1).
Figure S267. 'H NMR spectrum of polyethylene coumarate (Table S2, entry 35) Figure S268. 'H NMR spectrum of polylactic acid (Table $3, entry 1).
Figure S270. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [60:40] (Table S3, entry 3).
Figure S270. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [60:40] (Table S3, entry 3).
Figure $271. 'd NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table S3, entry 4)
Figure $271. 'd NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table S3, entry 4)
Figure S272. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table $3, entry 5)
Figure S272. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table $3, entry 5)
Ee ee eee ee Ee Figure S273. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table S3, entry 7).
Ee ee eee ee Ee Figure S273. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table S3, entry 7).
Figure $274. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table S3, entry 8).
Figure $274. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table S3, entry 8).
Figure $275. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table $3, entry 9).
Figure $275. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table $3, entry 9).
Figure $276. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [20:80] (Table $3, entry 10).
Figure $276. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [20:80] (Table $3, entry 10).
Figure $277. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [90:10] (Table $3, entry 12).
Figure $277. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [90:10] (Table $3, entry 12).
Figure S278. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table $3, entry 13).
Figure S278. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table $3, entry 13).
NSE TSEC TINEES COU TEER A Epee ely Figure S279. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table S3, entry 14).
NSE TSEC TINEES COU TEER A Epee ely Figure S279. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table S3, entry 14).
Figure S280. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table $3, entry 15).
Figure S280. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table $3, entry 15).
Figure $281. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [20:80] (Table $3, entry 16).
Figure $281. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [20:80] (Table $3, entry 16).
Figure $282. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table S3, entry 18).
Figure $282. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table S3, entry 18).
Figure $283. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [80:20] (Table $3, entry 19).
Figure $283. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [80:20] (Table $3, entry 19).
Figure S284. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure S284. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
a eee ee ee ee Figure $285. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
a eee ee ee ee Figure $285. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table S3, entry 21).
Figure S286. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [20:80] (Table S3, entry 22).
Figure S286. 'H NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [20:80] (Table S3, entry 22).
Figure S287. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure S287. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure $288. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure $288. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure $289. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure $289. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3).
Figure 8290. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4).
Figure 8290. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4).
Figure $291. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5).
Figure $291. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5).
Figure S292. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6)
Figure S292. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6)
Figure S293. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7 C1412
Figure S293. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7 C1412
Figure $294. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure $294. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure $295. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9).
Figure $295. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9).
Figure $296. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4 hours (Table S4, entry 10). $149
Figure $296. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4 hours (Table S4, entry 10). $149
Figure 8297. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entry 11).
Figure 8297. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entry 11).
Figure $298. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure $298. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure S299. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13).
Figure S299. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13).
Figure $300. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure $300. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure $301. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15). g
Figure $301. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15). g
Figure S302. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16).
Figure S302. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16).
Figure $303. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure $303. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure $304. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table $4, entry 18).
Figure $304. 'H NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table $4, entry 18).
Figure $308. ‘°C NMR spectrum of hydroxyethylvanillic acid.
Figure $308. ‘°C NMR spectrum of hydroxyethylvanillic acid.
Figure $311. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3). Figure $310. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure $311. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [80:20] (Table S2, entry 3). Figure $310. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [90:10] (Table S2, entry 2).
Figure $312. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table S2, entry 4).
Figure $312. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [70:30] (Table S2, entry 4).
Figure $313. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure $313. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [60:40] (Table S2, entry 5).
Figure $315. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7) Figure S314. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure $315. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [40:60] (Table S2, entry 7) Figure S314. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] (Table S2, entry 6).
Figure $316. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure $316. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [30:70] (Table S2, entry 8).
Figure $318. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10). Figure $317. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S2, entry 9).
Figure $318. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [10:90] (Table S2, entry 10). Figure $317. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [20:80] (Table S2, entry 9).
Figure $319. '°C NMR spectrum of polyethylene syringate (Table $2, entry 11).
Figure $319. '°C NMR spectrum of polyethylene syringate (Table $2, entry 11).
Figure $320. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S3, entry 12).
Figure $320. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [90:10] (Table S3, entry 12).
Figure S321. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure S321. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [80:20] (Table S2, entry 13).
Figure $322. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure $322. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [70:30] (Table S2, entry 14).
Figure $323. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [60:40] (Table S2, entry 15).
Figure $323. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [60:40] (Table S2, entry 15).
Figure $324. °C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [50:50] (Table S2, entry 16).
Figure $324. °C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [50:50] (Table S2, entry 16).
Figure $325. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure $325. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [40:60] (Table S2, entry 17).
Figure S326. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18).
Figure S326. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylvanillic acid) [30:70] (Table S2, entry 18).
Figure $327. '°C NMR spectrum of copoly(caprolactone/ hydroxyethyl ferulic acid) [90:10] (Table S2, entry 22).
Figure $327. '°C NMR spectrum of copoly(caprolactone/ hydroxyethyl ferulic acid) [90:10] (Table S2, entry 22).
Figure $328. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23).
Figure $328. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [80:20] (Table S2, entry 23).
Figure $329. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure $329. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [70:30] (Table S2, entry 24).
Figure S330. °C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure S330. °C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [60:40] (Table S2, entry 25).
Figure $331. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure $331. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [50:50] (Table S2, entry 26).
Figure $332. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27).
Figure $332. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [40:60] (Table S2, entry 27).
Figure S333. '*C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure S333. '*C NMR spectrum of copoly(caprolactone/ hydroxyethylferulic acid) [30:70] (Table S2, entry 28).
Figure $334. '°C NMR spectrum of polyethylene ferulate (Table S2, entry 31). Figure $335. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32).
Figure $334. '°C NMR spectrum of polyethylene ferulate (Table S2, entry 31). Figure $335. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [80:20] (Table S2, entry 32).
Figure S336. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33).
Figure S336. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylcoumaric acid) [50:50] (Table S2, entry 33).
Figure $337. '°C NMR spectrum of polyethylene coumarate (Table 82, entry 35).
Figure $337. '°C NMR spectrum of polyethylene coumarate (Table 82, entry 35).
Figure S338. '°C NMR spectrum of polylactic acid (Table $3, entry 1).
Figure S338. '°C NMR spectrum of polylactic acid (Table $3, entry 1).
Figure $339. °C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table $3, entry 2).
Figure $339. °C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [80:20] (Table $3, entry 2).
Figure $340. °C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [60:40] (Table S3, entry 3).
Figure $340. °C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [60:40] (Table S3, entry 3).
Figure S341. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table S3, entry 4).
Figure S341. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [40:60] (Table S3, entry 4).
Figure $342. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table S3, entry 5).
Figure $342. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylsyringic acid) [20:80] (Table S3, entry 5).
Figure S343. °C NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table $3, entry 7).
Figure S343. °C NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [80:20] (Table $3, entry 7).
Figure $344. °C NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table S3, entry 8).
Figure $344. °C NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [60:40] (Table S3, entry 8).
Figure $345. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table S3, entry 9).
Figure $345. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylvanillic acid) [40:60] (Table S3, entry 9).
Figure S346. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [90:10] (Table S3, entry 12).
Figure S346. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [90:10] (Table S3, entry 12).
Figure $347. °C NMR spectrum of c copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table $3, entry 13).
Figure $347. °C NMR spectrum of c copoly(L-lactide/ hydroxyethylferulic acid) [80:20] (Table $3, entry 13).
Figure $348. °C NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table $3, entry 14).
Figure $348. °C NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [70:30] (Table $3, entry 14).
Figure $349. °C NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table $3, entry 15).
Figure $349. °C NMR spectrum of copoly(L-lactide/ hydroxyethylferulic acid) [60:40] (Table $3, entry 15).
Figure $350. °C NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table S3, entry 18).
Figure $350. °C NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [90:10] (Table S3, entry 18).
Figure $351. '°C NMR spectrum of c copoly(L-lactide/ hydroxyethyleoumaric acid) [80:20] (Table S3, entry 19).
Figure $351. '°C NMR spectrum of c copoly(L-lactide/ hydroxyethyleoumaric acid) [80:20] (Table S3, entry 19).
Figure S352. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure S352. '°C NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [70:30] (Table S3, entry 20).
Figure S353. °C NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table 3, entry 21).
Figure S353. °C NMR spectrum of copoly(L-lactide/ hydroxyethylcoumaric acid) [60:40] (Table 3, entry 21).
Figure $354. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure $354. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1).
Figure S355. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure S355. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2).
Figure $356. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table $4, entry 3)
Figure $356. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 30 min. (Table $4, entry 3)
Figure $357. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4).
Figure $357. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4).
Figure $358. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5).
Figure $358. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5).
Figure $359. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6). 0171 ‘igure S359. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6).
Figure $359. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6). 0171 ‘igure S359. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6).
Figure $360. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure $360. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7).
Figure $361. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure $361. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8).
Figure S362. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entr 9).
Figure S362. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entr 9).
Figure $363. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4 hours (Table S4, entry 10).
Figure $363. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4 hours (Table S4, entry 10).
Figure $364. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entry 11).
Figure $364. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 4.5 hours (Table S4, entry 11).
Figure S365. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure S365. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 5 hours (Table S4, entry 12).
Figure S366. '*C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13).
Figure S366. '*C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 6 hours (Table S4, entry 13).
Figure $367. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure $367. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 7 hours (Table S4, entry 14).
Figure S368. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Figure S368. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 8 hours (Table S4, entry 15).
Figure $369. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16).
Figure $369. '°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 9 hours (Table S4, entry 16).
Figure S370. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure S370. °C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 10 hours (Table S4, entry 17).
Figure $371. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table S4, entry 10\
Figure $371. ‘°C NMR spectrum of copoly(caprolactone/ hydroxyethylsyringic acid) [50:50] at 13 hours (Table S4, entry 10\
Figure $372. 'H NMR spectra of copoly(caprolactone/hydroxyethylsyringic acid) with hydroxyethylsyringic acid (HESA’ feed fractions of 100%, 40%, and 0%.
Figure $372. 'H NMR spectra of copoly(caprolactone/hydroxyethylsyringic acid) with hydroxyethylsyringic acid (HESA’ feed fractions of 100%, 40%, and 0%.
Figure $374. 'H NMR spectra of copoly(caprolactone/hydroxyethylferulic acid) with hydroxyethylferulic acid (HEFA) feed fractions of 0%, 40%, and 100%.
Figure $374. 'H NMR spectra of copoly(caprolactone/hydroxyethylferulic acid) with hydroxyethylferulic acid (HEFA) feed fractions of 0%, 40%, and 100%.
Figure $378. 'H NMR spectra of copoly(L-lactide/hydroxyethylferulic acid) with hydroxyethylferulic acid (HEFA) feed fractions of 0%, 40%, and 100%.
Figure $378. 'H NMR spectra of copoly(L-lactide/hydroxyethylferulic acid) with hydroxyethylferulic acid (HEFA) feed fractions of 0%, 40%, and 100%.
Table S4. Kinetic study for ROP polycondensation for the copolymer of ¢-caprolactone and hydroxyethylsyring: acid prepared with a 50:50 ratio of monomers.
Table S4. Kinetic study for ROP polycondensation for the copolymer of ¢-caprolactone and hydroxyethylsyring: acid prepared with a 50:50 ratio of monomers.
Table S5. Relative abundance of monomers and oligomers as a function of time according to ESI mass spectrometry.
Table S5. Relative abundance of monomers and oligomers as a function of time according to ESI mass spectrometry.
Figure S380. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1)
Figure S380. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 10 min. (Table S4, entry 1)
Figure S381. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2)
Figure S381. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 20 min. (Table S4, entry 2)
Figure $382. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3)
Figure $382. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 30 min. (Table S4, entry 3)
Figure $383. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4)
Figure $383. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 1 hour (Table S4, entry 4)
Figure S384. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5)
Figure S384. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 1.5 hours (Table S4, entry 5)
Figure S385. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6)
Figure S385. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 2 hours (Table S4, entry 6)
Figure $386. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7)
Figure $386. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 2.5 hours (Table S4, entry 7)
Figure $387. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8)
Figure $387. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 3 hours (Table S4, entry 8)
Figure S388. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9)
Figure S388. ESI spectra of copoly(caprolactone/hydroxyethylsyringic acid) [50:50] at 3.5 hours (Table S4, entry 9)

Key takeaways
sparkles

AI

  1. Concurrent ring-opening polymerization and polycondensation yield random copolymers with tailored thermal properties.
  2. Monomer yields range from 62% to 94.9% across different formulations of hydroxyethyl derivatives.
  3. Polymerization conditions include temperatures up to 250 °C and dynamic vacuum to enhance degree of polymerization.
  4. Characterization techniques utilized include NMR, DSC, TGA, and GPC for comprehensive analysis of copolymers.
  5. This study aims to develop sustainable copolymers from bioaromatic hydroxy-acids and lactones.

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References (1)

  1. 9,200 23,200 2.5 13 293 355 14 7 200 14,700 33,600 2.3 15 301 354 15 8 200 20,300 45,600 2.2 15 304 353 16 9 200 23,200 50,500 2.2 17 311 353 17 10 200 27,100 55,800 2.1 20 314 353 18 13 200 28,800 57,200 2.0 20 315 359 a 1.2 eq. of P2O5; mixture was melted under argon for 5 hour temperature ramp from 150 to 200 °C; then dynamic vacuum was applied for 8 hours at 200 °C. b Obtained by GPC in hexafluoroisopropanol (HFIP) at 40 °C versus polymethyl methacrylate (PMMA) standards. c Determined by DSC. d Temperature at which 5% mass loss is observed under nitrogen. f Temperature at which 50% mass loss is observed under nitrogen.

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