Supplemental Information. Reactivity of Monovinyl (Meth)Acrylates Containing Cyclic Carbonates

Transcription

1 Supplemental Information Reactivity of Monovinyl (Meth)Acrylates Containing Cyclic Carbonates Kathryn A. Berchtold a, Jun Nie b, Jeffrey W. Stansbury c, d, and Christopher N. Bowman c, d, a Materials Science & Technology Division, Los Alamos National Laboratory, Mail Stop E-549, Los Alamos, New Mexico USA b State Key Laboratory of Chemical Resource Engineering and College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing, PR China c Department of Chemical & Biological Engineering, University of Colorado, Boulder, Colorado d Department of Craniofacial Biology, School of Dental Medicine, University of Colorado Denver, Denver, Colorado , Fax: , Christopher.Bowman@colorado.edu Synthesis & Purification Synthesis and purification of the monomer systems used in these studies is presented. Monomers are grouped by secondary functionality. Monomers with essentially identical synthetic methods are grouped under a single heading. Included in synthesis and purification sections are the 500 MHz 1 H NMR frequency shifts in ppm, the boiling point ( C), the pressure (mm Hg) at which the boiling point was determined, and the melting point, where applicable. The monomer abbreviations are the means of identification in the main manuscript. 1. Hydroxy Methacrylates 1.1 Hydroxy Propyl Methacrylate IUPAC name: (meth)acrylic acid 3-hydroxypropyl Common name: hydroxypropyl Abbreviation: hydroxy propyl MA Synthesis. 1,3-Propanediol, triethylamine, and chloroform were introduced into a three-necked flask in an ice water bath equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. An excess of the diol (1.5 mol diol : 1 mol acid chloride) was used in S- 1 each synthesis. Methacryloyl chloride was added dropwise to the solution while maintaining the temperature below 5 C. The reaction was continued at room temperature for 6 hours. The mixture was filtered and the liquid phase was washed with saturated NaCl solution followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by column chromatography on silica gel with hexane/ethyl acetate (1/1 by volume) mixture as the eluant. 1 H NMR (CDCl 3 ) (hydroxy propyl MA) δ: 6.1(s, 1H), 5.57(s, 1H), 4.22(t, 2H), 3.68(t, 2H), 1.9(s, 3H; m, 2H). B.P.: 57 C/0.5 mm Hg 2. Linear Carbonate Methacrylates 2.1 Ethyl Carbonate Methacrylate IUPAC name: (meth)acrylic acid 2- ethoxycarbonyloxy-ethyl Common name: ethylcarbonatoethyl (meth)acrylate Abbreviation: EtLC ethyl MA

2 Synthesis. 2-Hydroxyethyl, triethylamine and chloroform were introduced into a three-necked flask in an ice water bath equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. Ethyl chloroformate was added dropwise to the solution while maintaining the temperature below 5 C. The reaction was continued at room temperature for 6 hours. The mixture was filtered and the liquid phase was washed three times with a saturated NaCl solution followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by column chromatography on silica gel with hexane/ethyl acetate (2/1 by volume) mixture as the eluant. 1 H NMR (CDCl 3 ) (EtLC ethyl MA) δ: 6.1(s, 1H), 5.57(s, 1H), 4.3(s, 4H), 4.05(q, 2H), 1.9(s, 3H), 1.15(t, 3H). 2.2 Benzyl Carbonate Methacrylate IUPAC name: (2-Methyl)-acrylic acid 2- benzyloxycarbonyloxy-ethyl Common name: benzyl carbonate Abbreviation: benzyl OCO MA Synthesis. Five grams of 2-hydroxyethyl, 4 ml of triethylamine and 100 ml of dichloromethane were introduced into a three-necked flask in an ice water bath, equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. Five grams of benzyl chloroformate were added dropwise to the solution, while maintaining the temperature below 5 C. The reaction mixture was stirred at room temperature for 6 hours and then filtered. The liquid phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with saturated NaCl solution. The product was then dried over Na 2 SO 4 overnight. After filtering and removing the solvent, the crude product was purified by column chromatography on silica gel with a hexane/ethyl acetate eluant (3/1 by volume). The product was purified further by distillation at 0.5 mm Hg and 240 C. 1 H NMR (CDCl 3 ) (benzyl OCO MA) δ: 7.4(m, 5H), 6.05(s, 1H), 5.6(s, 1H), 5.2(s, 2H), 4.4(m, 4H), 1.9(s, 3H). 2.3 Phenyl Carbonate (Meth)acrylate phenoxycarbonyloxy-ethyl Common name: phenyl carbonate Abbreviation: phenyl OCO MA IUPAC name: Acrylic acid 2- phenoxycarbonyloxy-ethyl Common name: phenyl carbonate acrylate Abbreviation: phenyl OCO Acr Synthesis. 2-Hydroxyethyl (meth)acrylate, triethylamine and methylene chloride were bath equipped with a magnetic stirrer, reflux condenser, and N 2 gas purge. Phenyl chloroformate was added dropwise to the solution while maintaining the temperature below 5 C. The reaction mixture was continued at room temperature for 6 hours. The mixture was filtered and the liquid phase was washed with 1 wt % aqueous NaOH, 1 wt % aqueous HCl, and three times with saturated NaCl solution followed by drying the organic phase over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by column chromatography on silica gel with hexane/ethyl acetate (3/1 by volume) mixture as the eluant. The product was purified further via vacuum distillation at 0.5 mmhg and 260 C. NMR (CDCl 3 ) (phenyl OCO MA) δ (m, 5H), δ6.05(s, 1H), δ5.6(s, 1H), δ4.46(t, 2H), δ4.4(t, 2H), δ1.9(s, 3H). NMR (CDCl 3 ) (phenyl OCO Acr) δ (m, 5H), δ6.4(d, 1H), δ6.05(q, 1H), δ5.85(d, 1H), δ4.4(m, 4H). B.P.: 126 C/0.5 mmhg 3. Cycloalkyl (Meth)Acrylates 3.1 Cyclohexyl (Meth)Acrylates IUPAC name: 2-Methyl-acrylic acid cyclohexyl Common name: cyclohexyl Abbreviation: cyclohexyl MA IUPAC name: Acrylic acid cyclohexyl Common name: cyclohexyl acrylate Abbreviation: cyclohexyl Acr Synthesis. Five grams of cyclohexanol, 7 ml of triethylamine and 100 ml of methylene chloride were bath equipped with a magnetic stirrer, reflux condenser, and N 2 gas purge. (Meth)Acryloyl chloride was added dropwise to the solution while S- 2

3 maintaining the temperature below 5 C. The reaction was then stirred at room temperature for 6 hours. The mixture was filtered and the liquid phase was washed once with a 1 wt % aqueous NaOH solution and 1 wt % aqueous HCl solution, and three times with saturated NaCl. The product was then dried over Na 2 SO 4 overnight followed by solvent removal under vacuum. The crude product was purified by column chromatography on silica gel using a hexane/ethyl acetate (3/1 by volume) eluent. NMR (CDCl 3 ) (cyclohexyl MA) δ6.05(s, 1H), δ5.58(s, 1H), δ4.8(m, 1H), δ1.9(s, 3H), δ1.8(m, 2H), δ1.7(m, 2H), δ (m, 6H). NMR (CDCl 3 ) (cyclohexyl Acr) δ6.4(d, 1H), δ6.05(q, 1H), δ5.8(d, 1H), δ4.8(m, 1H), δ1.9(m, 2H), δ1.7(m, 2H), δ (m, 6H). 3.2 Cyclopentyl (Meth)Acrylate IUPAC name: 2-Methyl-acrylic acid cyclopentylmethyl Common name: cyclopentanemethanol Abbreviation: cyclopentyl MA IUPAC name: Acrylic acid cyclopentylmethyl Common name: cyclopentanemethanol (meth)acrylate Abbreviation: cyclopentyl Acr Synthesis. Two grams of cyclopentanemethanol, 3 ml of triethylamine and 100 ml of methylene chloride were introduced into a three-necked flask in an ice water bath, equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. (Meth)Acryloyl chloride was added dropwise to the solution while maintaining the temperature below 5 C. The reaction was continued for 6 hours at room temperature. The product was then filtered and the liquid phase washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with saturated NaCl solution. The product was dried over Na 2 SO 4 overnight and the solvent was removed under vacuum. The crude product was purified by column chromatography on silica gel using a hexane/ethyl acetate (3/1 by volume) eluent. NMR (CDCl 3 ) (cyclopentyl Acr) δ6.4(d, 1H), δ6.05(q, 1H), δ5.8(d, 1H), δ4.0(m, 2H), δ2.1(m, 1H), δ1.7(m, 2H), δ1.6(m, 4H), δ1.2(m, 2H). 4. Aliphatic Carbamate (NCO) Methacrylates ethylcarbamoyloxy-ethyl Common name: ethyl carbamate Abbreviation: ethyl NCO MA propylcarbamoyloxy-ethyl Common name: n-propyl carbamate Abbreviation: n-propyl NCO MA butylcarbamoyloxy-ethyl Common name: n-butyl carbamate Abbreviation: n-butyl NCO MA tertbutylcarbamoyloxy-ethyl Common name: t-butyl carbamate Abbreviation: t-butyl NCO MA Synthesis. Isocyanate (ethyl, n-propyl, n-butyl, t- butyl), two drops of triethylamine and 50 ml of dichloromethane were introduced into a three-necked flask in an ice water bath equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. A stoichiometric amount of 2-hydroxyethyl was added to the flask over one hour, and the reaction mixture was left to react at room temperature for 36 hours after the addition was complete. Following the reaction, the organic phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with saturated NaCl solution. The product was then dried over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by column chromatography on silica gel with a hexane/ethyl acetate (3/1 by volume) eluant. 1 H NMR (CDCl 3 ) (ethyl NCO MA) δ: 6.05(s, 1H), 5.58(s, 1H), 4.3(s, 4H), 3.2(m, 2H), 1.9(s, 3H), 1.1(t, 3H). M.P.: 28 C NMR (CDCl 3 ) (cyclopentyl MA) δ6.05(s, 1H), δ5.58(s, 1H), δ4.0(m, 2H), δ2.1(m, 1H), δ1.9(s, 3H), δ1.7(m, 2H), δ1.6(m, 4H), δ1.2(m, 2H). S- 3

4 1 H NMR (CDCl 3 ) (n-propyl NCO MA) δ: 6.05(s, 1H), 5.58(s, 1H), 4.3(s, 4H), 3.2(m, 2H), 1.9(s, 3H), 1.5(m, 2H), 1.3(m, 2H), 1.1(t, 3H). 1 H NMR (CDCl 3 ) (n-butyl NCO MA) δ: 6.05(s, 1H), 5.58(s, 1H), 4.3(s, 4H), 3.2(m, 2H), 1.9(s, 3H), 1.5(m, 2H), 1.4(m, 2H), 1.3(m, 2H), 1.1(t, 3H). 1 H NMR (CDCl 3 ) (t-butyl NCO MA) δ: 6.05(s, 1H), 5.58(s, 1H), 4.3(d, 4H), 1.9(s, 3H), 1.1(s, 9H). M.P.: 27 C 5. Aromatic Carbamates (NCO) 5.1 Benzyl Carbamate (NCO) Methacrylate IUPAC name: (2-Methyl)-acrylic acid 2- benzylcarbamoyloxy-ethyl Common name: benzyl carbamate Abbreviation: benzyl NCO MA Synthesis. Benzyl isocyanate (10 ml), two drops of dibutyltin dilaurate, and 50 ml of dichloromethane were introduced into a three-necked flask in an ice water bath equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. 2- Hydroxyethyl (12 ml) was added to the flask over a one-hour period. The reaction mixture was left to react at room temperature for 36 hours. After the reaction was completed, the organic phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with a saturated NaCl solution, followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by distillation at 0.5 mm Hg and 140 C to remove the lower boiling point impurities. The temperature was then raised to 260 C to distill the product. The distillate was recrystallized from a chloroform/hexane (1/4 by volume) solution. 1 H NMR (CDCl 3 ) (Benzyl NCO MA) δ: 7.3(m, 5H), 6.05(s, 1H), 5.58(s, 1H), 5.05(s, 1H), 4.3(m, 6H), 1.9(s, 3H). B.P.: 178 C/0.5 mm Hg M.P C 5.2 Phenyl Carbamate (NCO) (Meth)Acrylate phenylcarbamoyloxy-ethyl Common name: phenyl carbamate (NCO) Abbreviation: phenyl NCO MA S- 4 IUPAC name: Acrylic acid 2- phenylcarbamoyloxy-ethyl Common name: phenyl carbamate (NCO) acrylate Abbreviation: phenyl NCO Acr Synthesis. 2-Hydroxyethyl acrylate (5.5 g) (or 6.4 g of 2-hydroxyethyl ), two drops of dibutyltin dilaurate, and 50 ml of ethyl acetate were added to a three-necked flask under nitrogen purge with magnetic stirring at 0 C. Phenyl isocyanate (5 ml) was added to the solution dropwise over a onehour period. The reaction mixture was left to react at room temperature for 36 hours (until the isocyanate IR peak at 2270 cm -1 completely disappeared). After the reaction was completed, the organic phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with a saturated NaCl solution. It was then dried over Na 2 SO 4 overnight and the solvent was removed under vacuum. The crude product was purified by column chromatography on silica gel using hexane/ethyl acetate (3/1 by volume) eluent. Finally, the product was recrystallized from a chloroform /hexane (1/5 by volume) solution. NMR (CDCl 3 ) (phenyl NCO MA) δ7.4(m, 5H), δ7.05(m, 1H), δ6.7(s, 1H), δ6.05(s, 1H), δ5.58(s, 1H), δ4.4(m, 4H), δ1.9(s, 3H). M.P: C NMR (CDCl 3 ) (phenyl NCO Acr) δ7.4(m, 5H), δ7.05(m, 1H), δ6.7(s, 1H), δ6.42(d, 1H), δ6.05(q, 1H), δ5.82(d, 1H), δ4.4(s, 4H). M.P: 65 C 6. Aliphatic (tert-butyl) Carbamate (OCN) (Meth)Acrylate IUPAC name: (2-Methyl)-acrylic acid 2-tertbutoxycarbonylamino-ethyl Common name: tert-butyl carbamate Abbreviation: t-butyl OCN MA IUPAC name: Acrylic acid 2-tertbutoxycarbonylamino-ethyl Common name: tert-butyl carbamate acrylate Abbreviation: t-butyl OCN Acr Synthesis. Tert-butyl-N-(2-hydroxyethyl) carbamate(4 g), 100 ml of dichloro-methane, and 3.5 ml of triethylamine were introduced into a threenecked flask in an ice water bath, equipped with a

5 magnetic stirrer, reflux condenser and N 2 gas purge. (Meth)Acryloyl chloride (2.8 g) was added dropwise to the solution while maintaining the temperature below 5 C. The reaction proceeded at room temperature for 12 hours. At the end of 12 hours, the solution was filtered and the filtrate was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and a saturated NaCl solution. The organic phase was dried over Na 2 SO 4 overnight, and the solvent was removed under vacuum. The crude product was recrystallized from a chloroform/hexane (1/1 by volume) mixture. NMR (CDCl 3 ) (t-butyl OCN MA) δ6.05(s, 1H), δ5.58(s, 1H), δ4.2(t, 2H), δ3.4(d, 2H), δ1.9(s, 3H), δ1.4(d, 9H). M.P: 81 C NMR (CDCl 3 ) (t-butyl OCN Acr) δ6.4(d, 1H), δ6.05(q, 1H), δ5.8(d, 1H), δ4.2(t, 2H), δ3.4(d, 2H), δ1.4(d, 9H). M.P: 57 C 7. Aromatic Carbamates (OCN) 7.1 Benzyl Carbamate (OCN) Methacrylate benzyloxycarbonylamino-ethyl Common name: benzyl carbamate (OCN) Abbreviation: benzyl OCN MA Synthesis. Three grams of benzyl alcohol, 50 ml of dichloromethane, and two drops of triethylamine were introduced into a three-necked flask in an ice water bath, equipped with a magnetic stirrer, reflux condenser, and N 2 gas purge. 2-Isocyanatoethyl (4.5 grams) was added dropwise. The temperature of the reaction mixture was gradually raised to room temperature. The reaction was continued for three days, until the isocyanate was completely reacted, as evidenced by the disappearance of the isocyanate infrared absorption band at ca cm -1. After reaction completion, the organic phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with a saturated NaCl solution, followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by distillation at 0.5 mmhg and 140 C to remove the lower boiling point impurities. S- 5 The temperature was then raised to 280 C to isolate the product. NMR (CDCl 3 ) (benzyl OCN MA) δ7.3(m, 5H), δ6.05(s, 1H), δ5.58(s, 1H), δ5.05(d, 3H), δ4.2(t, 2H), δ3.5(t, 2H), δ1.9(s, 3H). B.P.: 170 C/0.5 mmhg 7.2 Diphenyl Carbamate (OCN) Methacrylate benzhydryloxycarbonylaminoethyl Common name: diphenyl carbamate (OCN) Abbreviation: diphenyl OCN MA Synthesis. Seven grams of benzhydrol, 50 ml of dichloromethane and two drops of triethylamine were introduced into a three-necked flask in an ice-water bath, equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. 2-Isocyanatoethyl (5 ml) was added dropwise and the temperature of the reaction mixture was gradually raised to room temperature. The reaction was followed for three days until the isocyanate IR peak at 2270 cm -1 completely disappears. The mixture was then washed with 1wt% aqueous NaOH, 1 wt % aqueous HCl and with saturated NaCl solution three times. The organic phase was dried over Na 2 SO 4 overnight. After removing the solvent, lower boiling point impurities were distilled off at 0.5 mmhg and 140 C. The product was obtained at a bath temperature of 300 C and 0.5 mm Hg pressure. NMR (CDCl 3 ) (diphenyl OCN MA) δ7.3(m, 10H), δ6.77(s, 1H), δ6.05(s, 1H), δ5.52(s, 1H), δ5.05(s, 1H), δ4.21(t, 2H), δ3.42(m, 2H), δ1.9(s, 3H). B.P.: 183 C/0.5 mmhg M.P.: 48 C 8. Aliphatic Carbamate (OCN) Methacrylates 8.1 Ethyl Carbamate (OCN) Methacrylate IUPAC name: ethyl 2-(methacryloyloxy) ethylcarbamate Common name: ethyl carbamate (OCN) Abbreviation: ethyl OCN MA

6 Synthesis. Ethanol, two drops of dibutyltin dilaurate, and 20 ml of methylene chloride were bath, equipped with a magnetic stirrer, and N 2 gas purge. 2-Isocyantoethyl was added dropwise to the solution while maintaining the temperature below 5 C. The reaction was continued for six hours at room temperature. The liquid phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with a saturated NaCl solution. The organic phase was dried over Na 2 SO 4 overnight and the solvent removed under vacuum. The crude product was purified by column chromatography on silica gel with a hexane/ethyl acetate (3/1 by volume) eluant. 1 H NMR (CDCl 3, 300 MHz) (ethyl OCN MA) δ:. 6.05(s, 1H), 5.6(s, 1H), 4.2(t, 2H), 4.1(q, 2H), 3.5(q, 2H), 1.9(s, 3H), 1.2(q, 3H). M.P.: C 9. Aromatic Carbamates (OCN) 9.1 Benzyl Carbamate (OCN) Methacrylate benzyloxycarbonylamino-ethyl Common name: benzyl carbamate (OCN) Abbreviation: benzyl OCN MA Synthesis. Three grams of benzyl alcohol, 50 ml of dichloromethane, and two drops of dibutyltin dilaurate were introduced into a three-necked flask in an ice water bath, equipped with a magnetic stirrer, reflux condenser, and N 2 gas purge. 2- Isocyanatoethyl (4.5 grams) was added dropwise. The temperature of the reaction mixture was gradually raised to room temperature. The reaction was continued for three days, until the isocyanate was completely reacted, as evidenced by the disappearance of the isocyanate infrared absorption band at ca cm -1. After reaction completion, the organic phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with a saturated NaCl solution, followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by distillation at 0.5 mmhg and 140 C to remove the lower boiling point impurities. The temperature was then raised to 280 C to isolate the product. 1 H NMR (CDCl 3 ) (benzyl OCN MA) δ: 7.3(m, 5H), 6.05(s, 1H), 5.58(s, 1H), 5.05(d, 3H), 4.2(t, 2H), 3.5(t, 2H), 1.9(s, 3H). B.P.: 170 C/0.5 mm Hg 10. Benzyl Ureas 10.1 Benzyl Urea Methacrylate (3-benzylureido)-ethyl Common name: benzyl urea Abbreviation: benzyl NCN MA Synthesis. Three grams of benzylamine and 100 ml of chloroform were added to a three-necked flask, equipped with a magnetic stirrer, reflux condenser and N 2 gas purge at 0 C. 2- Isocyanatoethyl (4.5 g) was added dropwise to the solution while maintaining the temperature below 5 C. The reaction was continued at room temperature for 12 hours. The product was then washed with 1 wt % aqueous NaOH and HCl solutions sequentially and three times with a saturated NaCl solution. The organic phase was then dried over Na 2 SO 4 overnight. After removing the solvent under vacuum, the crude product was purified by recrystallization from hexane/chloroform solution (2/1 by volume). 1 H NMR (CDCl3) (benzyl NCN MA) δ: 7.3(m, 5H), 6.05(s, 1H), 5.55(s, 1H), 4.3(s, 2H), 4.2(t, 2H), 3.5(t, 2H), 1.9(s, 3H). M.P.: 70 C 11. Aliphatic Ester Methacrylate 11.1 Propyl Ester Methacrylate IUPAC name: 2-(methacryloyloxy)ethyl butyrate Common name: propyl Abbreviation: propyl MA Synthesis. 2-Hydroxyethyl, triethylamine and 50 ml of methylene chloride were bath, and equipped with a magnetic stirrer, and argon gas purge. Butyrl chloride was diluted in 8 ml of methylene chloride, and added dropwise to the solution while maintaining the temperature below 5 C. The reaction continued at room temperature for 2 hours. The mixture was filtered and concentrated, leaving a mixture of a yellow liquid and additional S- 6

7 solid precipitate. The crude product was purified by column chromatography on silica gel by using hexane/ethyl acetate (3/1 by volume) solution as the eluent. The eluted solution was filtered through celite to leave a colorless solution. Solution was evaporated at reduced pressure to render the pure product. 1 H NMR (CDCl 3, 300MHz) (propyl MA) δ: 6.15(s, 1H), 5.6(s, 1H), 4.35(s, 4H), 2.3(t, 2H), 1.95(s, 3H), 1.65(m, 2H), 0.95(t, 3H). 12. Aryl Ester Methacrylates 12.1 Benzyl Ester Methacrylate IUPAC name: 2-Methylacrylic acid 2- phenylacetoxy-ethyl Common name: benzyl Abbreviation: benzyl MA Synthesis. 2-Hydroxyethyl, triethylamine and 100 ml of chloroform were bath, equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. Phenylacetyl chloride was added dropwise to the solution while maintaining the temperature below 5 C. The reaction continued at room temperature for 6 hours. After filtering the mixture, the liquid phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with saturated NaCl solution. Then, the organic phase was dried over Na 2 SO 4 overnight, and the solvent evaporated under vacuum. The crude product was purified by column chromatography on silica gel by using hexane/ethyl acetate (3/1 by volume) solution as the eluant. 1 H NMR (CDCl 3 ) (benzyl MA) δ: 7.3(m, 5H), 6.05(s, 1H), 5.5(s, 1H), 4.3(m, 2H), 3.6(s, 2H), 1.9(s, 3H). 13. Cyclic Carbonate Functionalized (Meth)Acrylates 13.1 Cyclic Carbonate (Meth)Acrylate Synthesis of 4-hydroxymethyl-1,3-dioxolanone (cyclic carbonate alcohol) IUPAC name: 4-Hydroxymethyl-[1,3]dioxolan-2- one Common name: cyclic carbonate alcohol Abbreviation: cc alcohol Synthesis. A mixture of 23 g of glycerol, 56 g of diethyl carbonate, 15 mg of NaOH and 2.5 ml of ethanol were introduced into a round bottom flask equipped with a reflux condenser and heated to 130 C. After 30 minutes, a clear, colorless solution resulted. The reflux condenser was then replaced by a Claisen distillation apparatus and the ethanol biproduct was distilled off at a bath temperature of C. After removal of all the ethanol by distillation, two drops of H 2 SO 4 were added to the residue. The excess diethyl carbonate was removed by house vacuum, and the resulting viscous liquid was separated by column chromatography on silica gel with ethyl acetate as the eluent. The deuterated version was obtained by substituting deuterated glycerol into the same synthetic method. NMR (CDCl 3 ) (cc Alcohol) δ4.8(m, 1H), δ4.47(m, 2H), δ3.95(d, 1H), δ3.66(d, 1H). NMR (CHCl 3 ) (cc Alcohol (d5)) δ4.9(s, 1D), δ4.55(s, 1D), δ4.4(s, 1D), δ4.3(s, 2D) Synthesis of cyclic carbonate (meth)acrylate oxo- [1,3]dioxolan-4-yl methyl Common name: cyclic carbonate Abbreviation: ccma IUPAC name: acrylic acid 2-oxo-[1,3]dioxolan-4- yl methyl Common name: cyclic carbonate acrylate Abbreviation: ccacr Synthesis. 4-Hydroxymethyl-1,3-dioxolan-one (18 g), 16 g of triethylamine, and 100 ml of chloroform were introduced into a three-necked flask in an ice water bath equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. 15 g of (meth)acryloyl chloride were added dropwise to the solution while maintaining the temperature below 5 C, and the reaction was continued at room temperature for 6 more hours. The mixture was filtered, and the liquid phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and saturated NaCl solution three times, followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by column chromatography on silica gel with hexane/ethyl acetate (3 /1 by volume) mixture as the eluent. The S- 7

8 deuterated monomer can be obtained from the deuterated cyclocarbonate alcohol using the same procedure. NMR (CDCl 3 ) (ccma) δ6.12(s, 1H), δ5.61(s, 1H), δ4.95(m, 1H), δ4.58(t, 1H), δ4.4(q, 1H), δ4.3(m, 2H), δ1.9(s, 3H). B.P.: 155 C/0.5 mmhg Safety note: Isocyanatoethyl should be used only with appropriate training and safeguards since it is listed as a Highly Toxic Chemical that is harmful in contact with skin, if swallowed or through inhalation. NMR (CDCl 3 ) (ccacr) δ6.42(d, 1H), δ6.15(q, 1H), δ5.9(d, 1H), δ4.95(m, 1H), δ4.58(t, 1H), δ4.4(q, 1H), δ4.3(m, 2H). B.P.: 130 C/0.5 mmhg 13.2 Cyclic Carbonate Carbamate (OCN) Methacrylate (2-oxo- [1,3]dioxolan-4- ylmethoxycarbonyl-amino)-ethyl Common name: cyclic carbonate carbamate Abbreviation: cyclic carbonate OCN MA Synthesis. Three grams of 4-hydroxymethyl-1,3- dioxolan-one, two drops of triethylamine and 50 ml of dicholoromethane were introduced into a threenecked flask in an ice water bath equipped with a magnetic stirrer, reflux condenser and N 2 gas purge. 2-Isocyanatoethyl (3.9 grams) was added into the flask over a one hour period. The reaction continued at room temperature for an additional 36 hours, until the reaction was completed, as evidenced by the disappearance of the infrared absorption of the isocyanate at ca cm -1. After the reaction was completed, the organic phase was washed with 1 wt % aqueous NaOH solution, 1 wt % aqueous HCl solution, and three times with a saturated NaCl solution followed by drying over Na 2 SO 4 overnight. After filtering and removing the solvent under vacuum, the crude product was purified by recrystallization from chloroform/hexane (1/4 by volume) solution. NMR (CDCl 3 ) (cyclic carbonate OCN MA) δ6.12(s, 1H), δ5.8(s, 1H), δ5.15(s, 1H), δ4.95(m, 1H), δ4.58(m, 1H), δ4.3(m, 5H), δ3.5(m, 2H), δ1.95(s, 3H). M.P: 67 C S- 8