1,3-dioxan-2-one

Conditions: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: ε-Caprolactone (40 g, 0.35 mole), trimethylene carbonate (10 g. 0.098 mole), lauryl alcohol (1.42 g, 7.6×10-3 mole) and stannous chloride dihydrate (10.1 mg, 4.5×10-5 mole) were combined in a flask and heated for 24 hours under nitrogen at 135° C. The resulting polymer had an inherent viscosity of 0.42 dl/g (0.5 g/dl in HFAS). The composition was determined by 1H NMR to be 86 wt. % caprolactone and 14 wt. % trimethylene carbonate.

Conditions: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: ε-Caprolactone (8.0 g, 0.070 mole), trimethylene carbonate (2.0 g, 0.020 mole), lauryl alcohol (0.283 g, 1.52×10-3 mole) and stannous chloride dihydrate (2.02 mg, 8.91×10-6 mole) were combined in a flask. The flask was flushed with nitrogen, evacuated and sealed. The flask was heated at 135° C. for 24 hours. The resulting polymer had a composition, as measured by 1H NMR, of 86 wt. % ε-caprolactone and 14 wt. % trimethylene carbonate. The ηinh of the copolymer was 0.26 dl/g (0.5 g/dl in HFAS). The flask was flushed with nitrogen evacuated sealed

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flame dried, 250 mL, round bottom single neck flask was charged with 102.7 grams (0.90 mole) of ε-caprolactone, 10.2 grams (0.10 mole) of trimethylene carbonate, 2.9 mL (40 mmol) of propylene glycol (USP), and 0.10 mL (34 pmol) of a 0.33M stannous octoate solution in toluene. The flask was fitted with a flame dried mechanical stirrer. The flask was purged with nitrogen three times before venting with nitrogen. The reaction mixture was heated to 160° C. and maintained at this temperature for about 18-20 hours. The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer. The copolymer had an inherent viscosity of 0.25 dL/g in HFIP at 25° C. The copolymer was a viscous liquid at room temperature. A flame dried The flask was fitted with a flame dried mechanical stirrer The flask was purged with nitrogen three times maintained at this temperature for about 18-20 hours The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer at 25° C at room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3-Di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-(2-hydroxyethoxy)-ethoxy)ethoxy)-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran (53.6 g, 0.08 mole) Photochromic A, trimethylene carbonate (146 g, 1.43 moles), anhydrous chloroform (400 mL) and aluminum isopropoxide (3.3 g, 0.016 mole) were added to a 1 liter 1 neck flask with a magnetic stir bar, purged with dry nitrogen, capped with rubber septum, and then allowed to stir at room temperature for 24 hrs. The resulting dark purple organic solution was washed by adding a solution of conc. HCl (16 g) in H2O (400 g) and stirring vigorously. Upon separation and removal of the aqueous phase, the organic layer was then washed with 10 weight % aqueous sodium bicarbonate solution (400 mL). The recovered organic layer was dried with magnesium sulfate, filtered, and poured into a 1 liter rotary evaporation flask. The molecular weight distribution by GPC was determined to be an Mn of 3,090, a Mw of 3960 and PDI of 1.28. After rotary evaporation for 1 hour at 90° C., the dark purple oil was diluted with anhydrous toluene (200 g), and to this solution was added 4 drops of dibutyltindilaurate and isocyanatoethylmethacrylate (12.6 g, 0.081 mole). The resulting reaction mixture was heated to 76° C., purged with dry nitrogen, capped with a rubber septum, stirred for 3 hrs at 76° C., followed by stirring overnight at room temperature. purged with dry nitrogen capped with rubber septum The resulting dark purple organic solution was washed by adding a solution of conc. HCl (16 g) in H2O (400 g) stirring vigorously Upon separation and removal of the aqueous phase the organic layer was then washed with 10 weight % aqueous sodium bicarbonate solution (400 mL) The recovered organic layer was dried with magnesium sulfate filtered poured into a 1 liter rotary evaporation flask After rotary evaporation for 1 hour at 90° C. the dark purple oil was diluted with anhydrous toluene (200 g) The resulting reaction mixture was heated to 76° C. purged with dry nitrogen capped with a rubber septum stirred for 3 hrs at 76° C. by stirring overnight at room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3,3-Di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-(2-hydroxyethoxy)-ethoxy)ethoxy)-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran (53.6 g, 0.08 mole) Photochromic A, trimethylene carbonate (146 g, 1.43 moles), anhydrous chloroform (400 mL) and aluminum isopropoxide (3.3 g, 0.016 mole) were added to a 1 liter 1 neck flask with a magnetic stir bar, purged with dry nitrogen, capped with rubber septum, and then allowed to stir at room temperature for 24 hrs. The resulting dark purple organic solution was washed by adding a solution of conc. HCl (16 g) in H2O (400 g) and stirring vigorously. Upon separation and removal of the aqueous phase, the organic layer was then washed with 10 weight % aqueous sodium bicarbonate solution (400 mL). The recovered organic layer was dried with magnesium sulfate, filtered, and poured into a 1 liter rotary evaporation flask. The molecular weight distribution by GPC was determined to be an Mn of 3,090, a Mw of 3960 and PDI of 1.28. After rotary evaporation for 1 hour at 90° C., the dark purple oil was diluted with anhydrous toluene (200 g), and to this solution was added 4 drops of dibutyltindilaurate and isocyanatoethylmethacrylate (12.6 g, 0.081 mole). The resulting reaction mixture was heated to 76° C., purged with dry nitrogen, capped with a rubber septum, stirred for 3 hrs at 76° C., followed by stirring overnight at room temperature. purged with dry nitrogen capped with rubber septum The resulting dark purple organic solution was washed by adding a solution of conc. HCl (16 g) in H2O (400 g) stirring vigorously Upon separation and removal of the aqueous phase the organic layer was then washed with 10 weight % aqueous sodium bicarbonate solution (400 mL) The recovered organic layer was dried with magnesium sulfate filtered poured into a 1 liter rotary evaporation flask After rotary evaporation for 1 hour at 90° C. the dark purple oil was diluted with anhydrous toluene (200 g) The resulting reaction mixture was heated to 76° C. purged with dry nitrogen capped with a rubber septum stirred for 3 hrs at 76° C. by stirring overnight at room temperature

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: L-Lactide (85.07 g; 0.945 moles) and water (100 mL; millipore) were placed in a 1 L 3-neck flask equipped with a mechanical stirrer, distillation head, and a thermometer. The reaction mixture was warmed to 80° C. and stirred under nitrogen overnight. The flask was then placed under vacuum (aspirator, 7 mmHg) and the temperature was raised to 140° C. to distill off water. After 2 hrs trimethylene carbonate (8.51 g, 0.083 moles) was added. Two hours later a second portion of trimethylene carbonate (8.52 g, 0.083 moles) was added and the reaction was allowed to proceed for 3 more hours. The reaction was cooled to 80° C. and 120 mL of acetic anhydride was added. The solution was stirred at 80° C. overnight under a slow nitrogen purge. After 18 hours the remaining acetic anhydride and acetic acid were removed under vacuum. After the acetic acid and acetic anhydride distillation was complete, 180 mL of tetrahydrofuran/water (85/15; v/v) was added with stirring and the flask temperature was allowed to drop to 60° C. After 15 min the reaction mixture was transferred to a round bottom flask and the tetrahydrofuran was removed under vacuum on a rotary evaporator. Chloroform (300 mL) was added and the resulting solution was extracted twice with 150 mL of millipore water in a separatory funnel and then dried with MgSO4. The mixture was filtered through a "d" fritted glass funnel and the solvent distilled from the oligomer by rotary evaporation. Final traces of solvents were removed under high vacuum (0.4 mmHg) on a Kugelrohr apparatus at 90° C. to yield acetyl-oligo(L-lactic acid-co-trimethylene carbonate) with trimethylene carbonate n=1.6, lactic acid n=7.6, MN =974, and MW =1684. equipped with a mechanical stirrer distillation head the temperature was raised to 140° C. to distill off water The reaction was cooled to 80° C. The solution was stirred at 80° C. overnight under a slow nitrogen purge After 18 hours the remaining acetic anhydride and acetic acid were removed under vacuum After the acetic acid and acetic anhydride distillation 180 mL of tetrahydrofuran/water (85/15; v/v) was added with stirring to drop to 60° C After 15 min the reaction mixture was transferred to a round bottom flask the tetrahydrofuran was removed under vacuum on a rotary evaporator Chloroform (300 mL) was added the resulting solution was extracted twice with 150 mL of millipore water in a separatory funnel dried with MgSO4 The mixture was filtered through a "d" fritted glass funnel the solvent distilled from the oligomer by rotary evaporation Final traces of solvents were removed under high vacuum (0.4 mmHg) on a Kugelrohr apparatus at 90° C.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: L-Lactide (85.07 g; 0.945 moles) and water (100 mL; millipore) were placed in a 1 L 3-neck flask equipped with a mechanical stirrer, distillation head, and a thermometer. The reaction mixture was warmed to 80° C. and stirred under nitrogen overnight. The flask was then placed under vacuum (aspirator, 7 mmHg) and the temperature was raised to 140° C. to distill off water. After 2 hrs trimethylene carbonate (8.51 g, 0.083 moles) was added. Two hours later a second portion of trimethylene carbonate (8.52 g, 0.083 moles) was added and the reaction was allowed to proceed for 3 more hours. The reaction was cooled to 80° C. and 120 mL of acetic anhydride was added. The solution was stirred at 80° C. overnight under a slow nitrogen purge. After 18 hours the remaining acetic anhydride and acetic acid were removed under vacuum. After the acetic acid and acetic anhydride distillation was complete, 180 mL of tetrahydrofuran/water (85/15; v/v) was added with stirring and the flask temperature was allowed to drop to 60° C. After 15 min the reaction mixture was transferred to a round bottom flask and the tetrahydrofuran was removed under vacuum on a rotary evaporator. Chloroform (300 mL) was added and the resulting solution was extracted twice with 150 mL of millipore water in a separatory funnel and then dried with MgSO4. The mixture was filtered through a "d" fritted glass funnel and the solvent distilled from the oligomer by rotary evaporation. Final traces of solvents were removed under high vacuum (0.4 mmHg) on a Kugelrohr apparatus at 90° C. to yield acetyl-oligo(L-lactic acid-co-trimethylene carbonate) with trimethylene carbonate n=1.6, lactic acid n=7.6, MN =974, and MW =1684. equipped with a mechanical stirrer distillation head the temperature was raised to 140° C. to distill off water The reaction was cooled to 80° C. The solution was stirred at 80° C. overnight under a slow nitrogen purge After 18 hours the remaining acetic anhydride and acetic acid were removed under vacuum After the acetic acid and acetic anhydride distillation 180 mL of tetrahydrofuran/water (85/15; v/v) was added with stirring to drop to 60° C After 15 min the reaction mixture was transferred to a round bottom flask the tetrahydrofuran was removed under vacuum on a rotary evaporator Chloroform (300 mL) was added the resulting solution was extracted twice with 150 mL of millipore water in a separatory funnel dried with MgSO4 The mixture was filtered through a "d" fritted glass funnel the solvent distilled from the oligomer by rotary evaporation Final traces of solvents were removed under high vacuum (0.4 mmHg) on a Kugelrohr apparatus at 90° C.

Conditions: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: ε-Caprolactone (40 g, 0.35 mole), trimethylene carbonate (10 g. 0.098 mole), lauryl alcohol (1.42 g, 7.6×10-3 mole) and stannous chloride dihydrate (10.1 mg, 4.5×10-5 mole) were combined in a flask and heated for 24 hours under nitrogen at 135° C. The resulting polymer had an inherent viscosity of 0.42 dl/g (0.5 g/dl in HFAS). The composition was determined by 1H NMR to be 86 wt. % caprolactone and 14 wt. % trimethylene carbonate.

Conditions: temp:135.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: ε-Caprolactone (8.0 g, 0.070 mole), trimethylene carbonate (2.0 g, 0.020 mole), lauryl alcohol (0.283 g, 1.52×10-3 mole) and stannous chloride dihydrate (2.02 mg, 8.91×10-6 mole) were combined in a flask. The flask was flushed with nitrogen, evacuated and sealed. The flask was heated at 135° C. for 24 hours. The resulting polymer had a composition, as measured by 1H NMR, of 86 wt. % ε-caprolactone and 14 wt. % trimethylene carbonate. The ηinh of the copolymer was 0.26 dl/g (0.5 g/dl in HFAS). The flask was flushed with nitrogen evacuated sealed

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flame dried, 250 mL, round bottom single neck flask was charged with 102.7 grams (0.90 mole) of ε-caprolactone, 10.2 grams (0.10 mole) of trimethylene carbonate, 2.9 mL (40 mmol) of propylene glycol (USP), and 0.10 mL (34 pmol) of a 0.33M stannous octoate solution in toluene. The flask was fitted with a flame dried mechanical stirrer. The flask was purged with nitrogen three times before venting with nitrogen. The reaction mixture was heated to 160° C. and maintained at this temperature for about 18-20 hours. The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer. The copolymer had an inherent viscosity of 0.25 dL/g in HFIP at 25° C. The copolymer was a viscous liquid at room temperature. A flame dried The flask was fitted with a flame dried mechanical stirrer The flask was purged with nitrogen three times maintained at this temperature for about 18-20 hours The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer at 25° C at room temperature

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flame dried, 250 mL, round bottom single neck flask was charged with 102.7 grams (0.90 mole) of ε-caprolactone, 10.2 grams (0.10 mole) of trimethylene carbonate, 2.9 mL (40 mmol) of propylene glycol (USP), and 0.10 mL (34 μmol) of a 0.33M stannous octoate solution in toluene. The flask was fitted with a flame dried mechanical stirrer. The flask was purged with nitrogen three times before venting with nitrogen. The reaction mixture was heated to 160° C. and maintained at this temperature for about 18-20 hours. The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer. The copolymer had an inherent viscosity of 0.25 dL/g in HFIP at 25° C. The copolymer was a viscous liquid at room temperature. A flame dried The flask was fitted with a flame dried mechanical stirrer The flask was purged with nitrogen three times maintained at this temperature for about 18-20 hours The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer at 25° C at room temperature

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flame dried, 250 mL, round bottom single neck flask was charged with 57.1 grams (0.50 mole) of ε-caprolactone, 51.0 grams (0.50 mole) of trimethylene carbonate, 4.4 mL (60mmol) of propylene glycol (USP), and 0.10 mL (34 μmol) of a 0.33M solution of stannous octoate in toluene. The flask was fitted with a flame dried mechanical stirrer. The flask was purged with nitrogen three times before venting with nitrogen. The reaction mixture was heated to 160° C. and maintained at this temperature for about 18-20 hours. The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer. The copolymer had an inherent viscosity of 0.20 dL/g in HFIP at 25° C. The copolymer was a viscous liquid at room temperature. A flame dried The flask was fitted with a flame dried mechanical stirrer The flask was purged with nitrogen three times maintained at this temperature for about 18-20 hours The copolymer was dried under vacuum (0.1 mm Hg) at 80° C. for about 16 hours to remove any unreacted monomer at 25° C at room temperature