Synthesis and Characterization of Poly(glyceric Acid Carbonate): A Degradable Analogue of Poly(acrylic Acid)

Abstract

The synthesis and characterization of a degradable version of poly(acrylic acid), poly(glyceric acid carbonate), are reported. Specifically, atactic and isotactic poly(benzyl glycidate carbonate)s are obtained via the ring-opening copolymerization of rac-/(R)-benzyl glycidate with CO2 using a bifunctional rac-/(S,S)-cobalt salen catalyst in high carbonate linkage selectivity (>99%) and polymer/cyclic carbonate selectivity (∼90%). Atactic poly(benzyl glycidate carbonate) is an amorphous material with a T(g) (glass transition temperature) of 44 °C, while its isotactic counterpart synthesized from enantiopure epoxide and catalyst is semicrystalline with a T(m) (melting temperature) = 87 °C. Hydrogenolysis of the resultant polymers affords the poly(glyceric acid carbonate). Poly(glyceric acid carbonate) exhibits an improved cell cytotoxicity profile compared to poly(acrylic acid). Poly(glyceric acid carbonate)s also degrade remarkably fast (t(1/2) ≈ 2 weeks) compared to poly(acrylic acid). Cross-linked hydrogels prepared from poly(glyceric acid carbonate) and poly(ethylene glycol) diaziridine show significant degradation in pH 8.4 aqueous buffer solution compared to similarly prepared hydrogels from poly(acrylic acid) and poly(ethylene glycol) diaziridine.

Poly(Alkyl Glycidate Carbonate)s as Degradable Pressure‐Sensitive Adhesives

“…These low TOFv alues are similar to the value reported for the polymerization of poly(benzyl glycidate carbonate) (TOF = 11 h À1 )u nder the same temperature and catalyst loading. [20] Upon screening the polymerization conditions,similar trends are observed for all monomers.R aising the reaction temperature increases turnover rates but diminishes polymer selectivity,preferring the formation of cyclic carbonate.Increasing catalyst loading affords abell curve with an optimal polymer selectivity centered at 500:1 monomer/catalyst loading (Supporting Information, Tables S1-S3).…”

“…[14][15][16][17][18][19][20][21][22][23] Glycerol is listed as "generally recognized as safe" (GRAS) by the Food and Drug Administration, and as such, linear, branched, hyperbranched, and dendritic polyglycerols are being investigated for aw ide-variety of medical and non-medical use. [14][15][16][17][18][19][20][21][22][23] Glycerol is listed as "generally recognized as safe" (GRAS) by the Food and Drug Administration, and as such, linear, branched, hyperbranched, and dendritic polyglycerols are being investigated for aw ide-variety of medical and non-medical use.…”

“…Polymers incorporating ag lycerol backbone are of significant interest owing to their degradability,b iocompatibility,a nd chemical tunability. [14][15][16][17][18][19][20][21][22][23] Glycerol is listed as "generally recognized as safe" (GRAS) by the Food and Drug Administration, and as such, linear, branched, hyperbranched, and dendritic polyglycerols are being investigated for aw ide-variety of medical and non-medical use. [24][25][26][27][28][29][30][31][32][33] To install the carbonate moiety within the polymer backbone,w es elected ap olymerization methodology pioneered and brought to fruition by Coates, [34] Darensbourg, [35] Frey, [36] Inoue, [37,38] Lu, [39,40] and Nozaki.…”

Chopping high‐molecular weight poly(1,4‐butylene carbonate‐co‐aromatic ester)s for macropolyol synthesis

“…The utilization of carbon dioxide is an issue being addressed in both the academic and industrial fields . One method that is currently under investigation for the useful consumption of CO 2 involves its copolymerization with propylene oxide or ethylene oxide to form aliphatic polycarbonates . Alternatively, CO 2 can be reacted to form dimethyl carbonate (DMC), which is subsequently converted to diphenyl carbonate and further to the conventional aromatic polycarbonate .…”

“…[1][2][3][4] One method that is currently under investigation for the useful consumption of CO 2 involves its copolymerization with propylene oxide or ethylene oxide to form aliphatic polycarbonates. [5][6][7][8][9][10][11][12][13][14] Alternatively, CO 2 can be reacted to form dimethyl carbonate (DMC), which is subsequently converted to diphenyl carbonate and further to the conventional aromatic polycarbonate. 15 The former process is currently undergoing commercialization, whereas the latter is already under operation industrially.…”