Synthesis and Modification of Functional Polycarbonates with Pendant Allyl Groups

Abstract

Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt2 and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO2 or by the terpolymerization of AGE, IGE and CO2 were oxidized with m‐chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss.

Poly(carbonate) copolymers with a tailored number of hydroxyl groups from glycidyl ethers and CO2

“…38 A solution of pyrogallol (0.47 g, 4 mmol) in 10 mL of 1,4-dioxane was slowly added to a stirred solution of ZnEt 2 (2 mmol) in 35 ml of dioxane at room temperature. 38 A solution of pyrogallol (0.47 g, 4 mmol) in 10 mL of 1,4-dioxane was slowly added to a stirred solution of ZnEt 2 (2 mmol) in 35 ml of dioxane at room temperature.…”

Functional Polycarbonates from Carbon Dioxide and Tailored Epoxide Monomers: Degradable Materials and Their Application Potential

“…Listos and co‐workers synthesized CO 2 /allyl glycidyl ether (AGE) copolymers in the presence of a catalyst system based on ZnEt 2 and pyrogallol at a molar ratio of 2:1 . The functionality of some polycarbonates could be tailored by replacing a fraction of AGE with saturated glycidyl ethers, e.g., butyl glycidyl ether or isopropyl glycidyl ether ( 16 ) . Furthermore, oxidation of the double bond and hydrolytic stability were tested.…”

Polymer cyclization inhibits thermal decomposition of carbon-dioxide-derived poly(propylene carbonate)s

“…The synthesis of polycarbonates (PCs) by CO 2 –epoxide alternating copolymerization discovered by Inoue and coworkers can be considered as one of the ideal systems for utilizing CO 2 as a carbon source . Continuous efforts have been devoted to control over properties of CO 2 ‐derived PCs either by expanding the scope of available epoxides or by postpolymerization modifications . Alternating copolymer of CO 2 and propylene oxide (PO), poly(propylene carbonate) (PPC), is one of the well‐studied aliphatic PCs.…”