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

Abstract

Aliphatic polycarbonates synthesized from carbon dioxide (CO 2 ) and epoxides are resource-saving, highly biocompatible and biodegradable polymers. Since the discovery of the copolymerization of epoxides and CO 2 in 1969 by Inoue et al., this has become an important and useful technology for the large-scale utilization of CO 2 in chemical synthesis, employing mainly propylene oxide, and cyclohexene oxide (CHO). Only in recent years, functionalized polycarbonates have become an emerging topic with a broad scope of potential applications. This review summarizes synthetic routes and properties of numerous functionalized polycarbonates synthesized from CO 2 and functional epoxide monomers. Implications for new materials and possible applications, for instance for pharmaceutical purposes and membranes are reviewed. Besides polycarbonates based on oxirane and CHO derivatives, particular emphasis is placed on the manifold synthetic approaches and postpolymerization modifications of glycidyl ether based polycarbonates. Not only functionalized linear polycarbonates are presented but also a variety of novel polycarbonate architectures, e.g., star and hyperbranched polymers.

CO2-fixation into cyclic and polymeric carbonates: principles and applications

“…Additionally, other strategies can be considered for tuning the physicochemical properties of CO 2 /epoxide polycarbonates, including (i) terpolymerisation (i.e. reaction of CO 2 with an epoxide and a third monomer that can be another epoxide, an anhydride or caprolactone); [251][252][253] (ii) block-copolymerisation (i.e. sequential growth of a polymer consisting of different blocks of which at least one is based on CO 2 /epoxide copolymerisation) 86,243,254 (iii) post-polymerisation modification of the functional groups that might be present along the backbone; 252 (iv) end-group modification by using functional compounds as chain transfer agents (if the functional compound contains two or more groups that can give chain transfer, polymer extension or branching can be achieved 17,255 ); (v) blending of polycarbonates with other polymers or with inorganic solids.…”

Surface Modification of a MOF-based Catalyst with Lewis Metal Salts for Improved Catalytic Activity in the Fixation of CO2 into Polymers

“…One of the most sustainable strategies for utilizing CO 2 is the copolymerization of CO 2 with epoxides to produce poly(alkylene carbonates). These materials are commercially viable owing to their vast number of applications, such as in adhesives, packing and coating materials, and ceramic binders [18][19][20][21][22]. Furthermore, these polycarbonates are biodegradable and are useful in biomedical applications [19].…”

“…These materials are commercially viable owing to their vast number of applications, such as in adhesives, packing and coating materials, and ceramic binders [18][19][20][21][22]. Furthermore, these polycarbonates are biodegradable and are useful in biomedical applications [19]. The alternating copolymerization of CO 2 with epoxides was first reported by Inoue et al, who used a diethylzinc-water system as a catalyst [23,24].…”

A Zn-MOF-Catalyzed Terpolymerization of Propylene Oxide, CO2, and β-butyrolactone

“…The conversion of CO 2 into chemical commodities, particularly the synthesis of biodegradable poly(alkylene carbonates) by the alternating copolymerization of an epoxide and CO 2 , is regarded as one of the most sustainable approaches for the use of CO 2 as a source material in large-scale industrial processes [1][2][3][4][5][6][7][8][9][10][11]. Poly(alkylene carbonates) are characterized by a variety of properties, e.g., lightness, strength, durability, high transparency, heat resistance, and good electrical insulating ability.…”

“…They are applied as adhesives, coating and packing materials, and binders in ceramic industries. Furthermore, they are important candidates for biomedical applications because of their low toxicity, biocompatibility, and biodegradability [1,7,12,13].…”