Cationic Copolymerization Behavior of Glycidyl Phenyl Ether with Seven‐Membered Cyclic Carbonate

Abstract

Summary: To clarify the cationic copolymerization behavior of epoxide and cyclic carbonate, the copolymerization behavior of glycidyl phenyl ether (GPE) with seven‐membered cyclic carbonate (7CC) was carried out using methyl trifluoromethanesulfonate (MeOTf) as a cationic initiator. The addition of 7CC accelerated the consumption rate of GPE, and the resulting copolymers were richer in 7CC‐derived unit compared to the feed ratio of 7CC. During the copolymerization, a large amount of five‐membered cyclic carbonate having a phenoxymethyl group (PM‐5CC) was produced as a by‐product, which suggests the corresponding spiroorthocarbonate was formed as an intermediate and that residual oxytetramethylene (OTM) unit was incorporated into the copolymer sequence. From 1H NMR analysis, it was found that the copolymers had a statistically random sequence consisting of GPE, 7CC, and OTM units. magnified image

Metal‐free ring‐opening polymerization of glycidyl phenyl ether initiated by tetra‐n‐butylammonium acetate and its application to the hydroxyl‐terminated telechelic polymer

“…The ring‐opening polymerization of glycidyl phenyl ether (GPE), a common epoxide widely used as a monofunctional diluent in epoxy resins and as a modifier for dyes and fibers, has been investigated by many researchers as a polymerization technique for developing effective curing systems 8–12. The presence of metal initiators during curing often results in polymers that have low insulation and that tend to rust out.…”

“…[8][9][10][11][12] The presence of metal initiators during curing often results in polymers that have low insulation and that tend to rust out. It should also be noted that the polymerization of GPE is accompanied by frequent side reactions (i.e., chain transfer and termination reactions) that limit the increase in the molecular weights of poly(GPE).…”

Cationic copolymerization behavior of epoxide and 3-isochromanone

“…In addition to the homopolymerization that has been used for such practical applications, cationic copolymerizations of epoxides with other monomers have attracted much attention for the decades . The comonomers that have been reported so far include cyclic ethers, bicyclic ethers, lactones, cyclic carbonate, cyclic anhydrides, and several vinyl monomers . These copolymerizations have several advantages such as: (1) introduction of comonomer‐derived functions into the resulting copolymers, (2) formation of main chain structures that are totally different from that of the homopolymers of epoxides, leading to the drastic changes in physical properties, and (3) reduced volume shrinkage.…”