Cationic Ring-Opening Polymerization of an Exomethylene Group Carrying Cyclic Carbonate. Pseudo-Living Polymerization of 5-Methylene-1,3-dioxan-2-one by the Assistance of the Exomethylene Group

Abstract

Cationic ring-opening polymerization of a cyclic carbonate carrying an exomethylene moiety, 5-methylene-1,3-dioxan-2-one (ExTMC), was carried out, and its behavior was compared with a cyclic carbonate having no exomethylene group, 1,3-dioxan-2-one (TMC). ExTMC afforded the polymers with larger molecular weights than TMC under any conditions. The observed molecular weights of the polymers agreed well with the calculated ones in the polymerization of ExTMC with TfOH at 0 °C. A linear relationship was observed between the conversion and number-average molecular weight of the polymer obtained in the polymerization of ExTMC, which could not be observed in the polymerization of TMC. After ExTMC was completely converted, the polymerization took place again when the same amount of ExTMC was introduced into the polymerization mixture. The effect of the exomethylene group on the polymerization behavior was analyzed by an ab initio molecular orbital calculation to determine the possibility of the presence of an allylic cationic intermediate. It was suggested that the stabilization of the propagating cation by the exomethylene group caused the living character of the cationic polymerization of ExTMC. Furthermore, a block copolymer of ExTMC with a vinyl ether was synthesized as an application of the pseudo-living polymerization of ExTMC.

Volume‐expandable monomer 5,5‐dimethyl‐1,3‐dioxolan‐2‐one: Its copolymerization behavior with epoxide and its applications to shrinkage‐controlled epoxy‐curing systems

“…Six‐membered cyclic carbonate (6CC) undergoes both cationic and anionic polymerizations1–7 and thus is expected to be adopted to various curing systems under a wide range of reaction conditions 8–10. A more attractive feature of 6CC is its intrinsic volume‐expandable nature during polymerizations (degree of expansion = 3.3–7.7%) 9…”

Nucleophile-initiated and thermal bulk polymerizations of cyclic trimethylene carbonate in the absence of added catalysts

“…The polymerization can be achieved using a large variety of intiators: anionic, [1][2][3][4][5][6][7] cationic [4,[8][9][10] and of coordination-insertion type. [11][12][13][14][15][16][17] Very recently the enzymatic polymerization has also been developed.…”

Functional Polycarbonate of a d-Glucal-Derived Bicyclic Carbonate via Organocatalytic Ring-Opening Polymerization

“…APCs can be synthesized via ring-opening polymerization (ROP) in a controlled manner, for which anionic, , cationic, , enzymatic, metal-catalyzed, and organo-catalyzed , methods are known. For instance, poly­(trimethylene carbonate) (PTMC), used in commercial applications as degradable sutures and orthopedic fixation devices, is a structurally simple form of APC synthesized by ROP of the six-membered cyclic carbonate monomer, TMC.…”