Expanding vinyl ether monomer repertoire for ring‐expansion cationic polymerization: Various cyclic polymers with tailored pendant groups. Issue 18 (15th May 2017)

• Record Type: Journal Article
• Authors: Kammiyada, Hajime; Ouchi, Makoto; Sawamoto, Mitsuo
• Is Part Of: Journal of polymer science. Volume 55:Issue 18(2017)
• Page Start: 3082
• Page End: 3089
• Publication Date: 2017-05-15
• Subjects: cationic polymerization -- cyclic polymers -- graft copolymers -- living radical polymerization -- ring‐expansion polymerization -- vinyl ethers; 547
• DOI: 10.1002/pola.28648
• Languages: English
• ISSNs: 0887-624X

Abstract

ABSTRACT: Herein, we clarified the ring‐expansion cationic polymerization with a cyclic hemiacetal ester (HAE)‐based initiator was versatile in terms of applicable vinyl ether monomers. Although there was a risk that higher reactive vinyl ethers may incur β‐H elimination of the HAE‐based cyclic dormant species to irreversibly give linear chains, the polymerizations were controlled to give corresponding cyclic polymers from various alkyl vinyl ethers of different reactivities. Functional vinyl ether monomers were also available, and for instance a vinyl ether monomer carrying an initiator moiety for metal‐catalyzed living radical polymerization in the pendant allowed construction of ring‐linear graft copolymers through the grafting‐from approach. Furthermore, ring‐based gel was prepared via the addition of divinyl ether at the end of the ring‐expansion polymerization, where multi HAE bonds cyclic polymers or fused rings were crosslinked with each other. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2017, 55, 3082–3089 Abstract : Various vinyl ether monomers were precisely polymerized via ring‐expansion cationic polymerization with a cyclic hemiacetal ester‐based initiator toward cyclic macromolecular engineering. Design of the pendant group of the vinyl ether monomer allowed introduction of various alkyl chains to control properties of the resultant cyclic topology such as softness and hardness as well as reactive sites such as an initiator for another living polymerization or a crosslinking group.