journal article

Journal Article

Macromolecules. 2014, 47(24), p. 8531-8540

Alkoxyoxirane, a unique cyclic monomer: Controlled cationic homopolymerization mediated by long-lived species and copolymerization with vinyl ether via alkoxy group transfer

American Chemical Society

English

2014-12-23

https://doi.org/10.1021/ma502151q

Kanazawa A., Kanda S., Kanaoka S., et al. Alkoxyoxirane, a unique cyclic monomer: Controlled cationic homopolymerization mediated by long-lived species and copolymerization with vinyl ether via alkoxy group transfer. Macromolecules 47, 8531 (2014); https://doi.org/10.1021/ma502151q.

1-Methoxy-2-methylpropylene oxide (MOMPO), an alkoxyoxirane that can generate a carbocation adjacent to an alkoxy group via ring-opening, was demonstrated to polymerize in a controlled manner with the use of a metal chloride as a Lewis acid catalyst. The choice of the initiating system is critical for the successful controlled homopolymerization of this alkoxyoxirane; a GaCl3/THF system was observed to be the best combination for the initiating system. Furthermore, the copolymerization of MOMPO with isopropyl vinyl ether (IPVE) generated long-lived species when CF3SO3H/nBu4NI was used as the initiating system. Surprisingly, the reaction proceeded via the transfer of the alkoxy group in the IPVE unit. More specifically, the isopropoxy group at the penultimate IPVE unit transferred to the MOMPO-derived propagating cation after the crossover reaction from the IPVE-derived carbocation to MOMPO. This type of reaction creates a side group that possesses the ring-opened MOMPO structure with the isopropoxy group. The generation of copolymers via the "alkoxy-group transfer" mechanism is unique to the copolymerization in this study and was confirmed by 1H, 13C, and 2D NMR analyses and by the acid hydrolysis and subsequent reacetalization reactions of the products.

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/ma502151q

100926

Alkoxyoxirane, a unique cyclic monomer: Controlled cationic homopolymerization mediated by long-lived species and copolymerization with vinyl ether via alkoxy group transfer

American Chemical Society

English

2014-12-23

Macromolecules

47

24

8531

8540

https://doi.org/10.1021/ma502151q

https://hdl.handle.net/11094/100926