Issue 3, 2021

Sequence-regulated vinyl polymers via iterative atom transfer radical additions and acyclic diene metathesis polymerization

Abstract

A new strategy for the synthesis of sequence-regulated vinyl polymers based on a combination of iterative atom transfer radical additions (ATRAs) of vinyl monomers and acyclic diene metathesis (ADMET) polymerization was developed. A molecularly defined vinyl monomer sequence at the single monomer unit level was constructed in telechelic diene sequence-regulated oligomers by iterative metal-catalyzed ATRAs of vinyl monomers to dichloride followed by allylation of both carbon–chloride terminals. ADMET polymerization of the obtained telechelic diene oligomer with a symmetrical monomer sequence resulted in polymers with an embedded vinyl monomer sequence that was repeatedly connected by an olefin formed by olefin metathesis polymerization. The subsequent hydrogenation of the main-chain olefins led to polymers that mimicked sequence-regulated vinyl polymer structures consisting of saturated C–C main chains. In particular, this study enabled the synthesis of sequence-regulated vinyl polymer mimics that have perfect and periodic styrene–acrylate–styrene–ethylene–methylene sequences, no statistical distributions of the comonomer compositions and sequences in polymer chains, relatively high molecular weights, and only carbon–carbon single bonds in the main chain. The thermal properties of the sequence-regulated vinyl polymer mimics were evaluated and compared with those of hypothetical random copolymers of styrene, acrylate, and ethylene units with the same comonomer contents.

Graphical abstract: Sequence-regulated vinyl polymers via iterative atom transfer radical additions and acyclic diene metathesis polymerization

Supplementary files

Article information

Article type
Paper
Submitted
11 Nov 2020
Accepted
03 Dez 2020
First published
07 Dez 2020

Polym. Chem., 2021,12, 423-431

Sequence-regulated vinyl polymers via iterative atom transfer radical additions and acyclic diene metathesis polymerization

M. Miyajima, K. Satoh and M. Kamigaito, Polym. Chem., 2021, 12, 423 DOI: 10.1039/D0PY01564D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements