Issue 12, 2022

The influence of thiocarbonylthio compounds on the B(C6F5)3 catalyzed cationic polymerization of styrene

Abstract

“Living” cationic polymerization techniques based on reversible termination of propagating carbocations have been known for a number of decades but more recently degenerative chain transfer systems have been reported for the controlled polymerization of a number of monomers including vinyl ethers and p-methoxystyrene. In this work we demonstrate that when applied to the cationic polymerization of styrene, thiocarbonylthio compounds can lead to a dual control mechanism, where degenerative chain transfer occurs concurrent with a reversible addition mechanism. Using a B(C6F5)3/ROH initiating system it is shown that the addition to the thiocarbonylthio compound coupled with the high stability of the cationic intermediate allows for a limited degree of control directly, even in the absence of the degenerative transfer process, with the concentration of the alcohol initiator determining the molar mass. Unlike more stable carbocations formed from vinyl ethers and p-methoxystyrene, the dormant nature of the cationic intermediate formed in the presence of thiocarbonylthio compounds leads to a decrease in the rate of polymerization but can be used advantageously to induce control of polymerizations that employ efficient initiators.

Graphical abstract: The influence of thiocarbonylthio compounds on the B(C6F5)3 catalyzed cationic polymerization of styrene

Supplementary files

Article information

Article type
Paper
Submitted
04 Jan 2022
Accepted
28 Feb 2022
First published
07 Mar 2022

Polym. Chem., 2022,13, 1739-1750

The influence of thiocarbonylthio compounds on the B(C6F5)3 catalyzed cationic polymerization of styrene

A. Destephen, E. González de San Román and N. Ballard, Polym. Chem., 2022, 13, 1739 DOI: 10.1039/D2PY00016D

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