Dibromomaleimide End Functional Polymers by RAFT Polymerization Without the Need of Protecting Groups

Mathew P Robin; Mathew W Jones; David M Haddleton; Rachel K O'Reilly

doi:10.1021/mz200164x

Dibromomaleimide End Functional Polymers by RAFT Polymerization Without the Need of Protecting Groups

ACS Macro Lett. 2012 Jan 17;1(1):222-226. doi: 10.1021/mz200164x. Epub 2011 Dec 23.

Authors

Mathew P Robin¹, Mathew W Jones¹, David M Haddleton¹, Rachel K O'Reilly¹

Affiliation

¹ Department of Chemistry, Gibbet Hill Road, University of Warwick, Coventry, CV4 7AL United Kingdom.

PMID: 35578484
DOI: 10.1021/mz200164x

Abstract

Polymers bearing the dibromomaleimide (DBM) group as a functional chain end have been synthesized by RAFT polymerization. A DBM functional chain transfer agent (CTA) was utilized to afford well-defined P^tBA, PMA, and PTEGA, without the requirement of protecting group chemistry. It was found that RAFT polymerization of NIPAM and styrene with this CTA was severely retarded/inhibited which is ascribed to their relatively low propagation rate constants compared to acrylates. This observation is accounted for by a reversible trapping of propagating radicals by the DBM group in RAFT polymerizations using a monomer with low k_p. However, further attempts to synthesize DBM-terminated P^tBA and PMA by ATRP using an analogous initiator were unsuccessful, and broad PDI were observed. Furthermore, highly efficient postpolymerization functionalization of DBM-terminated PMA produced by RAFT, with the model compound thiophenol was also demonstrated.