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Monomer sequence control via living anionic copolymerization : synthesis of alternating, statistical, and telechelic copolymers and sequence analysis by MALDI ToF mass spectrometry.

Hutchings, Lian R. and Brooks, Paul P. and Parker, David and Mosely, Jackie A. and Sevinc, Serkan (2015) 'Monomer sequence control via living anionic copolymerization : synthesis of alternating, statistical, and telechelic copolymers and sequence analysis by MALDI ToF mass spectrometry.', Macromolecules., 48 (3). pp. 610-628.

Abstract

Diphenylethylene (DPE) is a monomer which has attracted significant interest from both academia and industry. DPE can undergo (co)polymerization by living anionic polymerization but is incapable of forming a homopolymer due to steric hindrance. Herein the copolymerization of DPE and 1,1-bis(4-tert-butyldimethylsiloxyphenyl)ethylene (DPE-OSi) with styrene or butadiene is described in order to produce (functional) copolymers with controlled comonomer sequences—either alternating or telechelic. The copolymer sequences are inherently controlled by relative reactivity ratios, which in turn can be tuned by both monomer structure and the polarity of the polymerization solvent. The compositions of the copolymers prepared in this study were analyzed by 1H NMR spectroscopy and MALDI ToF mass spectrometry, the latter offering a unique opportunity to demonstrate perfect alternating sequences and insight into other sequences such as telechelic polymers.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:http://dx.doi.org/10.1021/ma5016038
Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © 2015 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ma5016038.
Date accepted:No date available
Date deposited:30 January 2015
Date of first online publication:22 January 2015
Date first made open access:22 January 2016

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