Development of branching in living radical copolymerization of vinyl and divinyl monomers

Bannister, Iveta, Billingham, Norman C, Armes, Steven P, Rannard, Steven P and Findlay, Paul (2006) Development of branching in living radical copolymerization of vinyl and divinyl monomers. Macromolecules, 39 (22). pp. 7483-7492. ISSN 0024-9297

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Abstract

The branching copolymerization of 2-hydroxypropyl methacrylate ( HPMA) with either ethylene glycol dimethacrylate (EGDMA) or bisphenol A dimethacrylate (BPDMA) as the branching agent has been carried out using atom transfer radical polymerization (ATRP) in methanol at 20 C. With EGDMA, soluble branched copolymers were obtained provided that less than one branching agent was incorporated per primary chain: higher levels of EGDMA led to gelation, as expected. Analysis of the changes in the molecular weight and polydispersity of the polymers shows that the formation of highly branched chains occurs only at high (> 90%) conversions. Chain coupling is close to the ideal behavior predicted by the Flory-Stockmayer theory, suggesting that all double bonds are equally reactive and that there is no significant cyclization, in contrast to conventional free radical polymerization. This analysis is confirmed by comparison of the consumption of the EGDMA branching agent with predictions from both theory and simulation. With BPDMA as the branching agent, similar results are obtained although branching is slightly less efficient.

Item Type: Article
Additional Information: EPSRC CASE grant with Unilever to NCB and SPA (directed by NCB, after SPA moved to Sheffield). Experimental and theoretical work all done at in Sussex. First detailed study of statistics of branching in controlled radical polymerisations. First ever analysis of brancher consumption.
Schools and Departments: School of Life Sciences > Chemistry
Depositing User: Iveta Bannister
Date Deposited: 06 Feb 2012 21:11
Last Modified: 29 Mar 2012 09:26
URI: http://sro.sussex.ac.uk/id/eprint/30103
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