University CrestBranched Polymers via Living Polymerisation ChemistryArmes Research Group
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  4 September 2005

We have recently explored the 'Sherrington' approach to branched copolymers in the context of various types of living polymerisation chemistry [V. Bütün et al., Chem. Commun. 2004; V. Bütün et al., Macromolecules, 2005; Y. Li and S. P. Armes, Macromolecules, 2005]. Fundamental differences between living and non-living polymerisations have been identified. Normally, the Sherrington-type synthesis of a branched copolymer involves conventional free radical polymerisation; the gel point of a copolymerising mixture of a monovinyl and divinyl monomer is suppressed by the addition of an efficient chain transfer agent such as a thiol. In a living polymerisation, no thiol is required since the primary chain is controlled by the monomer/initiator molar ratio. Provided that there is less than one brancher per copolymer chain, gelation does not occur and the sole product is a soluble branched copolymer. However, since the final copolymer molecular weight is only achieved at the end of a living polymerisation, this means that branching occurs very late in the copolymerisation, whereas branched copolymers are formed in the early stages of copolymerisations conducted using conventional (non-living) free radical polymerisation chemistry. This new concept has been explored in the context in detail in the context of ATRP. Particular insight has been gained by using a disulfide-based dimethacrylate as a cleavable branching agent in conjunction with a light scattering GPC detector to probe the redox-mediated degradation of the branched copolymer chains [see below; Y. Li and S. P. Armes, Macromolecules, 2005, in the press]. This 'retro-synthesis' approach confirmed that the original branched copolymer simply comprised a series of randomly linked near-monodisperse primary chains, which suggests that little or no chain transfer to polymer occurs during copolymerisation.

Selected Publications
"Synthesis of branched methacrylic copolymers: comparison between RAFT and ATRP and effect of varying the monomer concentration"
J. Rosselgong, S. P. Armes, W. R. S. Barton and D. Price
Macromoecules 2010, 43, 2145
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"RAFT synthesis of branched acrylic copolymers"
C. D. Vo, J. Rosselgong, S. P. Armes, N. C. Billingham
Macromolecules 2007, 40, 7119
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"Synthesis and peptide-induced degradation of biocompatible fibers based on highly branched poly(2-hydroxyethyl methacrylate)."
L. Wang, C. Li, A. J. Ryan, S. P. Armes
Advanced Materials 2006, 18, 1566
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"Development of Branching in Living Radical Copolymerization of Vinyl and Divinyl Monomers."
I. Bannister, N. C. Billingham, S. P. Armes, S. P. Rannard, P. Findlay
Macromolecules 2006, 39, 7483
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"Synthesis of branched water-soluble vinyl polymers via oxyanionic polymerization"
Y. Li and S. P. Armes
Macromolecules 2005, 38, 5002
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"Synthesis and characterization of branched water-soluble homopolymers and diblock copolymers using group transfer polymerization"
V. Butun, I. Bannister, N. C. Billingham, D. C. Sherrington and S. P. Armes
Macromolecules 2005, 38, 4977
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"Synthesis of branched poly(methyl methacrylate)s via controlled/living polymerisations exploiting ethylene glycol dimethacrylate as branching agent"
F. Isaure, P. A. G. Cormack, S. Graham, D. C. Sherrington, S. P. Armes and V Butun
Chemical Communications 2004, 9, 1138
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