The synthesis of long-chain branched polymers has long been of interest to both academic and industry. In the past decade we have reported the synthesis of well-defined, nearly monodisperse DendriMacs1,2 which were designed and synthesised for structure-property correlation studies. The synthesis of DendriMacs is extremely tedious and exploits time-consuming methodologies based on the coupling of AB2 macromonomers. We have also reported the synthesis of HyperMacs3 and HyperBlocks4 by a more facile and scalable one-pot coupling reaction of AB2 macromonomers, which results in rather polydisperse branched polymers with defined linear segments between branch points. However, we report here today a new synthetic strategy for the production of randomly-branched, long-chain polymers prepared by anionic chain-transfer polymerisation. The described methodology is an adaption of the previously reported “Strathclyde route” developed by Sherrington et al in which highly branched polymers were prepared by free radical polymerisation using a divinyl comonomer in presence of a chain transfer agent to prevent gelation5. We will describe how living anionic polymerisation may be adapted to allow the copolymerisation of simple commercial monomers with readily availabe difunctional comonomers to produce branched, soluble polymers by a commercially scalable approach. This new approach has been shown to be viable for the synthesis of branched polymers from dienes, methylmethacrylate and for the production of branched copolymers from styrene/diene. References 1. L. R. Hutchings, S. J. Roberts-Bleming, Macromolecules 2006, 39, 2144-2152. 2. L. R. Hutchings, S. M. Kimani, D. M. Hoyle, D. J. Read, C. Das, T. C. B. McLeish, T. Chang, H. Lee, D. Auhl, ACS Macro Letters 2012, 1, 404-408 3. L. R. Hutchings, J. M. Dodds, S. J. Roberts-Bleming, Macromolecules 2005, 38, 5970-5980. 4. L. R. Hutchings, J. M. Dodds, D. Rees, S. M. Kimani, J. J. Wu, E. Smith, Macromolecules 2009, 42, 8675-8687. 5. N. O'Brien, A. McKee, D. C. Sherrington, A. T. Slark, A. Titterton. Polymer 2000, 41 (15), 6027-6031.

Synthesis of randomly branched polymers by anionic chain-transfer polymerisation

251st National Meeting (2016)

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