Using temperature to modify the reaction conditions and outcomes of polymers formed using transfer-dominated branching radical telomerisation (TBRT).

A clear trend towards lower weight average molecular weights ( M w ) was observed as with increasing reaction temperature, with values ranging from M w = 2 061 000 g mol −1 at 70 °C to 266 330 g mol −1 at 100 °C ( Table 1 ).

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As TBRT is highly dominated by chain-transfer reactions, this may be significant for reaction optimisation.

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During TBRT reactions, the variation in vinyl group and telogen consumption with increasing reaction temperature was highly significant, with the relative rate of telogen consumption increasing at higher vinyl group conversions at higher reaction temperatures, effectively suppressing intermolecular branching.

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