Geometry-directed cyclisation within the transfer-dominated branching radical telomerisation of dimethacrylates†

The use of Transfer-dominated Branching Radical Telomerisation (TBRT) in the homopolymerisation of neopentyl glycol dimethacrylate has shown the formation of highly cyclised structures even at relatively highly concentrated reaction conditions. This is contrary to previous reports of the TBRT of unconstrained multi-vinyl taxogens and is the first indication of geometry directed cyclisation within the formation of branched polyesters via TBRT methods. Surprisingly, there was limited impact of increased reaction temperature on recovered samples. Dilution led to an expected increase in cyclisation, however, the recovered polymer samples are unprecedented in the extent of cyclisation and the reduction in the use of telogen required to suppress gelation and form soluble branched polymers.