Abstract
Abstract The polymerisation of diethylene glycolbis-allyl carbonate to high conversion was investigated by ESR, FTIR and DMA techniques. The ESR spectrum was simulated using a two line, a three line and a broad line spectral component. These spectral components were assigned to the propagating radical, a mobile allyl radical and a less mobile allyl radical formed on a crosslink. The change in the resonance frequency of the ESR cavity during polymerisation was demonstrated to be sensitive to gel formation. ESR and FTIR data show that the restriction in the mobility of the system occurred well after gel formation making this system different from the vinyl systems. The ESR and FTIR data were used to calculate the rate constants for propagation, termination, transfer and reinitiation at high conversion. The chain transfer constant was not found to change with conversion. The DMA data shows that the extent of cyclisation during the polymerisation is about 20–25%.
Published Version
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