The kinetics of the free radical copolymerization of HEMA, EGDMA and TEGDA with MMA have been studied using NIR spectroscopy to follow the reduction in the total C=C concentration with time and 1H NMR to distinguish between the monofunctional and difunctional monomers. ESR measurements of the concentrations of propagating radicals during polymerization have been combined with the conversion results to derive values for the rate constants kp (propagation) and kt (termination). HEMA decreases the gel time of MMA, but the initial rate is unchanged, whereas EGDMA and TEGDA decrease the gel‐time and increase the initial rate of polymerization.
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