Abstract
The chain-transfer reaction of trisubstituted hydrides of silicon, germanium and tin (R 3MeH) have been studied in the polymerizations of vinyl monomers having different double bond polarities e. The rate constant of this reaction strongly depends on the type of the substituent R present in R 3MeH, the central atom Me, and the monomer polarity. Quantitative correlations have been established for the first time between the reactivity C p and the induction effect of the substituent ( Σσ s* —Taft constant) present in these metal hydrides; this is regarded as experimental proof of the hypothesis that polarity has a decisive effect in the intermediate stage of the chain-transfer reaction. The R 3MeH addition does not affect the stationary rate and reduces gelling during high-conversion polymerization. The possibility is shown of a block copolymer synthesis by a radical polymerization over poly-functional group IV B metal compounds.
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