Abstract
The radical copolymerization of allyl chloroacetates with vinyl acetate has been studied in the feed range from 10 to 90 mol% allyl chloroacetates. The following values were obtained by the Kelen-Tüdös method for the reactivity ratios: allyl acetate (M1)-vinyl acetate (M2), r1=0.43, r2=1.8; allyl chloroacetate (M1)-vinyl acetate (M2), r1=0.69, r2=0.77; allyl dichloro-acetate (M1)-vinyl acetate (M2), r1=0.54, r2=0.57; allyl trichloroacetate (M1)-vinyl acetate (M2), r1=0.28, r2=0.41; The Q-e parameters were calculated from the allyl (M1)-vinyl acetate (M2) reactivity ratios. The e parameters of allylic monomers have been found to be well correlated with parameters such as Taft’s σ* constants of the chloroalkyl group an acids, 13C NMR chemical shift values of the γ carbon in the allylic monomers, and frR for the γ carbon of allyl group in the allylic monomers. The rate of copolymerization of allyl chloroacetates and conversion to copolymers increased as one goes from allyl alkanoates, such as allyl acetate, allyl butyrate, and allyl trimethylacetate, to allyl chloroacetates, though molecular weights of the copolymers diminished due to the chlorine abstraction by a growing chain.
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Shigetomi, Y., Ono, N., Kato, H. et al. Allylic Polymers II. Effects of Chloro-Substituents on Copolymerization of Allyl Chloroacetates with Vinyl Acetate. Polym J 24, 87–98 (1992). https://doi.org/10.1295/polymj.24.87
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DOI: https://doi.org/10.1295/polymj.24.87