Collect. Czech. Chem. Commun. 1982, 47, 785-792

The effect of substitution on the reactivity of the monomer in the copolymerization of styrene with 2,3-unsatured aldehydes and ketones

Otakar Seyčeka, Bohumil Bednářb, Milan Houskac and Jaroslav Kálalc

a Chemopetrol, Synthetic Rubber Research Institute 278 52 Kralupy nad Vltavou
b Institute of Chemical Technology, Department of Polymers, 166 28 Prague 6
c Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, 162 06 Prague 6


The monomer reactivity ratios of the copolymerization of styrene with propenal, 2-methylpropenal, 2-ethylpropenal, methylvinyl ketone and methylisopropenyl ketone were determined and their reliability was checked. For copolymerization conducted to low conversions, a simple procedure was proposed in order to rule out the effect of the conversion heterogeneity of copolymers on the determination of r1, r2 by calculation using a differential copolymerization equation. When comparing aldehydes and ketones with reference monomers having a similar skeleton of the molecule, the effect of substitution on the monomer reactivity in the copolymerization was examined, and a new correlation, en, was suggested, interpreting the influence of polar effects of substituents on the monomer reactivity. It was proved that the copolymerization kinetics of 2-ethylpropenal is affected by the steric hindrance from the part of the too bulky substituent.