Quaternary ammonium and sulfonium derivatives of 2-chloromethylbutadiene and poly-2-chloromethylbutadiene†

TLDR: In this article, 2-Chloromethylbutadiene has been converted to quaternary ammonium and sulfonium monomers which have been polymerized at room temperature.

Abstract: 2-Chloromethylbutadiene has been converted to quaternary ammonium and sulfonium monomers which have been polymerized at room temperature. They show a very great tendency to dimerize on heating in water solution. The aqueous quaternary monomer dimerized 25 times as fast as the aqueous sulfonium monomer and nearly 105 times as fast as neat isoprene at 50°C. The quaternary monomer dimerized with itself in a water solution to which 2-hydroxymethylbutadiene has been added as an example of a nonionic diene. The latter monomer did not dimerize rapidly in water, nor did 2-aminomethylbutadiene. The hydrochlorides of 2-aminomethylbutadiene and 2-dimethylaminomethylbutadiene dimerized at rates comparable to that of the sulfonium monomer. Poly 2-chloromethylbutadiene contains reactive chlorine except for the structure resulting from the minor extent of 1,2 addition. Water-soluble derivatives have been made from it with nucleophilic tertiary amines and sulfides. Cationic polymers are substantive to paper pulp, and the sulfonium polymers can be cured in paper to give improved wet strength.