DIACETYLENE-CONTAINING POLYMERS .9. HALOGENATION OF SOME DIACETYLENE-CONTAINING POLYESTERS

The chlorination and bromination of some diacetylene-containing polyes ters in the solid state and solution were investigated. The solid stat e bromination of the crystalline poly(octa-3,5-diynylenesebacate) took place smoothly at room temperature giving a new polyester containing 1,2,3,4-tetrabromobutadiene units, while chlorination caused the topoc hemical crosspolymerization of the diacetylene groups instead of addit ion of chlorine atoms. The solid state bromination of the amorphous po lyester was very slow, but both chloronation and bromination in chloro form solutions readily took place giving tetrahalogenated butadiene-co ntaining, totally amorphous polymers. Degradation during halogenation was minimum. The mechanisms of these halogen addition reactions are di scussed based on the results of spectroscopic studies.