Topochemistry of the solid-state polymerization of diacetylenes containing unsaturated side groups

Abstract

The electronic spectra of polymers in the monomer matrix have been investigated for two structurally similar diacetylenes one of which has side substituents containing the allyl bond which is responsible for degradative chain transfer in the case of liquid-phase polymerization. Melting points and phase transition temperatures were determined for the monomers and polymers by the DSC method. A study of the integral absorption of the polymers in the visible portion of the spectrum shows that the photopolymerization rate for the diacetylene containing the allyl double bond is only one-third of that for the diacetylene that is without the allyl bond. This fact is attributed to a high degree of topotacticity of the solid-state polymerization of crystalline diacetylenes.