Stereospecific Polymerization of 1,3-Diene Monomers in the Crystalline State

Abstract

This article deals with the features and mechanism of the polymerization of 1,3-diene monomers in the crystalline state. First, I refer to the characteristics and classification of solid-state polymerization, including the definition of several key terms such as ‘topochemical reaction’ and ‘crystal engineering’. The topochemical polymerization of muconic and sorbic acid derivatives, which are 1,3-diene monomers with one or two carboxylates at each end of a butadiene or pentadiene moiety, is then described. The polymerization behaviour and reactivity are discussed, as well as the structure and properties of the polymer crystals obtained as the polymerization product. The relationship between the crystal structure and the reactivity is discussed on the basis of the concept of crystal engineering, which is a useful method to design the reactivity, structure, and properties of organic solids. In the final part, the stereochemical control of polymers as well as the application of the polymer crystals obtained by topochemical polymerization are described. The polymer crystals are capable of repeated and reversible intercalation, which may allow the design of new organic solids for applications such as molecular recognition, separation, and catalysis and extend the range and practical utility of current intercalation compounds.