Polymerization benzyl muconates

In this chapter, we describe the isomerization, dimerization, and topochemical polymerization of benzyl muconates with various kinds of substituents on the benzyl ester group (Scheme 24.1), in order to reveal the solid-state reaction mechanism by the direct observation of crystal structures which change during the reactions. 

Matsumoto, A., Tanaka, T. and Oka, K. (2005) Stereospecific radical polymerization of substituted benzyl muconates in the solid state under topochemical control. Synthesis, 1479-1489. 

Matsumoto, A., Furukawa, D. and Nakazawa, H. (2006) Stereocontrol of diene polymers hy topochemical polymerization of substituted benzyl muconates and their crystallization properties. J. Polym. Sci. Part A Polym. Chem., 44, 4952-4965. 

Figure 1 summarizes the chemical structures of the topochemically polymerizable 1,3-diene monomers providing stereoregular 1,4-trans polymer (Scheme 6) [ 16]. Most of the polymerizable monomers contain benzyl, naphthylmethyl, and long alkyl-chain substituents in their chemical structures. The (ZyZ)-, (E,Z)-, and ( , )-muconic and sorbic acids as well as the other diene carboxylic acids are used as the ester, amide, and ammonium derivatives. In contrast to this, the carboxylic acids themselves have crystal structures unfavorable for polymerization while they undergo [2-1-2] photodimerization, as has already been described in the preceding sections.

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