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The photopolymerization reactivity and the polymer structure control of several benzylammonium sorbates as the 1,3-diene monomers in the crystalline state are described. The polymerization of the 4-methyl-substituted benzylammonium derivative proceeds to give a stereoregular polymer in the crystalline state under UV irradiation, similar to naphthylmethylammonium sorbate. We have also succeeded in the synthesis of a ladder polymer by topochemical polymerization of p-xylylenediammonium disorbate as the bifunctional monomer under similar conditions. The polymerization mechanism and the stereochemical structure of the resulting polymers are discussed based on the results of the X-ray single crystal structure analysis as well as IR, NMR, and ESR spectroscopic studies. We have demonstrated a unique twodimensional polymer synthesis by topochemical polymerization via a radical chain mechanism based on polymer crystal engineering, which is useful for the control and design of the polymerization reactivity and the polymer chain and crystal structures.

Polymer crystal engineering for controlling photoreactivity and polymer chain structures in the crystalline state