Proceedings of the Japan Academy, Series B
Online ISSN : 1349-2896
Print ISSN : 0386-2208
ISSN-L : 0386-2208
Polymer crystal engineering for controlling photoreactivity and polymer chain structures in the crystalline state
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2001 Volume 77 Issue 6 Pages 110-114


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 two-dimensional 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.

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