Polymerization of Diacetylenes in Orderd Reaction Medium

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Diacethylene derivative carrying a mesogenic core has been prepared and its kinetic behavior of the nematic phase polymerization has been investigated. The obtained results are as follows.1) Diacethylene trimer carrying cyclopropene rings was isolated. The trimer generates a biradical, which has a thermally accessible tripler state (D=0.00253 cm^<-1>, E=0.00041 cm^<-1>), through the ring cleavage by UV irradiation or by heating at temperatures higher than 90ﾟC.2) The molecular and electronic structure of the biradical was calculated by GVB method in collaboration with Prof.S.Nagase (Yokohoma National Univ.). The calculated result is consistent with the experimental result.3) Template effect of the trimer or the pentamer on the oligomerization process of diacethlenes was discovered.These kinetic features can be well rationalized by the flexibility and orderness of the reaction environment of the nematic phase.