Polymerization of Diacetylenes in Orderd Reaction Medium

制备了带有介介核的二乙烷衍生物，并对其向列相聚合动力学行为进行了研究。所得结果如下：1)分离出携带环丙烯环的二乙基三聚体。该三聚体通过紫外辐射或高于90℃的加热产生双自由基，其具有热可达的三重态（D=0.00253 cm^<-1>， E=0.00041 cm^<-1>）。2)与Yokohoma国立大学nagase教授合作，用GVB方法计算了双自由基的分子和电子结构。计算结果与实验结果吻合较好。3)发现了三聚体或五聚体对二乙烯低聚过程的模板效应。向列相反应环境的灵活性和有序性可以很好地解释这些动力学特征。

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.