Development of Synthetic Method on Sequence-Ordered Polymers with Controlled Molecular Weights

1)分子量可控聚酯的合成研究以三氟环氧丙烷（TFPO）和邻苯二甲酸酐（PHA）为原料，采用季铵盐和冠醚配合物，在甲苯中进行开环聚合。使用四丁基溴化铵（TBAB）或四丁基乙酸铵（TBAAc）的反应以75%产率提供聚合物。在使用TBAAc的反应的情况下，所得聚合物（P-1）的分子量和多分散性分别为6400和1.10。2）环氧乙烷插入P-1合成有序聚酯研究了在季铵盐催化下，环氧乙烷插入P-1合成分子量可控的有序聚酯。用四戊基溴化铵使300 mol%的缩水甘油苯基醚（GPE）与P-1反应，转化率达100%，得到了具有A-C-B结构单元的有序聚合物。通过插入GPE对所得聚酯进行转化是制备具有A-C-B单元的有序聚合物的有用的合成方法。

1) Synthesis of Polyesters with Controlled Molecular WeightA ring-opening polymerization of trifluoropropyrene oxide (TFPO) and phthalic anhydride (PHA) was carried out in toluene using quaternary onium salts and crown ether complexes. The reaction using tetrabutylammonium bromide (TBAB) or tetrabutylammonium acetate (TBAAc) provided the polymer in 75% yield. In the case of the reaction using TBAAc, the molecular weight and polydispersity of the obtained polymer (P-1) was 6400 and 1.10, respectively. It was proved that the polymerization has a living nature.2) Synthesis of Sequence-Ordered Polyesters Using the Insertion of oxiranes into P-1The synthesis of sequence-ordered polyesters with controlled molecular weight using the insertion of oxiranes into P-1 with quaternary onium salts as catalysts was investigated. The reaction of 300-mol% of glycidyl phenyl ether (GPE) into P-1 using tetraamylammonium bromide proceeded with 100% of conversion to provide sequence-ordered polymers with A-C-B unit.It was found that the living ring-opening copolymerization of oxiranes with dicarboxylic anhydrides using suitable quaternary onium salts as initiators provides the corresponding polyesters with controlled molecular weight and molecular weight distribution. The transformation of the obtained polyesters using insertion of GPE is a useful synthetic method to prepare sequence-ordered polymers with A-C-B unit.