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

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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.