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

可控分子量有序聚合物合成方法的进展

• 批准号: 11650915
• 负责人: KAMEYAMA Atsushi
• 金额: $ 2.05万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650915/
• 关键词: Sequence-Ordered Polymer; Alternating Copolymerization; Transformation of Polymer Backbone; Oxiranes; Insertion Reaction; Molecular Weight; 挿入反応; 配列順序; 分子量; 分子量分布

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.

1) 控制分子量聚酯的合成三氟氧化丙烯(TFPO)和邻苯二甲酸酐(PHA)在甲苯中使用季鎓盐和冠醚配合物进行开环聚合。使用四丁基溴化铵(TBAB)或四丁基乙酸铵(TBAAc)的反应以75%的产率提供聚合物。使用TBAAc进行反应时，得到的聚合物(P-1)的分子量为6400，多分散度为1.10。证明该聚合反应具有活性。2)P-1中环氧乙烷插入合成有序聚酯P-1中季铵插入环氧乙烷合成可控分子量的序列有序聚酯研究了盐作为催化剂。使用四戊基溴化铵将 300 mol% 缩水甘油基苯基醚 (GPE) 反应生成 P-1，转化率达到 100%，得到具有 A-C-B 单元的有序聚合物。使用合适的季鎓盐作为引发剂的二羧酸酐提供了具有受控分子量和分子量分布的相应聚酯。使用 GPE 插入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合成方法。