Synthesis of New Sequence-Ordered Polymers by Stepwise Insertion of Epoxides into Polymer Backbone

1997年，以四丁基氯化膦（TBPC）为催化剂，在甲苯中进行环氧化物与聚芳硅醚（P-1）的插入反应，反应48 h，转化率达100%。以双酚和苯基膦酸二氯化物为原料，通过缩聚反应合成了聚芳膦酸酯（P-2），然后在P-2的端羟基上引入乙酰基，得到了聚芳膦酸酯（P-3）。研究了缩水甘油苯基醚（GPE）对P-3（M_n：3900，M_w/M_n：1.42）的插入反应。在氯苯溶剂中，以二苯并-18-冠-6-醚/CsBr络合物为催化剂，于130 ℃反应96 h，得到定量产率的聚膦酸烷基酯。聚合物的数均分子量（Mn：7400，Mw/Mn：1.63）高于预聚物的数均分子量。1998<13>年，为了实现聚合物主链的逐步转化，以氧化三氟丙烯（TFPO）与双（氯苯基）苯基膦酸酯（BCPP）的反应为模型反应进行了研究。使用二苯并-18-冠-6-醚/CsF络合物在氯苯中在70 ° C下进行反应72小时，以100%的转化率提供目标产物。获得的产物将使用GPE的插入进行转化，以产生具有多个序列的相应产物。

The synthesis of ordered polymers with multiple sequence on the basis of stepwise transformation of polymer backbones was investigated.In 1997, insertion reaction of epoxides into poly(arylsilyl ether) (P-1) using tetrabutyiphosphonium chloride (TBPC) in toluene for 48 h proceeded with 100 % conversion to produce sequence-ordered polymers. Poly(aryl phosphonate) (P-2) were prepared by polycondensation of bisphenols with phenylphosphonic dichioride, then the terminal phenolic hydroxy groups of P-2 were capped with acetyl group to provide the starting polymer (P-3). The insertion reaction of glycidyl phenyl ether (GPE) into P-3 (M_n : 3900, M_w/M_n : 1.42) was carried out under various reaction conditions. When the reaction was carried out using dibenzo- 18-crown-6-ether/CsBr complex as a catalyst in chlorobenzene at 130= for 96 h, the corresponding poly(alkyl phosphonate) was obtained in quantitative yield. It was also found that the number-average molecular weight (M_n : 7400, M_w/M_n : 1.63) of the obtained polymer was higher than that of the prepolymer. Furthermore, H-NMR and ^<13>C-NMR spectra of the resulting polymer proved that the insertion re action proceeded quantitatively and regioselectively to give the sequence-ordered poly(alkyl phosphonate).In 1998, to achieve stepwise transformation of polymer backbone, the reaction of trifluoropropyrene oxide (TFPO) with bis(chlorophenyl)phenylphosphonate (BCPP) was investigated as a model reaction. The reaction proceeded using dibenzo-18-crown-6-ether/CsF complex in chlorobenzene at 70= for 72 h to provide the targeted product with 100 % of conversion. The obtained product would be transformed using insertion of GPE to produce the corresponding product with multiple sequence.