Novel Syntheses of Poly(phosphonate)s and Poly(phosphate)s by Addition Reactions of Bisepoxides with Phosphonic Dichlorides and Dichlorophosphates
Novel Syntheses of Poly(phosphonate)s and Poly(phosphate)s by Addition Reactions of Bisepoxides with Phosphonic Dichlorides and Dichlorophosphates
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双环氧化物与二氯化膦和二氯磷酸盐的加成反应新合成聚膦酸酯和聚磷酸盐
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发表时间：
1995
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通讯作者：
Shoji Minegishi
中科院分区：
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作者：
T. Nishikubo;Atsushi Kameyama;Shoji Minegishi
通过双环氧化物分别与二氯膦和二氯磷酸盐的加成反应，合成了具有活性侧链氯甲基的聚膦酸酯S和聚磷酸盐S。双酚A二缩水甘油醚(BPGE)与苯基二氯膦(PPDC)在甲苯中于90℃无催化剂作用下发生聚合反应，但产物的产率和相对分子质量较低。另一方面，以季铵盐或季膦盐为催化剂，BPGE与PPDC在甲苯中于90℃反应24 h，可得到相对分子质量较高的聚合物，反应非常顺利，区域选择性较高(90-96%)。三乙胺、三苯基膦或冠醚络合物的加入促进了多加成反应的进行，但这些化合物的催化活性低于季铵盐。双环氧化物如BPGE和乙二醇二缩水甘油醚与一定量的二氯膦和二氯磷酸盐在相同的反应条件下也可以顺利地进行区域选择性地加成，得到相应的聚合物。
Poly(phosphonate)s and poly(phosphate)s with reactive pendant chloromethyl groups were synthesized by polyadditions of bisepoxides with phosphonic dichlorides and dichlorophosphates, respectively. The polyaddition of Bisphenol A diglydcidyl ether (BPGE) with phenylphosphonic dichloride (PPDC) occurred without any catalyst at 90°C for 24 h in toluene ; however, the yield and molecular weight of the resulting polymer were relatively low. On the other hand, the polyadditions of BPGE with PPDC proceeded very smoothly and regioselectively with high yields (90-96%) to give the polymers with relatively high molecular weights in toluene at 90°C for 24 h when quaternary ammonium or phosphonium salts were used as catalysts. The polyaddition was enhanced by the addition of triethylamine, triphenylphosphine, or crown ether complex ; however, the catalytic activities of these compounds were lower than those of quaternary onium salts. Polyadditions of bisepoxides such as BPGE and ethylene glycol diglycidyl ether with certain phosphonic dichlorides and dichlorophosphates also proceeded smoothly and regioselectively to give the corresponding polymers under the same reaction conditions.