Preparation of poly(arylene ether pyrimidine)s by aromatic nucleophilic substitution reactions
Preparation of poly(arylene ether pyrimidine)s by aromatic nucleophilic substitution reactions
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DOI：
10.1021/ma960741d
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发表时间：
1996-11-18
期刊：
影响因子：
5.5
通讯作者：
Connell, JW
中科院分区：
文献类型：
--
作者：
Herbert, CG;Bass, RG;Connell, JW
作为制备新型热稳定高性能聚合物的持续努力的一部分，聚（亚芳基醚嘧啶）已由4,6-双（4-（三甲基硅氧基）苯基）嘧啶和一系列活化的双（芳基氟）在二苯砜中使用催化量的氟化铯制备而成。这些聚合物在空气和氦气气氛中均表现出良好的热稳定性，在 480-540 摄氏度范围内重量损失为 10%。记录了中等到高比浓对数粘度（eta(inh)：0.40-0.92 dL/g），并且由这些样品溶液浇铸出透明的淡黄色柔性指甲可折皱薄膜。该系列中含有苯基氧化膦键的聚合物表现出良好的薄膜拉伸性能和耐氧等离子体性能。 4,6-双(4-氟苯基)嘧啶和对甲酚的模型反应以及对该化合物的 F-19 NMR 位移值的研究表明，嘧啶环有足够的能力来激活芳基氟化物与双(酚)聚合。使用嘧啶双（芳基氟）单体通过碳酸钾介导的芳香族亲核取代反应与选定的双（酚）制备一系列聚合物。含有芴部分的一个实例表现出高比浓对数粘度(eta(inh)：0.80 dL/g)；然而，用这种方法制备的聚合物只能铸造脆性薄膜。
As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether pyrimidine)s have been prepared with 4,6-bis(4-(trimethylsiloxy)phenyl)pyrimidine and a series of activated bis(aryl fluoride)s using a catalytic amount of cesium fluoride in diphenyl sulfone. These polymers exhibited good thermal stability in both air and helium atmospheres with 10% weight losses in the range 480-540 degrees C. Moderate to high inherent viscosities (eta(inh): 0.40-0.92 dL/g) were recorded, and clear pale yellow flexible fingernail creasable films were solution cast from these samples. A polymer in this series containing a phenylphosphine oxide linkage exhibited good thin film tensile properties and resistance to oxygen plasma. Model reactions with 4,6-bis(4-fluorophenyl)pyrimidine and p-cresol along with studies of this compound's F-19 NMR shift values indicated sufficient capacity of the pyrimidine ring to activate aryl fluorides toward polymerization with bis(phenol)s. The pyrimidine bis(aryl fluoride) monomer was used to prepare a series of polymers with selected bis(phenol)s by potassium carbonate-mediated aromatic nucleophilic substitution reactions. One example containing the fluorene moiety exhibited a high inherent viscosity (eta(inh): 0.80 dL/g); however, only brittle films could be cast from polymers prepared by this approach.