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本文研究了芳香腈(苯腈和苯乙腈)在傅氏试剂(BF_3,TiCl_4)及BF_3—C_6H_5OCH_3络合物等催化剂作用下的聚合反应。作者观察到,苯乙腈在BF_3和TiCl_4作用下于200—300℃范围内可以进行聚合反应,生成聚苯乙腈,而BF_3-C_6H_5OCH_3不能引起其聚合;苯腈在博氏试剂作用下主要进行环化三聚反应,生成2、4、6—三苯基均三嗪。但BF_3-C_6H_5OCH_3络合物却可在高温(350℃)下导致苯腈同时进行聚合反应和三聚化。对苯腈的聚合和环化三聚反应之间的关系进行了过一步的探讨,表明苯腈三聚体可在BF_3-C_6H_5OCH_3作用下发生开环聚合。根据这些结果,作者建议腈类的聚合反应历程可能经这环化三聚体的中间阶段。对于聚苯腈的若干性能(半导性、催化性等)也进行了测定。
In this paper, the polymerization of aromatic nitriles (benzonitrile and phenylacetonitrile) under the action of Friedens reagent (BF_3, TiCl_4) and BF_3-C_6H_5OCH_3 complexes was studied. The authors observed that under the action of BF_3 and TiCl_4, benzeneacetonitrile can polymerize in the temperature range of 200-300 ℃ to form polybenzimidazole, while BF_3-C_6H_5OCH_3 can not cause its polymerization. Benzonitrile mainly cyclizes under the action of Boehringer’s reagent Trimerization reaction to generate 2,4,6-triphenyl triazine. But the BF_3-C_6H_5OCH_3 complex can lead to the simultaneous polymerization and trimerization of benzonitrile at high temperature (350 ℃). The relationship between the polymerization of cyanobenzene and the reaction of cyclization was explored further, indicating that the ring-opening polymerization of benzonitrile trimer can be carried out under the action of BF_3-C_6H_5OCH_3. Based on these results, the authors suggest that the course of the polymerization of nitriles may pass through the intermediate stage of this cyclized trimer. Several properties (semiconducting, catalytic, etc.) of polybenzonitrile were also determined.