Novel Preparative Method of Aromatic Polyesters and Polyamides using Aromatic Bisketene Compounds

9,10-二羰基-9,10-二氢蒽(1)和1,4-二羰基-1,4-二氢萘(2)在室温下反应过于活跃，无法作为纯晶体分离，但在脱气苯中能够保持不变。1与四种苯醌在室温下反应，得到相应的聚合物，产率中等，根据它们的表征，发现它们是芳香聚酯。发现1能通过直接加成反应与醌类自发反应形成酯键。浓度高的苯溶液2不能得到，因为它的反应活性比1高。在这个反应中，用2的前体化合物——氯化酸代替。在氯酸与醌或醌二亚胺的混合溶液中加入碱，得到相应的中等产率的聚合物，根据它们的表征，分别发现它们是芳香族聚酯和聚酰胺。2能与醌类和醌二亚胺自发反应，通过直接加成反应分别生成酯类和酰胺类。3、在体系中由苯并环丁烯二酮辐照产生，与醌类或醌类二亚胺反应生成相应的聚合物，产率中等，根据其表征分别为芳香族聚酯和聚酰胺。通过对3-苯并醌体系反应的ESR测定，发现聚合过程是自由基反应。所得聚合物的分子量随时间的增加而增加。这些事实表明聚合是通过双自由基偶联机制进行的。然而，长时间的辐照会引起聚合物的分解，导致分子量下降。

9,10-Dicarbonyl-9,10-dihydroanthracene (1) and 1,4-dicarbonyl-1,4-dihydronaphthalene (2) were too reactive to isolate as pure crystals at room temperature, but they were capable of keeping unchanged in degassed benzene. 1 reacted with four kinds of benzoquinones at room temperature to give corresponding polymers in moderate yields, which were found to be aromatic polyesters on the basis of their characterizations. It was found that 1 is able to react spontaneously with quinones to form ester linkage via direct addition reaction. The benzene solution of 2 with its high concentration is not available because of higher reactivity compared to 1. Acid chloride, precursor compound of 2, was used instead in this reaction. The addition of base to the mixture solution of acid chloride and quinones or quinone diimines gave corresponding polymers in moderate yields, which were found to be aromatic polyesters and polyamides, respectively, on the basis of their characterizations. 2 is able to react spontaneously with quinones and quinone diimines to form ester and amide likage, respectively, via direct addition reaction. 3, produced in the system by the irradiation of benzocyclobutenedione, reacted with quinones or quinone diimines to give corresponding polymers in moderate yields, which were found to be aromatic polyesters and polyamides, respectively, on the basis of their characterizations. By the ESR measurement in the reaction of the 3-benzoquinone system, it was found that the polymerization proceeds radical mechanism. And also, the molecular weights of polymers obtained increased with the time. These facts suggested that polymerization proceeds via diradical coupling mechanism. However, long time irradiation induced the decomposition of polymer, leading to decrease of the molecular weights.