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

利用芳香族双烯酮化合物制备芳香族聚酯和聚酰胺的新方法

基本信息

批准号：
07651083
负责人：
ITOH Takahito
金额：
$ 1.34万
依托单位：
Mie University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651083/
关键词：
Aromatic Bisketene Quinone Quinone Diimine Aromatic Polyester Aromatic Polyamide Synthesis Photoreaction

项目摘要

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.

9,10-二羰基-9,10-二氢蒽 (1) 和 1,4-二羰基-1,4-二氢萘 (2) 反应活性太高，无法在室温下分离为纯晶体，但它们能够在脱气苯中保持不变。 1与四种苯醌在室温下反应，以中等收率得到相应的聚合物，根据其表征发现其为芳香族聚酯。研究发现1能够通过直接加成反应自发地与醌反应形成酯键。 2的高浓度苯溶液由于与1相比具有更高的反应性而无法获得。该反应中使用2的前体化合物酰基氯代替。在酰基氯和醌或醌二亚胺的混合溶液中加入碱，以中等收率得到相应的聚合物，根据其表征发现它们分别是芳香族聚酯和聚酰胺。 2能够通过直接加成反应自发地与醌和醌二亚胺反应分别形成酯和酰胺类。 3是在苯并环丁烯二酮辐照体系中生成的，与醌或醌二亚胺反应，以中等收率得到相应的聚合物，根据其表征发现它们分别是芳香族聚酯和聚酰胺。通过3-苯醌体系反应中的ESR测量，发现聚合反应以自由基机理进行。而且，所得聚合物的分子量随着时间的推移而增加。这些事实表明聚合通过双自由基偶联机制进行。然而，长时间的照射会引起聚合物的分解，导致分子量下降。