Synthesis and Polymerization Behavior of New Monomers based on Highly Conjugated Quinoid Structure

在室温下成功合成了7-烷氧羰基-7,8,8-三氰喹啉二甲烷、7,7-双（烷氧羰基）、8,8-二氰喹啉二甲烷和7,8-双（苄基氧羰基）-7,8 -环氰喹啉二甲烷。7,7双（烷氧羰基）-8,8-二氰喹诺二甲烷具有与7,7,8,8-四氰喹诺二甲烷相同的电子接受性质，并与苯乙烯交替共聚。由于苯基的存在，7,8-双（苄基氧羰基）-7,8-环氰喹啉二甲烷均聚物是可光降解的。在室温下成功合成了7-烷氧羰基-7-环氰苯醌和7-氰基-7（苯基）苯醌。结果表明，7-烷氧羰基-7-环氰苯醌类化合物的可聚合性主要取决于烷氧基的空间效应。7-氰基-7-（苯基）苯醌与苯乙烯的自发聚合机理可以用引发步骤中形成键的双自由基中间体形成机理和传播步骤中类似于传统自由基共聚的链加成机理来解释。在脱气苯中原位生成1,4-二羰基-1,4-二氢萘与苯醌和苯醌二亚胺自发和交替共聚，分别生成芳香聚酯和聚酰胺。在室温下成功合成了2,5-二（二氨基乙烯）-2,5-二氢呋喃、2,5-二亚甲基-2,5-二氢噻吩[3,2-b]和2,5-二（1.3-二硫代-2-酰基）-2,5-二氢噻吩。指出苯类结构和醌类结构之间的能量差对聚合物的聚合性有显著影响。发现2,5-二（1.3-二硫代-2-酰基）-2,5-二氢噻吩的聚合是由环应变能和芳构化能的释放共同驱动的。

7-Alkoxycarbonyl-7,8,8-tricyanoquinodimethanes, 7,7-bis (alkoxycarbonyl), 8,8-dicyanoquinodimethanes, and 7,8-bis (benzyloxycarbonyl)-7,8 cicyanoquinodimethane were synthesized successfully as isolable crystals at room temperature. 7,7 Bis (alkoxycarbonyl)-8,8-dicyanoquinodimethane with meldrum acid unit at the exocyclic position had same electron-accepting property to 7,7,8,8-tetracyanoquinodimethane and copolymerized with styrene in an alternating fashion. Homopolymer of 7,8-bis (benzyloxycarbonyl)-7,8-cicyanoquinodimethane was photodegaradable due to existence of phenyl groups.7-Alkoxycarbonyl-7-cicyanobenzoquinone methides and 7-cyano-7(phenyl)benzoquinone methide were synthesized successfully as isolate crystals at room temperature. It was concluded that polymerizability of 7-Alkoxycarbonyl-7-cicyanobenzoquinone methides depends significantly on the steric effect of the alkoxy groups. Spontaneous polymerization mechanism of 7-cyano-7-(phenyl)benzoquinone with styrene could be explained well by both diradical intermediate formation in the initiation step by the bond-forming initiation mechanism and chain addition like a conventional radical copolymerization in the propagation step.1,4-Dicarbonyl-1,4-dihydronaphthalene generated in situ in a degassed benzene copolymerized with benzoquinones and benzoquinone diimines spontaneously and alternatingly to give aromatic polyesters and polyamides, respectively.2,5-Bis(dicyanomethylene)-2,5-dihydrofuran, 2,5-dimethylene-2,5-dihydrothieno[3,2-b]thiophenes, and 2,5-bis(1.3-dithiolan-2-ylidene)-2,5-dihydrothiopene were synthesized successfully as isolable crystals at room temperature. It was pointed out that polymerizability depends significantly on the energy difference between benzenoid structure and quinonoid structure. Polymerization of 2,5-Bis(1.3-dithiolan-2-ylidene)-2,5-dihydrothiophene was found to be driven by both release of ring strain energy and aromatization energy.