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

基于高共轭醌结构的新型单体的合成及聚合行为

基本信息

批准号：
09650978
负责人：
ITOH Takahiro
金额：
$ 2.18万
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：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

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.

在室温下成功地合成了7-烷氧羰基-7，8，8-三氰基醌二甲烷、7，7-双（烷氧羰基）、8，8-二氰基醌二甲烷和7，8-双（苄氧羰基）-7，8-氰基醌二甲烷的可分离晶体。在环外含有马来酸单元的7，7-双烷氧羰基-8，8-二氰基对苯二酚二甲烷与7，7，8，8-四氰基对苯二酚二甲烷具有相同的吸电子性能，并与苯乙烯以交替方式共聚。7，8-二（苄氧羰基）-7，8-氰基对苯醌二甲烷均聚物由于苯基的存在而具有光降解性，在室温下成功合成了7-烷氧羰基-7-氰基对苯醌甲基化物和7-氰基-7-苯基对苯醌甲基化物。结果表明，7-烷氧羰基-7-氰基苯醌甲基化物的聚合性主要取决于烷氧基的空间位阻效应。7-氰基-7-（苯基）苯醌与苯乙烯的自发聚合机理可以很好地解释为在引发步骤中通过成键引发机理形成双自由基中间体和在增长步骤中类似于常规自由基共聚的链加成。4-脱气苯中原位生成的二氢萘与苯醌和苯醌二亚胺自发交替共聚在室温下成功地合成了2，5-二（二氰基亚甲基）-2，5-二氢呋喃、2，5-二亚甲基-2，5-二氢噻吩并[3，2-B]噻吩和2，5-二（1，3-二硫杂环戊烷-2-亚基）-2，5-二氢噻吩的可分离晶体。指出苯环结构与五元结构的能量差对聚合性能有重要影响。发现2，5-双（1，3-二硫戊环-2-亚基）-2，5-二氢噻吩的聚合是由环应变能和芳构化能的释放驱动的。