高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (8): 1908.

• 研究论文 • 上一篇    

含4-叔丁基环己基和烯烃共轭结构的双苯并噻唑类聚合物的合成及性能

黄炜, 杜春苹, 谢美然, 张以群, 张俊美   

  1. 华东师范大学化学系, 上海 200062
  • 收稿日期:2010-09-10 修回日期:2010-12-04 出版日期:2011-08-10 发布日期:2011-07-19
  • 通讯作者: 黄炜 E-mail:whuang@chem.ecnu.edu.cn
  • 基金资助:

    高等学校博士学科点专项科研基金(新教师基金课题)(批准号: 20090076120005)和上海市自然科学基金(批准号: 11ZR1410600)资助.

Synthesis and Characterization of New Poly(bisbenzothiazole)s Containing 4-tert-Butylcyclohexylidene and Alkene Units

HUANG Wei*, DU Chun-Ping, XIE Mei-Ran, ZHANG Yi-Qun, ZHANG Jun-Mei   

  1. Department of Chemistry, East China Normal University, Shanghai 200062, China
  • Received:2010-09-10 Revised:2010-12-04 Online:2011-08-10 Published:2011-07-19
  • Contact: HUANG Wei E-mail:whuang@chem.ecnu.edu.cn
  • Supported by:

    高等学校博士学科点专项科研基金(新教师基金课题)(批准号: 20090076120005)和上海市自然科学基金(批准号: 11ZR1410600)资助.

摘要: 一类新型的含4-叔丁基环己基和烯烃共轭结构的双苯并噻唑类聚合物PBTs III1,2由1,1’-双(4-氨基-3-巯基苯基)-4-叔丁基环己烷二盐酸盐(BAMPBCH?2HCl)与烯烃二元酸经过缩聚反应制备得到。聚合物的结构都经过了红外(IR)、核磁(NMR)、元素分析(EA)的表征。4-叔丁基环己基的引入提高了此类聚合物的溶解性并保持了较好的热稳定性,失重10%的温度在419 oC以上。相比聚苯撑苯并双噻唑(PBZT),PBTs III1,2的紫外吸收波长发生了蓝移,相对聚2,2’-对苯撑-6,6’-(4-叔丁基)环己基双苯并噻唑(PBT)则发生了红移,光学能带隙分别为2.56eV和2.53eV,大侧基和烯烃结构的引入扩大了苯并噻唑类聚合物光学能带隙的可调范围。PBTs III1,2的荧光发射波长较PBT发生了红移,大侧基的引入降低了固态时聚合物分子链的聚集程度。顺磁共振(EPR)的结果表明,PBTs III1,2都有明显的顺磁共振信号,顺磁中心是它们本身所固有的。

关键词: 聚苯并噻唑, 光学带隙, 共轭聚合物

Abstract: A new series of poly(bisbenzothiazole)s (PBTs III1,2) containing 4-tert-butylcyclohexylidene and alkene units were prepared from 1,1-bis(4-amino-3-mercaptophenyl)-4-tert-butylcyclohexane dihydrochloride (BAMPBCH?2HCl) and alkene dicarboxylic acids by direct polycondensation. Their chemical structures were characterized by IR, 1H NMR and EA. These polymers exhibited improved solubility due to the introduction of 4-tert-butylcyclohexene group into their structures. They also maintained good thermal stability. The decomposition temperatures at 10 % weight loss of them were above 419 oC. In comparison with poly(p-phenylene-6,6’-(4-tert-butylcyclohexene)bisbenzothiazole) (PBT), the UV absorption spectra of PBTs III1,2 showed the λmax were red shifted. And compared with poly(p-phenylene benzobisthiazole) (PBZT), the λmax were blue shifted. The bandgaps of PBTs III1,2 were 2.56 eV and 2.53eV. The introduction of 4-tert-butylcyclohexene and alkene units widened the optical bandgap range of the benzothiazole polymers. The emission wavelengths of PBTs III1,2 were red shifted in contrast to PBT. The bulky pendant group decreased the aggregation degree of polymer chains. The results of EPR studies showed the intrinsic paramagnetic defects in PBTs III1,2.

Key words: Poly(benzobisthiazole), Optical bandgap, Conjugated polymer

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