化学学报 ›› 2013, Vol. 71 ›› Issue (07): 979-990.DOI: 10.6023/A13010071 上一篇    下一篇

综述

含非典型性生色团的发光聚合物

黄田a, 汪昭旸a, 秦安军a, 孙景志a, 唐本忠b   

  1. a 浙江大学高分子合成与功能构造教育部重点实验室高分子科学与工程学系 杭州 310027;
    b 香港科技大学化学系香港九龙清水湾
  • 收稿日期:2013-01-15 出版日期:2013-07-14 发布日期:2013-03-15
  • 通讯作者: 孙景志, E-mail: sunjz@zju.edu.cn, Tel.: 0571-87953734, Fax: 0571-87953734;唐本忠, tanbenz@ust.hk, Tel.: 0852-23587375; Fax: 0852-23581594. E-mail:sunjz@zju.edu.cn; tanbenz@ust.hk
  • 作者简介:黄田, 女, 汉族. 2010 年7 月毕业于中南民族大学材料化学系, 获工学学士学位. 同年9 月进入浙江大学高分子科学与工程学系攻读硕士学位, 开展含非典型性荧光生色团的超支化聚酰胺胺的合成与发光机理研究.
  • 基金资助:

    项目受国家自然科学基金(No. 21074113)和科技部973项目(No. 2013CB834704)资助

Luminescent Polymers Containing Unconventional Chromophores

Huang Tiana, Wang Zhaoyanga, Qin Anjuna, Sun Jingzhia, Tang Benzhongb   

  1. a MOE Key Laboratory of Macromolecule Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China;
    b Department of Chemistry, Institute of Molecular Functional Materials, the Institute for Advanced Study (IAS), The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
  • Received:2013-01-15 Online:2013-07-14 Published:2013-03-15
  • Contact: 10.6023/A13010071 E-mail:sunjz@zju.edu.cn; tanbenz@ust.hk
  • Supported by:

    Projects supported by the National Natural Science Foundation of China (No. 21074113) and the Ministry of Science and Technology of China (No. 2013CB834704).

发光聚合物一般是由具有大p电子系统的共轭基元作为发光单元, 通过共价键连接而成的高分子. 近年来, 研究者发现: 另一类仅含有脂肪胺、羰基、酯基、酰胺等传统意义上的助色团的聚合物在适当条件下也能发射强的荧光. 树枝状聚酰胺胺(PAMAM)和超支化聚酰胺胺(hb-PAMAM)是最早和最广泛被研究的含非典型性荧光生色团的聚合物. 最近, 这类聚合物被扩展到含有叔胺基元的聚氨酯、聚醚酰胺、聚脲体系. 这些体系的生色团被认定为其结构中的叔胺基元, 叔胺的氧化是荧光产生的根源. 同时, 也有文献报道马来酸酐与醋酸乙烯酯交替共聚物、异丁烯与顺丁烯二酸酐共聚物、聚多糖动态高分子、聚酰腙以及通过RAFT试剂制备的含聚三硫碳酸酯的多嵌段共聚物等也可以发射荧光. 这些聚合物的一个共同特点是结构中不含叔胺基元, 而仅含羰基和酯基, 其发光机理通常用多个羰基聚集效应或羰基和苯环之间的相互作用来解释.

关键词: 生色团, 叔胺, 羰基, 荧光, 超支化聚酰胺胺

Luminescent polymers are referred to as conjugated polymers, which are constructed by p-aromatic building blocks functioning as emitting units. But in recent years, it has been found that a few kinds of polymers only containing auxochromophores or unconventional chromophores such as aliphatic tertiary amine, carbonyl, ester, and amide demonstrate strong luminescence under proper conditions. Poly(amido amine) (PAMAM) dendrimers and hyperbranched poly(amido amine)s are the first reported and most investigated luminescent polymers containing unconventional chromophores. Lately, this kind of polymers have been extended to hyperbranched poly(amino ester)s (hb-PAEs), hyperbranched poly(ether amide)s (hb-PEAs), and polyurea dendrimers (PUREs) containing tertiary amine moieties. The luminogen of PAMAMs, hb-PAEs, hb-PEAs and PUREs is associated with the N-branched tertiary amine moiety and the oxidation of the tertiary amine is assigned to the emitting source. Meanwhile, some distinct polymers had been also reported to be luminescent. Poly[(maleic anhydride)-alt-(vinyl acetate)], polyisobutene succinic anhydrides, glycodynamer analogues of poly(acrylhydrazone)s and multiblock polymer derived by poly(trithiocarbonate) mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropyl-acrylamide. A common feature of these polymers is that only carbonyl and ester groups rather than tertiary amine are involved in the polymer structure. Aggregation of multiple carbonyl groups induced emission is usually adopted to explain the mechanism of the emission, and the interaction between carbonyl and phenyl groups was also used to explain the unconventional emission.

Key words: chromophore, tertiary amine, carbonyl, fluorescence, hyperbranched poly(amido amine)