化学学报 ›› 2014, Vol. 72 ›› Issue (1): 35-40.DOI: 10.6023/A13111161 上一篇    下一篇

研究论文

聚溴化炔丙基喹啉及聚溴化炔丙基吖啶的简便高效制备及其结构与性质表征

周常明a,b, 陈道勇a,b   

  1. a 复旦大学高分子科学系 上海 200433;
    b 聚合物分子工程国家重点实验室 上海 200433
  • 收稿日期:2013-11-16 出版日期:2014-01-14 发布日期:2013-12-17
  • 通讯作者: 陈道勇,E-mail:chendy@fudan.edu.cn;Tel.:+86-21-65643989 E-mail:chendy@fudan.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 91127030,21334001)及科技部973项目基金(No. 2011CB932503)资助.

Facile and Efficient Catalyst-Free Preparation of Poly(propargyl quinolinium bromide) and Poly(propargyl acridinium bromide) and Characterizations of Their Structures and Properties

Zhou Changminga,b, Chen Daoyonga,b   

  1. a Department of Macromolecular Science, Fudan University, Shanghai 200433;
    b State Key Laboratory of Molecular Engineering of Polymer, Shanghai 200433
  • Received:2013-11-16 Online:2014-01-14 Published:2013-12-17
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 91127030 and 21334001) and the Ministry of Science and Technology of China (No. 2011CB932503).

在本研究工作中,我们发展了通过溴丙炔(propargyl bromide)分别与喹啉(quinoline)、吖啶(acridine)直接反应来制备聚溴化炔丙基喹啉[poly(propargyl quinolinium bromide),PPQB]和聚溴化炔丙基吖啶[poly(propargyl acridinium bromide),PPAB]的新方法. PPQB与PPAB的主链均为聚乙炔结构,侧链分别为季铵化喹啉盐和吖啶盐基团,是一类单取代的聚电解质型聚乙炔(polyelectrolyte polyacetylenes,PE-PAs). 我们提出了上述反应的机理,即溴丙炔与喹啉或吖啶反应生成季铵盐产物并导致产物结构中炔基基团的活化,使得季铵盐发生自聚合反应生成PPQB或PPAB. PPQB及PPAB具有较高的分子量(PPQB及PPAB的分子量分别为1.8×105和8.1×104 g/mol). 进一步的表征表明,PPQB和PPAB均具有良好的荧光活性和导电性能.

关键词: 聚电解质, 单取代聚乙炔, 无催化剂, 荧光, 导电性

In this paper, we report facile and efficient preparation of poly(propargyl quinolinium bromide) (PPQB) and poly(propargyl acridinium bromide) (PPAB). Both PPQB and PPAB are conjugated polymers with polyacetylene as backbones. Besides, they are polyelectrolytes since the side groups of PPQB and PPAB are quaternized quinolinium and acridinium, respectively. Therefore, PPQB and PPAB are conjugated polyelectrolytes, which are promising in many important applications. PPQB was prepared by reaction of the mixture of propargyl bromide (PB) and quinoline in DMF at 60 ℃ for 100 h. PPAB was synthesized under the same conditions via the same process except that acridine was used in the place of quinoline. The preparations are very simple and efficient, which need no any catalyst or initiator. The as-prepared PPQB and PPAB were characterized by elemental analysis and GPC-MALLS. Elemental analysis confirmed that PPQB and PPAB were the respective homopolymers of propargyl quinolinium bromide (PQB) and propargyl acridinium bromide (PAB). The molecular weights of the PPQB and PPAB were measured to be 1.8×105 and 8.1×104 g/mol, respectively, indicating efficient polymerizations of the respective monomers PQB and PAB. A tentative mechanism for the polymerizations was proposed as follows: firstly, the tertiary amine group of quinoline or acridine was quaternized by PB, leading to activation of the carbon-carbon triple bonds of the resultant quaternized salt; then, the nucleophilic attack on the triple bonds by pyridine resulted in carbon anions, which initiated the anionic polymerization of the quaternized salt. Furthermore, fluorescent and conductive properties of PPQB and PPAB were studied. Fluorescent measurements revealed that both PPQB and PPAB solutions had relatively strong fluorescent emissions, and the conductivity measurements demonstrated good conductivities of PPQB and PPAB films. Compared with poly(propargyl pyridinium bromide) that we reported previously, PPQB and PPAB are much less hygroscopic when exposed to air, so that PPQB and PPAB films are stable in the air. This broadens the applications of the two polymers.

Key words: polyelectrolyte, mono-substituted polyacetylene, catalyst-free, fluorescence, conductivity