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

doi:10.6023/A13111161

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

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

投稿日期:2013-11-16 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 Changming^a,b, Chen Daoyong^a,b

a Department of Macromolecular Science, Fudan University, Shanghai 200433;
b State Key Laboratory of Molecular Engineering of Polymer, Shanghai 200433

Received:2013-11-16 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).

文章分享

1. 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.PDF(220KB)

摘要/Abstract

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

引用此文

周常明, 陈道勇. 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[J]. 化学学报, 2014, 72(1): 35-40.

Zhou Changming, Chen Daoyong. Facile and Efficient Catalyst-Free Preparation of Poly(propargyl quinolinium bromide) and Poly(propargyl acridinium bromide) and Characterizations of Their Structures and Properties[J]. Acta Chimica Sinica, 2014, 72(1): 35-40.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Jiang, H.; Taranekar, P.; Reynolds, J. R.; Schanze, K. S. Angew. Chem. Int. Ed. 2009, 48, 4300.

[2] Ye, H. Y.; Li, W.; Li, W. S. Chin. J. Org. Chem. 2012, 32, 266. (叶怀英, 李文, 李维实, 有机化学, 2012, 32, 266.)

[3] Huo, Y. P.; Zeng, H. P.; Jiang, H. F. Chin. J. Org. Chem. 2004, 24, 1191. (霍延平, 曾和平, 江焕峰, 有机化学, 2004, 24, 1191.)

[4] Chen, L.; Shen, X. X.; Chen, Y. W. Chin. J. Chem. 2012, 30, 2219.

[5] Zeng, W. N.; Qi, J. P.; Wang, L. Y.; Cao, D. R. Chin. J. Org. Chem. 2009, 29, 1858. (曾文南, 亓金萍, 汪凌云, 曹德榕, 有机化学, 2009, 29, 1858.)

[6] Chen, Y. G.; Xu, B. M.; He, Z. K.; Xie, W. H. Acta Chim. Sinica 2011, 69, 1361. (陈彦国, 徐保明, 何治柯, 谢卫红, 化学学报, 2011, 69, 1361.)

[7] Xiao, Y.; Hu, Y. Q.; Huang, H. M.; Yin, D. L.; Xiao, X. M. Acta Chim. Sinica 2011, 69, 838. (肖毅, 胡玉琴, 黄红梅, 尹笃林, 肖小明, 化学学报, 2011, 69, 838.)

[8] Du, J.; Zhao, D.; Chen, Y. G.; He, Z. K. Acta Chim. Sinica 2006, 64, 963. (杜鹃, 赵丹, 陈彦国, 何治柯, 化学学报, 2006, 64, 963.)

[9] Hao, D.; Sun, L. L.; Jin, Y. Q.; Zhu, C. Q. Acta Chim. Sinica 2010, 68, 2215. (郝丹, 孙礼林, 晋英琼, 朱昌青, 化学学报, 2010, 68, 2215.)

[10] Jin, Y. Q.; Sun, L. L.; Hao, D.; Yu, R.; Qian, Z. S.; Zhu, C. Q. Chin. J. Chem. 2011, 29, 575.

[11] Ito, T.; Shirakawa, H.; Ikeda, S. J. Polym. Sci., Polym. Chem. Ed. 1974, 12, 11.

[12] Chiang, C. K.; Fincher, C. R.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis, E. J.; Gau, S. C.; Macdiarmid, A. G. Phys. Rev. Lett. 1977, 39, 1098.

[13] Shirakawa, H.; Louis, E. J.; Macdiarmid, A. G.; Chiang, C. K.; Heeger, A. J. J. Chem. Soc., Chem. Commun. 1977, 578.

[14] Shirakawa, H. Angew. Chem. Int. Ed. 2001, 40, 2575.

[15] MacDiarmid, A. G. Angew. Chem. Int. Ed. 2001, 40, 2581.

[16] Heeger, A. J. Angew. Chem. Int. Ed. 2001, 40, 2591.

[17] Choi, S. K.; Gal, Y. S.; Jin, S. H.; Kim, H. K. Chem. Rev. 2000, 100, 1645.

[18] Mayershofer, M. G.; Nuyken, O. J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5723.

[19] Masuda, T.; Higashimura, T. Acc. Chem. Res. 1984, 17, 51.

[20] Lam, J. W. Y.; Tang, B. Z. J. Polym. Sci., Part A: Polym. Chem. 2003, 41, 2607.

[21] Lam, J. W. Y.; Tang, B. Z. Acc. Chem. Res. 2005, 38, 745.

[22] Masuda, T. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 165.

[23] Li, C. H.; Li, Y. L. Macromol. Chem. Phys. 2008, 209, 1542.

[24] Liu, J. Z.; Lam, J. W. Y.; Tang, B. Z. Chem. Rev. 2009, 109, 5799.

[25] Kawasaki, M.; Masuda, T.; Higashimura, T. Polym. J. 1983, 15, 767.

[26] Gal, Y. S.; Choi, S. K. Eur. Polym. J. 1995, 31, 941.

[27] Kang, K. L.; Kim, S. H.; Cho, H. N.; Choi, K. Y.; Choi, S. K. Macromolecules 1993, 26, 4539.

[28] Kim, S. H.; Choi, S. J.; Park, J. W.; Cho, H. N.; Choi, S. K. Macromolecules 1994, 27, 2339.

[29] Choi, D. C.; Kim, S. H.; Lee, J. H.; Cho, H. N.; Choi, S. K. Macromolecules 1997, 30, 176.

[30] Kargin, V. A.; Kabanov, V. A. US 3658942, 1972 [Chem. Abstr. 1972, 74, 88376].

[31] Subramanyam, S.; Blumstein, A. Macromolecules 1991, 24, 2668.

[32] Gal, Y. S.; Lee, W. C.; Choi, S. K. Bull. Korean Chem. Soc. 1997, 18, 265.

[33] Gal, Y. S.; Lee, W. C.; Kim, S. Y.; Park, J. W.; Jin, S. H.; Koh, K. N.; Kim, S. H. J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 3151.

[34] Kwak, G.; Jin, S. H.; Park, J. W.; Gal, Y. S. Macromol. Chem. Phys. 2008, 209, 1770.

[35] Gal, Y. S.; Jin, S. H.; Park, J. W.; Lim, K. T. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 6153.

[36] Zhou, C. M.; Gao, Y.; Chen, D. Y. J. Phys. Chem. B 2012, 116, 11552.

[37] Huang, R.; Chen, D. Y.; Jiang, M. J. Mater. Chem. 2010, 20, 9988.

[38] Chen, D. Y.; Peng, H. S.; Jiang, M. Macromolecules 2003, 36, 2576.

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

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

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	葛凤洁, 张开志, 曹清鹏, 徐慧, 周涛, 张文浩, 班鑫鑫, 张晓波, 李娜, 朱鹏. 柔性芴基嵌段型延迟荧光二聚体的设计、合成及电致发光性能[J]. 化学学报, 2023, 81(9): 1157-1166.
[2]	车飞达, 赵晓茗, 张馨, 丁琪, 王昕, 李平, 唐波. 抑郁症相关活性分子的荧光成像^★[J]. 化学学报, 2023, 81(9): 1255-1264.
[3]	王一诺, 邵世洋, 王利祥. 窄谱带多重共振有机高分子荧光材料研究进展^★[J]. 化学学报, 2023, 81(9): 1202-1214.
[4]	王晓, 王星文, 肖乐辉. 单分子荧光成像研究单颗粒纳米催化机制[J]. 化学学报, 2023, 81(8): 1002-1014.
[5]	武虹乐, 郭锐, 迟涵文, 唐永和, 宋思睿, 葛恩香, 林伟英. 喹啉基粘度荧光探针的合成及其检测应用[J]. 化学学报, 2023, 81(8): 905-911.
[6]	郑文山, 高冠斌, 邓浩, 孙涛垒. Ag₂Se@Ag₂S核壳量子点的室温合成及其近红外荧光性能优化[J]. 化学学报, 2023, 81(7): 763-770.
[7]	刘振宇, 饶俊峰, 祝守加, 王兵洋, 余帆, 冯全友, 解令海. 溶液加工型自主体热活化延迟荧光材料的研究进展[J]. 化学学报, 2023, 81(7): 820-835.
[8]	王银凤, 李猛, 陈传峰. 基于手性三蝶烯的红光热激活延迟荧光聚合物及其有机发光二极管研究^★[J]. 化学学报, 2023, 81(6): 588-594.
[9]	梁攀, 张宏淑, 黄宏升, 李飒英, 张笑恬, 王英, 李连庆, 刘志宏. 一种高效窄带蓝色荧光粉Ba₃Y₂B₆O₁₅:Bi³⁺及其应用研究[J]. 化学学报, 2023, 81(4): 371-380.
[10]	吕鑫, 吴仪, 张勃然, 郭炜. 过氧化氢激活型近红外氟硼二吡咯光敏剂的设计、合成及光动力治疗研究[J]. 化学学报, 2023, 81(4): 359-370.
[11]	张少秦, 李美清, 周中军, 曲泽星. 多共振热激活延迟荧光过程的理论研究[J]. 化学学报, 2023, 81(2): 124-130.
[12]	贾彦荣, 徐凯, 赵彦英, 倪华钢, 吴滢, 夏敏. 推拉电子基团区域异构苯并咪唑的发射行为与力致荧光变色性能研究[J]. 化学学报, 2023, 81(12): 1716-1723.
[13]	黄艳琴, 栗丽君, 杨书培, 张瑞, 刘兴奋, 范曲立, 黄维. HA-AuNPs/FDF用于透明质酸酶的高灵敏检测、肿瘤靶向细胞荧光成像和光疗[J]. 化学学报, 2023, 81(12): 1687-1694.
[14]	贺晓梦, 袁方, 张素雅, 张健健. 基于尼罗红类ONOO^–近红外荧光探针的开发及其成像应用[J]. 化学学报, 2023, 81(11): 1515-1521.
[15]	孙丽, 王亚静, 李涛, 郭英姝, 张书圣. 金纳米笼探针用于线粒体成像和光热损伤细胞^★[J]. 化学学报, 2023, 81(10): 1301-1310.