SIOC English
化学学报
高级检索

化学学报 >

2013 , Vol. 71 >Issue 01: 114 - 120

DOI: https://doi.org/10.6023/A12100805

研究论文

乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物合成及其胶束化研究

  • 康宏亮 ,
  • 刘瑞刚 ,
  • 黄勇
展开
  • a 中国科学院化学研究所 高分子物理与化学国家重点实验室 北京分子科学中心 北京 100190;
    b 中国科学院理化技术研究所 工程塑料国家工程研究中心 北京 100190

收稿日期: 2012-10-22

  网络出版日期: 2012-12-18

基金资助

项目受国家自然科学基金(Nos. 20974114, 21174156)和中国科学院知识创新工程(No. KJCX2-YW-H19)资助.

收起

Synthesis of Ethyl Cellulose Grafted Poly(N-isopropylacrylamide) Copolymer and Its Micellization

  • Kang Hongliang ,
  • Liu Ruigang ,
  • Huang Yong
Expand
  • a State Key Laboratory of Polymer Physics and Chemistry, Beijing National Laboratory of Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190;
    b National Engineering Research Center of Engineering Plastics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190

Received date: 2012-10-22

  Online published: 2012-12-18

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 20974114, 21174156) and the Knowledge Innovation Program of the Chinese Academy of Sciences (No. KJCX2-YW-H19).

Fold

摘要

通过单电子转移“活性”/可控自由基聚合的方法制备了具有双亲性及温度响应性的乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物(EC-g-PNIPAm). 通过凝胶渗透色谱、核磁氢谱和红外光谱等对合成的接枝共聚物进行了表征. 我们发现此反应在混合溶剂四氢呋喃/甲醇的混合溶剂中是活性可控的. EC-g-PNIPAm接枝共聚物能够在选择性溶剂水中发生自组装现象, 形成稳定的以乙基纤维素为核、聚N-异丙基丙烯酰胺为壳的球形胶束. 并且随着温度的升高, 支链聚N-异丙基丙烯酰胺发生塌缩使得球形胶束发生收缩.

关键词： 乙基纤维素; 聚N-异丙基丙烯酰胺; 单电子转移“活性”/可控自由基聚合; 接枝聚合反应; 温敏性

本文引用格式

康宏亮 , 刘瑞刚 , 黄勇 . 乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物合成及其胶束化研究[J]. 化学学报, 2013 , 71(01) : 114 -120 . DOI: 10.6023/A12100805

Abstract

Thermo-responsive graft copolymers, ethyl cellulose grafting poly(N-isopropylacrylamide) (EC-g-PNIPAm), were synthesized by single-electron transfer living radical polymerization (SET-LRP) in THF/methanol mixed solvent. Ethyl cellulose macro-initiators (EC-Br) for SET-LRP were synthesized by the esterification between the hydroxyl groups on EC backbones and 2-bromoisobutyryl bromides. The degree of substitution of the EC-Br macro-initiator was tailored by varying the feeding mole ratio of 2-bromoisobutyryl bromide to the hydroxyl group on ethyl cellulose. Three EC-Br macro-initiators with different Br substitutions were used as the macro-initiators and it was found that the converting degree of the initiator sites was efficient and the graft density of graft copolymer was controllable. The SET-LRP of NIPAm was efficient that the monomer conversion was above 60% within 25 h. The linear plot of ln([M]0/[M]t) versus the conversion indicated that the reaction was living and controllable. The graft copolymers were characterized by means of gel permeation chromatography (GPC), 1H NMR and FTIR spectroscopy. GPC peak of the graft copolymer became narrower and shifted to the low elution time with the increase of reactive time. The molecular weight of the side-chain linearly increased with the reaction time. EC-g-PNIPAm copolymers were typical amphiphilic graft copolymers, having the hydrophobic EC backbone and the hydrophilic PNIPAm side chains. They could be self-assembled and form stable micelles in a selective solvent, water. The micelles were in spherical shape with typical diameter around 100 nm. Rod-like and flower shaped particles were also observed, which was probably due to the fusion of the spherical shaped micelles. The structure of the spherical shaped micelles was that the EC backbone collapsed to form the core of the micelles and the hydrophilic PNIPAm chains stayed in the outside of the micelles to stabilize the micelles. Due to the thermoresponsive branch chains of PNIPAm, the micelles could shrink with rising temperature due to the collapses of the PNIPAm side chains.

Key words： ethyl cellulose; poly(N-isopropylacrylamide); single-electron transfer living radical polymerization (SET-LRP); graft polymerization; thermoresponsive

参考文献

[1] Gupta, K. C.; Sahoo, S. Biomacromolecules 2001, 2, 239.
[2] Braunecker, W. A.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93.
[3] Hua, M.; Yang, W.; Xue, Q.; Chen, M. Q.; Liu, X. Y.; Yang, C. Acta Chim. Sinica 2005, 63, 631. (华慢, 杨伟, 薛乔, 陈明清, 刘晓亚, 杨成, 化学学报, 2005, 63, 631.)
[4] Dang, L.; Liu, S. X.; Yang, X.; Qi, X. J.; Wang, H. M.; Lu, H. Y.; Tian, R. Acta Chim. Sinica 2011, 69, 2755. (党莉, 刘守信, 杨曦, 齐晓君, 王红梅, 吕海燕, 田荣, 化学学报, 2011, 69, 2755.)
[5] Lei, Z. L.; Liu, Y. L. Acta Chim. Sinica 2006, 64, 2403. (雷忠利, 刘亚兰, 化学学报, 2006, 64, 2403.)
[6] Qi, X. J.; Liu, S. X.; Liu, T.; Dang, L.; Yang, X.; Yu, W. N.; Wang, H. M. Acta Chim. Sinica 2011, 69, 1803. (齐晓君, 刘守信, 刘腾, 党莉, 杨曦, 雨薇娜, 王红梅, 化学学报, 2011, 69, 1803.)
[7] Zhu, Y. M.; Zhang, Y.; Liu, Z. L.; Lang, M. D. Acta Chim. Sinica 2010, 68, 2449. (朱亚明, 张琰, 刘子路, 郎美东, 化学学报, 2010, 68, 2449.)
[8] Zhao, F. B.; Liu, Z. L.; Feng, L.; Sun, J. P.; Hu, J. W. Acta Polym. Sinica 2009, 166. (赵发宝, 刘志雷, 冯良, 孙建平, 胡继文, 高分子学报, 2009, 166.)
[9] Huang, X. W.; Gu, L. N.; Lu, G. L.; Huang, X.; Zhang, Y. Q.; Huang, X. Y. Acta Chim. Sinica 2009, 67, 1363. (黄晓炜, 顾丽娜, 陆国林, 黄啸, 张亚琴, 黄晓宇, 化学学报, 2009, 67, 1363.)
[10] Qu, G.; Jiang, F. S.; Zhang, S. Y. Acta Polym. Sin. 2007, 541 (in Chinese). (屈刚, 姜复松, 张姝妍, 高分子学报, 2007, (6), 541.)
[11] Lu, R. F.; Hu, J. W.; Zhang, G. W.; Xiao, D. S. Acta Polym. Sin. 2012, 239. (卢汝烽, 胡继文, 张干伟, 肖定书, 高分子学报, 2012, 239.)
[12] Yi, Z.; Xi, F.; Chen, Y. M. Acta Polym. Sin. 2011, 494. (伊卓, 习复, 陈永明, 高分子学报, 2011, (5), 494.)
[13] Zhang, X. H.; Wang, B. D.; Yang, D.; Yuan, L.; Tang, Q. Q.; Hu, J. H. Chin. J. Chem. 2009, 27, 2273.
[14] Yang, T. T.; Xu, Y. Y.; Yao, L.; Peng, H.; Cheng, S. Y. Acta Polym. Sin. 2009, 1146. (杨婷婷, 徐莹莹, 姚丽, 彭慧, 程时远, 高分子学报, 2009, 1146.)
[15] Hu, N.; Ni, Z. B.; Chu, H.; Liu, X. Y.; Chen, M. Q. Chin. J. Chem. 2009, 27, 2249.
[16] Peng, D.; Li, Y. G.; Zhang, X. H.; Lu, G. L.; Feng, C.; Huang, X. Y. Acta Chim. Sinica 2007, 65, 2144. (彭丹, 李垚功, 张晓环, 陆国林, 冯纯, 黄晓宇, 化学学报, 2007, 65, 2144.)
[17] Huang, C. G.; Wan, X. L.; Ying, S. K. Acta Polym. Sin. 2000, 467. (黄昌国, 万小龙, 应圣康, 高分子学报, 2000, 467.)
[18] Sun, J. Y.; Huang, W. Y.; Xue, X. Q.; Jiang, B. B.; Zhai, G. Q.; Kong, L. Z.; Chen, J. H.; Yang, Y.; Zhang, D. L. Acta Polym. Sin. 2012, 749. (孙佳悦, 黄文艳, 薛小强, 蒋必彪, 翟光群, 孔立智, 陈建海, 杨扬, 张东亮, 高分子学报, 2012, 749.)
[19] Ge, Z.; Cai, Y.; Yin, J.; Zhu, Z.; Rao, J.; Liu, S. Langmuir 2006, 23, 1114.
[20] Yu, T.; Wang, Y.; Lu, D. R.; Bai, R. K.; Lu, W. Q. Acta Polym. Sin. 2006, 597. (于涛, 王筠, 鲁代仁, 白如科, 陆伟琪, 高分子学报, 2006, 597.)
[21] Gao, H.; Matyjaszewski, K. Macromolecules 2006, 39, 3154.
[22] Westlund, R.; Carlmark, A.; Hult, A.; Malmstrom, E.; Saez, I. M. Soft Matter 2007, 3, 866.
[23] Carlmark, A.; Malmstrom, E. J. Am. Chem. Soc. 2002, 124, 900.
[24] Carlmark, A.; Malmstrom, E. E. Biomacromolecules 2003, 4, 1740.
[25] Li, Q.; Kang, H.; Liu, R.; Huang, Y. Chin. J. Chem. 2012, 30, 2169.
[26] Vlcek, P.; Janata, M.; Latalova, P.; Kriz, J.; Cadova, E.; Toman, L. Polymer 2006, 47, 2587.
[27] Yan, Q.; Yuan, J. Y.; Kang, Y.; Yin, Y. W. Prog. Chem. 2010, 22, 449.
[28] Yuan, W. Z.; Zhang, J. C.; Zou, H.; Shen, T. X.; Ren, J. Polymer 2012, 53, 956.
[29] Shen, D. W.; Yong, H. Polymer 2004, 45, 7091.
[30] Shen, D. W.; Yu, H.; Huang, Y. J. Polym. Sci. Part A Polym. Chem. 2005, 43, 4099.
[31] Yan, Q.; Yuan, J. Y.; Zhang, F. B.; Sui, X. F.; Xie, X. M.; Yin, Y. W.; Wang, S. F.; Wei, Y. Biomacromolecules 2009, 10, 2033.
[32] Meng, T.; Gao, X.; Zhang, J.; Yuan, J. Y.; Zhang, Y. Z.; He, J. S. Polymer 2009, 50, 447.
[33] Yan, Q.; Yuan, J.; Kang, Y.; Yin, Y. Prog. Chem. 2010, 22, 449.
[34] Ostmark, E.; Harrisson, S.; Wooley, K. L.; Malmstrom, E. E. Biomacromolecules 2007, 8, 1138.
[35] Ostmark, E.; Lindqvist, J.; Nystrom, D.; Malmstrom, E. Biomacromolecules 2007, 8, 3815.
[36] Lindqvist, J.; Nystrom, D.; Ostmark, E.; Antoni, P.; Carlmark, A.; Johansson, M.; Hult, A.; Malmstrom, E. Biomacromolecules 2008, 9, 2139.
[37] Kang, H. L.; Liu, W. Y.; Liu, R. G.; Huang, Y. Macromol. Chem. Phys. 2008, 209, 424.
[38] Ma, L.; Kang, H. L.; Liu, R. G.; Huang, Y. Langmuir 2010, 26, 18519.
[39] Li, Y. X.; Liu, R. G.; Liu, W. Y.; Kang, H. L.; Wu, M.; Huang, Y. J. Polym. Sci. Part A Polym. Chem. 2008, 46, 6907.
[40] Ma, L.; Liu, R. G.; Tan, J. J.; Wang, D. Q.; Jin, X.; Kang, H. L.; Wu, M.; Huang, Y. Langmuir 2010, 26, 8697.
[41] Wang, D. Q.; Tan, J. J.; Kang, H. L.; Ma, L.; Jin, X.; Liu, R. G.; Huang, Y. Carbohydr. Polym. 2011, 84, 195.
[42] Liu, W. Y.; Liu, R. G.; Li, Y. X.; Kang, H. L.; Shen, D.; Wu, M.; Huang, Y. Polymer 2009, 50, 211.
[43] Liu, W. Y.; Liu, R. G.; Li, Y. X.; Wang, W.; Ma, L.; Wu, M.; Huang, Y. Polymer 2009, 50, 2716.
[44] Tan, J. J.; Li, Y. X.; Liu, R. G.; Kang, H. L.; Wang, D. Q.; Ma, L.; Liu, W. Y.; Wu, M.; Huang, Y. Carbohydr. Polym. 2010, 81, 213.
[45] Zhang, Y. W.; Jiang, M. Acta Polym. Sin. 2005, 650.
[46] Dou, H. J.; Jiang, M.; Peng, H. S.; Chen, D. Y.; Hong, Y. Angew. Chem., Int. Ed. 2003, 42, 1516.
[47] Dou, H.; Jiang, M. Polym. Int. 2007, 56, 1206.
[48] Wan, S.; Jiang, M.; Zhang, G. Z. Macromolecules 2007, 40, 5552.
[49] Liu, W. Y.; Liu, Y. J.; Hao, X. H.; Zeng, G. S.; Wang, W.; Liu, R. G.; Huang, Y. Carbohydr. Polym. 2012, 88, 290.
[50] Oupicky, D.; Reschel, T.; Koňák, č.; Oupická, L. Macromolecules 2003, 36, 6863.
[51] Ohya, S.; Nakayama, Y.; Matsuda, T. Biomacromolecules 2001, 2, 856.
[52] Chu, L. Y.; Zhu, J. H.; Chen, W. M.; Niitsuma, T.; Yamaguchi, T.; Nakao, S. Chin. J. Chem. Eng. 2003, 11, 269.
[53] Gu, J.; Xia, F.; Wu, Y.; Qu, X.; Yang, Z.; Jiang, L. J. Controlled Release 2007, 117, 396.
[54] Xie, G. M.; Song, X. Q.; Ma, Z. B.; Yang, C. Chem. Res. Appl. 2007, 19, 629. (解光明, 宋晓青, 马宗斌, 杨成, 化学研究与应用, 2007, 19, 629.)
[55] Li, X. J.; Yin, M. H.; Zhang, G. L.; Zhang, F. B. Chinese J. Chem. Eng. 2009, 17, 145.
[56] Bokias, G.; Mylonas, Y.; Staikos, G.; Bumbu, G. G.; Vasile, C. Macromolecules 2001, 34, 4958.
[57] Li, H.; Luo, J.; Zhu, D.; Zhou, D.; Liang, L.; Lv, M. Fine Chem. 2010, 27, 968. (李欢, 罗建新, 朱东雨, 周德文, 梁利岩, 吕满庚, 精细化工, 2010, 27, 968.)
[58] Xia, Y.; Yin, X.; Burke, N. A. D.; Stöver, H. D. H. Macromolecules 2005, 38, 5937.
[59] Percec, V.; Guliashvili, T.; Ladislaw, J. S.; Wistrand, A.; Stjerndahl, A.; Sienkowska, M. J.; Monteiro, M. J.; Sahoo, S. J. Am. Chem. Soc. 2006, 128, 14156.
[60] Zhai, S.; Wang, B.; Feng, C.; Li, Y.; Yang, D.; Hu, J.; Lu, G.; Huang, X. J. Polym. Sci. Part A Polym. Chem. 2010, 48, 647.
[61] Feng, C.; Shen, Z.; Li, Y.; Gu, L.; Zhang, Y.; Lu, G.; Huang, X. J. Polym. Sci. Part A Polym. Chem. 2009, 47, 1811.
[62] Wu, C. Polymer 1998, 39, 4609.
[63] Li, Y.; Zhang, Y.; Yang, D.; Li, Y.; Hu, J.; Feng, C.; Zhai, S.; Lu, G.; Huang, X. Macromolecules 2010, 43, 262.
[64] Zhang, Y.; Shen, Z.; Yang, D.; Feng, C.; Hu, J.; Lu, G.; Huang, X. Macromolecules 2010, 43, 117.
[65] Li, M.; Jahed, N. M.; Min, K.; Matyjaszewski, K. Macromolecules 2004, 37, 2434.
[66] Wu, T.; Zhang, Y.; Wang, X.; Liu, S. Chem. Mater. 2007, 20, 101.
[67] Schmidt, S.; Motschmann, H.; Hellweg, T.; von Klitzing, R. Polymer 2008, 49, 749.
[68] Strandman, S.; Luostarinen, M.; Niemela, K.; Tenhu, H.; Rissanen, K. J. Polym. Sci. Part A Polym. Chem. 2004, 42, 4189.
Options
文章导航

/

〈 〉