“活”的α-甲基苯乙烯共聚物: 聚合反应新化学和材料工程新技术

doi:10.6023/A12100846

化学学报 ›› 2013, Vol. 71 ›› Issue (02): 151-158.DOI: 10.6023/A12100846 上一篇下一篇

研究评论

“活”的α-甲基苯乙烯共聚物: 聚合反应新化学和材料工程新技术

马育红^a, 张冰^a, 赵长稳^a, 刘莲英^a, 蒋姗^b, 梁淑君^c, 杨万泰^a

a 北京化工大学碳纤维及功能高分子教育部重点实验室化工资源有效利用国家重点实验室北京 100029;
b 常州大学材料科学与工程系常州 213164;
c 太原工业学院材料工程系太原 030008

投稿日期:2012-10-31 发布日期:2012-12-18
通讯作者: 杨万泰 E-mail:yangwt@mail.buct.edu.cn
基金资助:
项目受国家自然科学基金委员会创新研究群体科学基金(No. 51221002-E03)资助.

A Novel Macroinitiator Based on the Copolymer of α-Methylstyrene Synthesis and Its Application in Preparing Block and Graft Polymers

Ma Yuhong^a, Zhang Bing^a, Zhao Changwen^a, Liu Lianying^a, Jiang Shan^b, Liang Shujun^c, Yang Wantai^a

a Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, China;
b Department of Materials Science and Engineering, Changzhou University, Changzhou 213164, China;
c Department of Materials and Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China

Received:2012-10-31 Published:2012-12-18
Supported by:
Project supported by the National Natural Science Foundation of China (No. 51221002-E03).

文章分享

摘要/Abstract

高于临界聚合反应温度时,α-甲基苯乙烯(AMS)单体和其聚合物处于聚合-解聚平衡. 基于AMS聚合物在受热时可裂解生成大分子链自由基的特性, 提出了含AMS结构单元的共聚物是一种“活”的, 可作为大分子自由基引发剂的概念, 并通过实验对AMS共聚物的引发性能和应用进行了研究. 首先, 合成了AMS与(甲基)丙烯酸酯类单体、丙烯酸、苯乙烯和马来酸酐等的共聚物. 然后以上述共聚物为大分子引发剂, 在90℃引发(甲基)丙烯酸酯类单体和苯乙烯等的本体聚合、溶液聚合和乳液聚合, 得到了嵌段共聚物. 用ESR谱证明了AMS的共聚物在加热时能裂解生成以碳原子为中心的大分子链自由基. 此外, 在聚合物的熔融共混中, AMS分解产生的大分子链自由基通过偶合反应形成接枝链, 原位生成相容剂. AMS共聚物还可以对碳纳米管及无机粒子进行表面原位接枝改性. AMS共聚物是一类无小分子残留的绿色自由基引发剂, 可以用于低成本制备两嵌段共聚物, 也可以用于聚合物的熔融共混增容.

关键词: 自由基聚合, 大分子引发剂, α-甲基苯乙烯, 嵌段聚合物, 接枝聚合, 反应性增容

Due to the steric hindrance effects in combination with stability of the tertiary benzylic α-methylstyryl radical, there is a dynamic equilibrium between the monomer α-methylstyrene (AMS) and its polymer (PAMS) when the temperature is greater than 61℃ (the ceiling polymerization temperature). Based on this unique feature, a novel strategy to prepare copolymers of AMS having liable bonds as potential macromolecular free radical initiators for synthesizing block and graft copolymers has been successfully developed in our laboratory. By conventional free radical polymerization, a series of AMS copolymers, including copolymers with (meth)acrylate, acrylic acid, styrene and maleic anhydride were synthesized. Typically, with the increasing of AMS fraction in monomer feed, the rate of copolymerization was significantly retarded and the molecular weight of the copolymers was reduced. However, the copolymer yield could be as high as 90% (w) with the increased addition of initiator, up to 4% (w), and the molar fraction of AMS structural unit in AMS copolymers could be up to 25% (mol%). It has been demonstrated that the copolymers containing AMS structural units are efficient free radical initiators when the temperature is greater than 80℃ (much better higher than 90℃). These copolymers could be exploited as macroinitiator in preparing block copolymers and core-shell polymer particles by bulk, solution and emulsion polymerization processes. In addition, the experimental results demonstrated that the molecular weight of copolymer products prepared with AMS copolymers as macromolecular initiators increased steadily with the monomer conversion. Though the polymerization initiated by AMS copolymers was not a well-controlled living system yet, it showed some characteristics of living polymerization. The ESR spectrum presented direct evidence of the generation of carbon centered radicals in the products of copolymer of AMS with glycidyl methacrylate (PAG) heated with N-t-butyl-α-phenylnitrone at 90℃ in toluene. Besides initiating the polymerization of vinyl monomer to prepare diblock copolymer, the AMS copolymers offered a practical pathway to synthesize grafting polymers in melting state. For example, with the addition of PAG in the PP/Nylon melten blending, it has been demonstrated a significant in situ compatibilization effect and the formation of graft polymer of PAG and PP. Furthermore, the AMS copolymers could also be used to modify MWCNT by free radical grafting onto mechanism. Instead of competing with the other existing controlled free radical polymerization technologies, the AMS copolymer method, with competitive cost and no small molecular residues, offers an alternative tool for polymer chemists to develop block copolymers on an industrial scale for some applications, such as dispersant and compatibilizer.

Key words: free radical polymerization, macroinitiator, α-methylstyrene, block copolymer, grafting polymerization, reactive compatibilization

引用此文

马育红, 张冰, 赵长稳, 刘莲英, 蒋姗, 梁淑君, 杨万泰. “活”的α-甲基苯乙烯共聚物: 聚合反应新化学和材料工程新技术[J]. 化学学报, 2013, 71(02): 151-158.

Ma Yuhong, Zhang Bing, Zhao Changwen, Liu Lianying, Jiang Shan, Liang Shujun, Yang Wantai. A Novel Macroinitiator Based on the Copolymer of α-Methylstyrene Synthesis and Its Application in Preparing Block and Graft Polymers[J]. Acta Chimica Sinica, 2013, 71(02): 151-158.

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

分享此文

参考文献

[1] Moad, G.; Solomon, D. H. The Chemistry of Radical Polymerization, 2nd ed., Elsevier, Oxford, UK, 2006, pp. 1～9.

[2] Greszta, D.; Mardare, D.; Matyjaszewski, K. Macromolecules 1994, 27, 638.

[3] Wade, A. B.; Matyjaszewski, K. Prog. Polym. Sci. 2007, 32, 93.

[4] Otsu, T.; Yoshida, M. Makromol. Chem. Rapid Commun. 1982, 3, 127.

[5] Otsu, T. J. Polym. Sci., Part A: Polym. Chem. 2000, 38, 2121.

[6] Solomon, D. H.; Rizzardo, E.; Cacioli, P. US Patent 4581429, 1985 [Chem. Abstr. 1985, 102, 221335].

[7] Wang, J. S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614.

[8] Kato, M.; Kamogato, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 1721.

[9] Percec, V.; Barboiu, B. Macromolecules 1995, 28, 7970.

[10] Chiefari, J.; Chong, K.; Ercole, F; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 1998, 31, 5559.

[11] Higashihara, T.; Hayashi, M.; Hirao, A. Prog. Polym. Sci. 2011, 36, 323.

[12] Kwon, Y.; Faust, R.; Chen, C. X.; Thomas, E. L. Macromolecules 2002, 35, 3348.

[13] Wieland, P. C.; Raether, B.; Nuyken, O. Macromol. Rapid Commun. 2001, 22, 700.

[14] Kos, T.; Strissel, C.; Yagci, Y.; Nugay, T.; Nuyken, O. Eur. Polym. J. 2005, 41, 1265.

[15] Luo, Y.-D.; Chou, I.-C.; Chiu, W.-Y.; Lee, C.-F. J. Polym. Sci.: Part A: Polym. Chem. 2009, 47, 4435.

[16] Chen, D.; Shi, Y.; Fu, Z.-F. J. Appl. Polym. Sci. 2009, 111, 1581.

[17] Guo, F. G.; Zhang, Q. Y.; Luo, S. B.; Zhang, H. P. Acta Polym. Sinica 2010, (5), 508.

[18] Wang, W. W.; Zhang, Q. Y. J. Colloid Interface Sci. 2012, 374, 54.

[19] Raether, B.; Nuyken, O.; Wieland, P. C.; Bremser, W. Macromol. Symp. 2002, 177, 25.

[20] Lowry, G. G. J. Polym. Sci. 1960, 42, 463.

[21] Worsfold, D. J.; Bywater, S. J. Polym. Sci. 1957, 26, 299.

[22] Madras, G.; Smith, J. M.; McCoy, B. J. Polym. Degrad. Stab. 1996, 52, 349.

[23] Yang, W.-T.; Jiang, S.; Liang, S.-J.; Deng, J.-P.; Ma, Y.-H.; Sun, Y.-F.; Liu, L.-Y.; He, C.-F. CN 200610012074, 2006 [Chem. Abstr. 2007, 146, 163609].

[24] Liang, S.-J. Ph. D. Dissertation, Beijing University of Chemical Technology, Beijing, 2007. (梁淑君, 博士论文, 北京化工大学, 北京, 2007.)

[25] Jiang, S. Ph. D. Dissertation, Beijing University of Chemical Technology, Beijing, 2009. (蒋姗, 博士论文, 北京化工大学, 北京, 2009.)

[26] Jiang, S.; Deng, J.-P.; Yang, W.-T. Polym. J. 2008, 40, 543.

[27] Liang, S.-J.; Deng, J.-P.; Yang, W.-T. Chin. J. Polym. Sci. 2010, 2 8, 323.

[28] Jiang, S.; Deng, J.-P.; Yu, Q.; Yang, W.-T. J. Appl. Polym. Sci. 2011, 120, 466.

[29] Jiang, S.; Sun, A.-P.; Deng, J.-P.; Yang, W.-T; Yu, Q. J. Macromol. Sci. Part A: Pure and Appl. Chem. 2011, 48, 846.

[30] Liang, S.-J.; Yang, W.-T. Acta Polym. Sinica 2011, (2), 180. (梁淑君, 杨万泰, 高分子学报, 2011, (2), 180.)

[31] Chen, C. M. S. Thesis, Beijing University of Chemical Technology, Beijing, 2011. (陈铖, 硕士论文, 北京化工大学, 北京, 2009.)

[32] Cao, L.-J.; Yin, M.-Z.; Ma, Y.-H.; Yang, W.-T. Acta Polym. Sinica 2012, (1), 75. (曹丽娟, 尹梅贞, 马育红, 杨万泰, 高分子学报, 2012, (1), 75.)

[33] Jiang, S.; Fang, X.-H.; Yu, Q.; Deng, J.-P.; Yang, W.-T. J. Appl. Polym. Sci. 2012, 12 4, 4121.

[34] Deng, J.-P.; Liang, S.-J.; Zhang, C.-R.; Yang, W.-T. Macromol. Rapid Commun. 2007, 28, 2163.

[35] Liang, S.-J.; Yang, W.-T. e-Polymers 2010, no. 092.

[36] Jiang, S.; Deng, J.-P.; Yang, W.-T. Macromol. Rapid Commun. 2008, 29, 1521.

[37] Liang, S.-J.; Yang, W.-T. Chin. Plast. 2010, 24, 34. (梁淑君, 杨万泰, 中国塑料, 2010, 24, 34.)

[38] Cui, L.-L.; Feng, S.-G.; Liu, Y.-F.; Wang, T.; Zhang, Q.-W. US 20120101218A1, 2012 [Chem. Abstr. 2012, 156, 534374].

“活”的α-甲基苯乙烯共聚物: 聚合反应新化学和材料工程新技术

A Novel Macroinitiator Based on the Copolymer of α-Methylstyrene Synthesis and Its Application in Preparing Block and Graft Polymers

PDF

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]	李雅宁, 王晓艳, 唐勇. 自由基聚合的立体选择性调控^★[J]. 化学学报, 2024, 82(2): 213-225.
[2]	易敬霖, 陈茂. 三氟氯乙烯与甲基异丙烯基醚的光诱导共聚反应^★[J]. 化学学报, 2024, 82(2): 126-131.
[3]	李乐乐, 向阳阳, 刘欢, 麻拴红, 李斌, 马正峰, 魏强兵, 于波, 周峰. 亚表面引发原子转移自由基聚合构筑温度响应型纳米纤维油水分离膜[J]. 化学学报, 2021, 79(3): 353-360.
[4]	李荣烨, Khiman Mehul, 盛力, 孙静. 两亲性聚氨基酸三嵌段共聚物构筑pH/溶剂可控多级纳米结构[J]. 化学学报, 2020, 78(11): 1235-1239.
[5]	范溦, 李敏, 洪春雁, 潘才元. 含香豆素基团超支化星形聚合物的合成与表征[J]. 化学学报, 2015, 73(4): 330-336.
[6]	丁妍春, 俞燕蕾, 韦嘉. 不同亲疏水比例的光响应性嵌段共聚物的合成及溶液组装行为研究[J]. 化学学报, 2014, 72(5): 602-608.
[7]	郝莹, 张洋, 何金林, 尚修娟, 张明祖, 倪沛红. 半乳糖胺修饰阳离子型刷形嵌段共聚物的合成与表征[J]. 化学学报, 2014, 72(5): 569-576.
[8]	潘高翔, 冯泽, 韦嘉, 俞燕蕾. 光/温度双响应三嵌段共聚物的合成及溶液自组装行为[J]. 化学学报, 2013, 71(05): 733-738.
[9]	高鹏, 王培境, 耿雪, 叶霖, 张爱英, 冯增国. γ-环糊精包结折叠双链PEG聚准轮烷材料的性能研究[J]. 化学学报, 2013, 71(03): 347-350.
[10]	房晓琳, 高保娇, 黄小卫, 张永奇, 顾来沅. 具有高离子识别能力的镉离子表面印迹材料的制备及其离子识别机理的研究[J]. 化学学报, 2013, 71(03): 409-416.
[11]	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.
[12]	吕会朝, 张成潘, 黄晋, 赵巧玲, 马志, 肖吉昌. 聚苯乙烯-co-聚(2,3,4,5,6-五氟苯乙烯)共聚物: 合成及其多孔薄膜的制备[J]. 化学学报, 2012, 70(9): 1125-1130.
[13]	杜俊玫, 高保娇, 黄小卫, 张永奇, 王明娟. 基于离子交换和表面引发接枝聚合制备阴离子表面印迹材料及其识别特性研究[J]. 化学学报, 2012, 70(17): 1831-1838.
[14]	王朝阳, 宁印, 陈云华, 童真. 光交联Pickering乳液中的粒子稳定剂制备胶体体微胶囊[J]. 化学学报, 2012, 70(16): 1721-1724.
[15]	张文建, 范溦, 李敏, 洪春雁, 潘才元. 多重响应性超支化星形聚合物的合成与组装以及控制释放研究[J]. 化学学报, 2012, 70(16): 1690-1696.