极性单体锂系阴离子嵌段共聚物的合成与表征

doi:10.7503/cjcu20140468

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (9): 2007.doi: 10.7503/cjcu20140468

极性单体锂系阴离子嵌段共聚物的合成与表征

陈波, 王继铭, 束民泽, 邹斌, 管涌, 郑安呐

华东理工大学材料科学与工程学院, 上海市先进聚合物材料重点实验室,超细材料制备与应用教育部重点实验室, 上海 200237

收稿日期:2014-05-19 出版日期:2014-09-10 发布日期:2019-08-01
作者简介:联系人简介: 郑安呐, 男, 博士, 教授, 博士生导师, 主要从事阴离子聚合及反应挤出研究. E-mail: zan@ecust.edu.cn
基金资助:
基金项目: 国家自然科学基金(批准号: 50933002)资助

Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium^†

CHEN Bo, WANG Jiming, SHU Minze, ZOU bin, GUAN Yong, ZHENG Anna^*

School of Materials Science and Engineering, Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

Received:2014-05-19 Online:2014-09-10 Published:2019-08-01
Contact: ZHENG Anna
Supported by:
Supported by the National Natural Science Foundation of China(No.50933002)

摘要/Abstract

摘要：

以酚锂作为副反应抑制剂, 以正丁基锂或1,1-二苯基乙烯盖帽的正丁基锂为引发剂, 通过顺次添加单体的方法, 合成了结构明确的聚异戊二烯-b-聚甲基丙烯酸甲酯(PI-b-PMMA)和聚甲基丙烯酸正丁酯-b-聚甲基丙烯酸甲酯(PBMA-b-PMMA)2种嵌段聚合物. 嵌段聚合反应中甲基丙烯酸甲酯(MMA)的转化率均高于90%, 通过核磁图谱计算的链节摩尔比与理论设计值吻合. PI-b-PMMA和PBMA-b-PMMA的分子量分别达到4×10⁴和1.6×10⁴. 在环己烷中, 通过顺次添加单体的方法, 合成了结构明确的聚苯乙烯-b-聚异戊二烯-b-聚甲基丙烯酸甲酯(PS-b-PI-b-PMMA)三嵌段共聚物, 各单体的转化率均达到100%, 并且产物中的链节摩尔比和理论设计值一致, 最终产物的分子量达到7.4×10⁴, 分子量分布仅为1.28, 为极性三嵌段热塑性弹性体以及有机玻璃透明增韧剂的工业化奠定了基础.

关键词: 阴离子活性聚合, 酚锂, 甲基丙烯酸甲酯, 嵌段共聚物

Abstract:

Well-defined block copolymers polyisoprene-b-poly(methyl methacrylate)(PI-b-PMMA) and poly(butyl methacrylate)-b-poly(methyl methacrylate)(PBMA-b-PMMA were synthesized in THF initiated by n-BuLi and DPHLi with the addition of P-Complex. The polymerizations were carried out under the conditions which could be achieved in industry through adding monomers by sequence. The conversion of MMA was higher than 90% both in PI-b-PMMA and PBMA-b-PMMA, and the molar ratios of each segment in block copolymers detected by ¹H NMR fit to those calculated. The M_n of PI-b-PMMA and PBMA-b-PMMA were 4.0×10⁴ and 1.6×10⁴, respectively. Well-defined triblock polymer PS-b-PI-b-PMMA was synthesized in cyclohexane under the condition which could be achieved in industry. The conversions of monomers were all completed, and the molar ratio in the final triblock polymer was consistent to the one calculated. The final M_n was 7.4×10⁴, and the molecular weight distribution(MWD) was only 1.28.

Key words: Living anionic polymerization, Lithium phenoxide, Methyl methacrylate, Block copolymer

中图分类号:

O632.1

TrendMD:

陈波, 王继铭, 束民泽, 邹斌, 管涌, 郑安呐. 极性单体锂系阴离子嵌段共聚物的合成与表征. 高等学校化学学报, 2014, 35(9): 2007.

CHEN Bo, WANG Jiming, SHU Minze, ZOU bin, GUAN Yong, ZHENG Anna. Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium^†. Chem. J. Chinese Universities, 2014, 35(9): 2007.

图/表 9

Table 1 Results of block copolymerization of Ip and MMA

Sample	Temperature^a/℃	Capping agent^b	n_Ip: $n MMA c$	Conversion of MMA(%)
1	50/50	None	1∶0.27	16.8
2	50/0	None	1∶0.26	16.2
3	50/0	St	1∶0.47	29.4
4	50/0	α-mSt	1∶1.32	78.5
5	50/0	DPE	1∶2.19	93.4
6^d	50/0	DPE		36.1

Table 1 Results of block copolymerization of Ip and MMA

Sample	Temperature^a/℃	Capping agent^b	n_Ip: $n MMA c$	Conversion of MMA(%)
1	50/50	None	1∶0.27	16.8
2	50/0	None	1∶0.26	16.2
3	50/0	St	1∶0.47	29.4
4	50/0	α-mSt	1∶1.32	78.5
5	50/0	DPE	1∶2.19	93.4
6^d	50/0	DPE		36.1

Fig.1 1H NMR spectra of PI-b-PMMA polymerized under different conditions

Fig.2 GPC curves(LS signal) of PI(a) and PI-b-PMMA(b) polymerized with DPE as capping agent in THF

Table 2 Results of PBMA-b-PMMA polymerized after different reaction time of BMA

Sample	$t 1 a$ /min	$t 2 b$ /min	n_BMA∶ $n MMA c$	Conversion^d (%)
1	1	20	1∶0.9	94.1
2	2	20	1∶0.87	93.7
3	4	20	1∶0.55	80.5
4	8	20	1∶0.38	72.1
5	16	20	1∶0.29	63.0

Table 2 Results of PBMA-b-PMMA polymerized after different reaction time of BMA

Sample	$t 1 a$ /min	$t 2 b$ /min	n_BMA∶ $n MMA c$	Conversion^d (%)
1	1	20	1∶0.9	94.1
2	2	20	1∶0.87	93.7
3	4	20	1∶0.55	80.5
4	8	20	1∶0.38	72.1
5	16	20	1∶0.29	63.0

Fig.3 1H NMR spectra of PBMA-b-PMMA with different reaction time of BMA at 0 ℃ in THF

Fig.4 GPC curves of PBMA(a) and PBMA-b-PMMA(b) with BMA polymerization time of 1 min at 0 ℃ in THF

Fig.5 Mechanism of lithium phenoxide to the polymerization

Fig.6 1H NMR spectrum of PS-b-PI-b-PMMA synthesized in CH at 50 ℃/50 ℃/0 ℃

Fig.7 GPC curves of PS-b-PI-b-PMMA synthesized in CH at 50 ℃/50 ℃/0 ℃

参考文献 25

[1]	Hirao A., Murano K., Oie T., Uematsu M., Goseki R., Matsuo Y., Polym. Chem., 2011, 2, 1219—1233
[2]	Hadjichristidis N., Iatrou H., Pitsikalis M., Mays J., Prog. Polym. Sci., 2006, 31, 1068—1132
[3]	Yoo H., Watanabe T., Matsunaga Y., Hirao A., Macromolecules,2012, 45, 100—112
[4]	Ito S., Goseki R., Senda S., Hirao A., Macromolecules,2012, 45, 4997—5011
[5]	Ito S., Goseki R., Ishizone T., Senda S., Hirao A., Macromolecules,2013, 46, 819—827
[6]	Zhang H., He J., Zhang C., Ju Z., Li J., Yang Y., Macromolecules,2012, 45, 828—841
[7]	Knoll K., Niessner N., Macromol. Symp., 1998, 132, 231—243
[8]	Sun G., Zhou Y.J., Zhang K., Liu C. Q., Zheng A. N.,Acta Polymerization Sinica, 2007, (9), 790—795
	(孙刚, 周颖坚, 张锴, 刘彩芹, 郑安呐. 高分子学报, 2007, (9), 790—795)
[9]	Zhang Y., Yan W., Gao S.S., Zheng A. N., Han Z. W.,Acta Polymerization Sinica, 2002, (5), 677—682
	(张鹰, 烟伟, 高士双, 郑安呐, 韩哲文. 高分子学报, 2002, (5), 677—682)
[10]	Zhou Y.J., Zhang K., Sun G., Wei D. F., Zheng A. N.,Acta Polymerization Sinica, 2006, (3), 437—442
	(周颖坚, 张锴, 孙刚, 危大福, 郑安呐. 高分子学报, 2006, (3), 437—442)
[11]	Yuan X., Guan Y., Li S., Zheng A.,J. Appl. Polym. Sci., 2013, doi: 10.1002/APP.39429
[12]	Zhuang R., Müller A. H. E., Macromolecules,1995, 28, 8035—8042
[13]	Webster O. W., Hertler W. R., Sogah D. Y., Farnham W. B., RajanBabu T. V., J. Am. Chem. Soc., 1983, 105, 5706—5708
[14]	Bandermann F., Beckelmann D., Broska D., Fieberg A., Roloff T., Wolters D., Macromol. Chem. Phys., 1995, 196, 2335—2347
[15]	Reetz M.T., Ostarek R., J. Chem. Soc.,Chem. Commun., 1988, 213—215
[16]	Liang J. G., Han B. Y., Yang W. T., Chem. J. Chinese Universities,2005, 26(9), 1780—1782
	(梁建国, 韩丙勇, 杨万泰. 高等学校化学学报, 2005, 26(9), 1780—1782)
[17]	Baskaran D., Müller A. H. E., Prog. Polym. Sci., 2007, 32, 173—219
[18]	Baskaran D., Prog. Polym. Sci., 2003, 28, 521—581
[19]	Lee S., Chang T., Eur. Polym. J., 2011, 47, 800—804
[20]	Yi L. M., Zhan X. L., Chen F. Q., Jiang B., Chen B., Chem. J. Chinese Universities,2007, 28(12), 2393—2397
	(易玲敏, 詹晓力, 陈丰秋, 蒋波, 陈碧. 高等学校化学学报, 2007, 28(12), 2393—2397)
[21]	Ruckdäschel H., Sandler J. K. W., Altstädt V., Rettig C Schmalz H., Abetz V., Müller A. H. E., Polymer,2006, 47, 2772—2790
[22]	Auschra C., Stadler R., Macromolecules,1993, 26, 6364—6377
[23]	Zheng A., Zhang J., Guan Y., Hu F., Wei D., Wang S., Method of Controlling Anionic Polymerization, US 8546503 B2,2013-10-01
[24]	Li T.Y., Chen B., Wu S. H., Shu M. Z., Guan Y., Zheng A. N.,Acta Polymerization Sinica, 2014, (9), 1210—1217
	(李天一, 陈波, 吴尚翰, 束民泽, 管涌, 郑安呐. 高分子学报, 2014, (9), 1210—1217)
[25]	Yuan X. Y., Zhang J. Y., Wang N., Wu Y., Zheng A. N., J. East China Univ. Sci. Tech., 2012, 38, 429—435
	(袁协尧, 张晋玉, 王宁, 吴洋, 郑安呐. 华东理工大学学报(自然科学版), 2012, 38, 429—435)

极性单体锂系阴离子嵌段共聚物的合成与表征

Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium^†

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极性单体锂系阴离子嵌段共聚物的合成与表征

Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium†

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Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium^†