席夫碱-铝配合物的合成及对丙交酯的立体选择性聚合

doi:10.7503/cjcu20130958

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 626.doi: 10.7503/cjcu20130958

席夫碱-铝配合物的合成及对丙交酯的立体选择性聚合

曲智^1,², 李想¹, 庞烜¹, 段然龙¹, 高波¹, 陈学思¹()

1. 中国科学院长春应用化学研究所, 生态环境高分子材料重点实验室, 长春 130022
2. 中国科学院大学, 北京 100049

收稿日期:2013-09-29 出版日期:2014-03-10 发布日期:2019-08-01
作者简介:联系人简介: 陈学思, 男, 博士, 研究员, 博士生导师, 主要从事生物医用材料研究. E-mail: xschen@ciac.ac.cn
基金资助:
国家自然科学基金(批准号: 21204082, 51173183, 21004061, 51021003)和国家“八六三”计划项目 (批准号: 2011AA02A202)资助

Synthesis of Aluminum-Schiff Base Catalyst and Their Stereoselective Polymerization of Lactides^†

QU Zhi^1,², LI Xiang¹, PANG Xuan¹, DUAN Ranlong¹, GAO Bo¹, CHEN Xuesi^1,^*()

1. Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2013-09-29 Online:2014-03-10 Published:2019-08-01
Contact: CHEN Xuesi E-mail:xschen@ciac.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21204082, 51173183, 21004061, 51021003) and the National High Technology Research and Development Program of China(No.2011AA02A202)

摘要/Abstract

摘要：

设计、合成了一系列不对称席夫碱配体, 得到了相应的金属铝配合物. 研究了配合物在外消旋丙交酯的开环聚合反应中的催化性能. 结果表明, 系列配合物对外消旋丙交酯(rac-LA)的聚合催化活性明显提高, 并具有立体选择性.

关键词: 丙交酯, 生物降解, 立体选择性聚合, 席夫碱

Abstract:

A series of asymmetric Schiff-base ligands and their aluminum Al(Ⅲ) complexes that contained different steric substituent were designed and synthesized. The structures of ligands and their complexes were characterized. One crystal of Schiff-base aluminum complex was obtained. X-Ray diffraction analyses showed that the central aluminum atoms of the complex adopt twisted four pyramid geometry. They were chiral but racemic complexes with two enantiomers in solid state. Their catalytic properties in the solution polymerization of racemic lactides(rac-LA) in the presence of 2-propanol were investigated in detail. All of the complexes had poor stereoselectivity for ring-opening polymerization(ROP) of rac-LA(P_m about 0.55), the polymerization rate of asymmetric complex was much faster than symmetric complex in ROP of rac-LA. The results evaluate that the substituent of ligands has great influence on the catalytic properties of the complex.

Key words: Lactide, Biodegradable, Stereoselective polymerization, Schiff-base

中图分类号:

O631

TrendMD:

曲智, 李想, 庞烜, 段然龙, 高波, 陈学思. 席夫碱-铝配合物的合成及对丙交酯的立体选择性聚合. 高等学校化学学报, 2014, 35(3): 626.

QU Zhi, LI Xiang, PANG Xuan, DUAN Ranlong, GAO Bo, CHEN Xuesi. Synthesis of Aluminum-Schiff Base Catalyst and Their Stereoselective Polymerization of Lactides^†. Chem. J. Chinese Universities, 2014, 35(3): 626.

图/表 6

Scheme 1 Syntheses of ligands and complexes

Fig.1 Perspective view of complex 2a with thermal ellipsoids drawn at 30% probability level Hydrogens are omitted for clarity.

Table 1 Polymerization data of rac-LA using complexes 1a—3aa

Complex	T/℃	t/h	[M]₀/[Cat]	Conv.^b(%)	10^-3M_n(GPC)^c	PDI^c	$P m d$
1a	70	60	50	95	6.8	1.16	0.53
1a	90	24	50	94	7.5	1.21	0.50
1a	110	14	50	93	8.6	1.35	0.46
2a	70	60	50	88	6.6	1.17	0.52
2a	90	24	50	87	7.9	1.23	0.49
2a	110	14	50	89	8.0	1.33	0.46
3a	70	60	50	96	6.5	1.19	0.52
3a	90	24	50	90	7.5	1.20	0.51
3a	110	14	50	95	8.5	1.30	0.45

Table 1 Polymerization data of rac-LA using complexes 1a—3aa

Complex	T/℃	t/h	[M]₀/[Cat]	Conv.^b(%)	10^-3M_n(GPC)^c	PDI^c	$P m d$
1a	70	60	50	95	6.8	1.16	0.53
1a	90	24	50	94	7.5	1.21	0.50
1a	110	14	50	93	8.6	1.35	0.46
2a	70	60	50	88	6.6	1.17	0.52
2a	90	24	50	87	7.9	1.23	0.49
2a	110	14	50	89	8.0	1.33	0.46
3a	70	60	50	96	6.5	1.19	0.52
3a	90	24	50	90	7.5	1.20	0.51
3a	110	14	50	95	8.5	1.30	0.45

Fig.2 1H NMR spectrum of PLA oligomer

Fig.3 Methine region of homonuclear decoupled 1H NMR spectrum of poly(rac-LA) using complex 2a

Fig.4 Kinetics curve of complex 2a with n(M0)/n(Al)/n(2-propanol)=50:1:1

参考文献 33

[1]	Finne A., Albertsson A. C., Biomacromolecules,2002, 3, 684—690
[2]	Jeong B., Kim S. W., Bae Y. H., Advanced Drug Delivery Reviews,2012, 64, 154—162
[3]	Cao W. X., Zhang H., Yuan X. Y., Chem. J. Chinese Universities,2011, 32(6), 1396—1400
	(曹文轩, 张红, 袁晓燕. 高等学校化学学报, 2011, 32(6), 1396—1400)
[4]	Zhao T. Y., Zhao J. P., Lei L. Y., Chen X. G., Wang L. C., Chen X. S., Wang L. P., Chem. J. Chinese Universities,2013, 34(1), 236—241
	(赵天倚, 赵继鹏, 雷莉妍, 陈晓光, 王立成, 陈学思, 王丽萍. 高等学校化学学报, 2013, 34(1), 236—241)
[5]	Agarwal S., Brandukova-Szmikowski N.E., Greiner A.,Polymers for Advanced Technologies, 1999, 10, 528—534
[6]	Chamberlain B. M., Jazdzewski B. A., Pink M., Hillmyer M. A., Tolman W. B., Macromolecules,2000, 33, 3970—3977
[7]	Liu C.B., Zhang D., Li D.G., Jiang D., Chen X., Chem. Res. Chinese Universities,2008, 24(5), 588—591
[8]	Zhuang X. L., Yu H. Y., Tang Z. H., Oyaizu K., Nishide H., Chen X. S., Chinese Journal of Polymer Science,2011, 29, 197—202
[9]	Brochu S., Prudhomme R. E., Barakat I., Jerome R., Macromolecules,1995, 28, 5230—5239
[10]	Tsuji H., Ikada Y., Journal of Applied Polymer Science,1994, 53, 1061—1071
[11]	Bero M., Dobrzynski P., Kasperczyk J., Journal of Polymer Science Part A: Polymer Chemistry,1999, 37, 4038—4042
[12]	Ovitt T. M., Coates G. W., J. Am. Chem. Soc., 1999, 121, 4072—4073
[13]	Cheng M., Attygalle A. B., Lobkovsky E. B., Coates G. W., J. Am. Chem. Soc., 1999, 121, 11583—11584
[14]	Slivniak R., Domb A. J., Biomacromolecules,2002, 3, 754—760
[15]	Fujiwara T., Mukose T., Yamaoka T., Yamane H., Sakurai S., Kimura Y., Macromolecular Bioscience,2001, 1, 204—208
[16]	Li S. M., Vert M., Macromolecules,2003, 36, 8008—8014
[17]	Slager J., Domb A. J., Advanced Drug Delivery Reviews,2003, 55, 549—583
[18]	Slager J., Domb A. J., Biomaterials,2002, 23, 4389—4396
[19]	Pang X., Chen X., Zhuang X., Jing X., Journal of Polymer Science Part A: Polymer Chemistry,2008, 46, 643—649
[20]	Yang Y. K., Tang Z. H., Pang X., Du H. Z., Chen X. S., Jing X. B., Chem. J. Chinese Universities,2006, 27(2), 352—355
	(杨永坤, 汤朝晖, 庞烜, 杜洪志, 陈学思, 景遐斌. 高等学校化学学报, 2006, 27(2), 352—355)
[21]	Bero M., Kasperczyk J., Jedlinski Z. J., Makromolekulare Chemie-Macromolecular Chemistry and Physics,1990, 191, 2287—2296
[22]	Chamberlain B. M., Cheng M., Moore D. R., Ovitt T. M., Lobkovsky E. B., Coates G. W., J. Am. Chem. Soc., 2001, 123, 3229—3238
[23]	Cai C.X., Amgoune A., Lehmann C. W., Carpentier J. F.,Chem. Commun., 2004, 330—331
[24]	Hormnirun P., Marshall E. L., Gibson V. C., White A. J. P., Williams D. J., J. Am. Chem. Soc., 2004, 126, 2688—2689
[25]	Spassky N., Wisniewski M., Pluta C., LeBorgne A., Macromolecular Chemistry and Physics,1996, 197, 2627—2637
[26]	Radano C. P., Baker G. L., Smith M. R., J. Am. Chem. Soc., 2000, 122, 1552—1553
[27]	Ovitt T. M., Coates G. W., J. Am. Chem. Soc., 2002, 124, 1316—1326
[28]	Ovitt T. M., Coates G. W., Journal of Polymer Science Part A: Polymer Chemistry,2000, 38, 4686—4692
[29]	Zhong Z. Y., Dijkstra P. J., Feijen J., Angew. Chem. Int. Ed., 2002, 41, 4510
[30]	Zhong Z. Y., Dijkstra P. J., Feijen J., J. Am. Chem. Soc., 2003, 125, 11291—11298
[31]	Wisniewski M., LeBorgne A., Spassky N., Macromolecular Chemistry and Physics,1997, 198, 1227—1238
[32]	Nomura N., Ishii R., Akakura M., Aoi K., J. Am. Chem. Soc., 2002, 124, 5938—5939
[33]	Pang X., Du H. Z., Chen X. S., Wang X. H., Jing X. B., Chemistry: A European Journal,2008, 14, 3126—3136

席夫碱-铝配合物的合成及对丙交酯的立体选择性聚合

Synthesis of Aluminum-Schiff Base Catalyst and Their Stereoselective Polymerization of Lactides^†

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席夫碱-铝配合物的合成及对丙交酯的立体选择性聚合

Synthesis of Aluminum-Schiff Base Catalyst and Their Stereoselective Polymerization of Lactides†

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Synthesis of Aluminum-Schiff Base Catalyst and Their Stereoselective Polymerization of Lactides^†