2-氨基吡啶镍配合物/MAO催化β-蒎烯与降冰片烯的共聚合反应

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (6): 1257.

2-氨基吡啶镍配合物/MAO催化β-蒎烯与降冰片烯的共聚合反应

黄增芳^1,2, 高海洋¹, 伍青¹

1. 新型聚合物材料设计合成与应用广东省高校重点实验室, 聚合物复合材料及功能材料教育部重点实验室, 中山大学化学与化学工程学院, 广州 510275;
2. 电子科技大学中山学院, 中山 528402

收稿日期:2009-09-30 出版日期:2010-06-10 发布日期:2010-06-10
通讯作者: 伍青, 男, 博士, 教授, 博士生导师, 主要从事高分子催化合成等方面研究. E-mail: ceswuq@mail.sysu.edu.cn
基金资助:
国家自然科学基金(批准号: 20734004)、广东省自然科学基金(批准号: 8251027501000018, 9452840301003542)、中山市科技计划项目(批准号: 20092A203)和电子科技大学中山学院科研启动基金(批准号: 408YKQ04)资助.

Copolymerization of β-Pinene and Norbornene with 2-Aminopyridine Nickel(Ⅱ) Complexes/MAO Catalysts

HUANG Zeng-Fang^1,2, GAO Hai-Yang¹, WU Qing^1*

1. Key Laboratory of Designed Synthesis and Application of Polymer Materials of Guangdong Higher Education Institues, Key Laboratory for Polymeric Composite and Functional Materierls of Ministry of Education, School of Chemistry and Chemical Engineering, Zhongshan University, Guangzhou 510275, China;
2. Zhongshan Institute, University of Electronic Science & Technology, Zhongshan 528402, China

Received:2009-09-30 Online:2010-06-10 Published:2010-06-10
Contact: Wu Qing. E-mail: ceswuq@mail.sysu.edu.cn
Supported by:
国家自然科学基金(批准号: 20734004)、广东省自然科学基金(批准号: 8251027501000018, 9452840301003542)、中山市科技计划项目(批准号: 20092A203)和电子科技大学中山学院科研启动基金(批准号: 408YKQ04)资助.

摘要/Abstract

摘要：

2-氨基吡啶镍配合物[(2-PyCH₂NAr)NiBr, Ar=2,6-二甲基苯基(a), 2,6-二异丙基苯基(b), 2,6-二氟苯基(c)]在助催化剂甲基铝氧烷(MAO)作用下能高活性催化β-蒎烯与降冰片烯共聚合, 得到分子量分布较宽(PDI ≈ 3.7～5.5)的共聚产物. 在相同条件下, 配体含F取代的配合物c对共聚合的催化活性最高. 对共聚产物用CHCl₃和四氢呋喃(THF)萃取分级, 得到2个分子量分布较窄(PDI ≈ 2.0)且组成差异较大的级分, 其中仅溶于CHCl₃而不溶于THF的级分的分子量较高, 具有高降冰片烯含量(x_N>90%); 而另一个溶于THF的级分的分子量较低, 具有较高的β-蒎烯含量. 结果表明, 共聚合体系中存在2种不同催化性质的活性中心. TGA分析显示, 共聚物有2个热分解温度, 随着降冰片烯含量的增加, 低温处的失重量逐渐减少.

关键词: 2-氨基吡啶; 镍配合物; β-蒎烯; 降冰片烯; 共聚合反应

Abstract:

In the presence of methylaluminoxane(MAO), 2-aminopyridine Ni(Ⅱ) complexes [(2-PyCH₂NAr)NiBr, Ar=2,6-dimethylphenyl(a), 2,6- diisopropylphenyl(b), 2,6-difluorophenyl(c)] presented highly catalytic activity for the copolymerizations of β-pinene and norbornene and afforded the copolymers with broad molecular weight distribution(PDI≈3.7—5.5). Complex c exhibited highest catalytic activity for the copolymerization under same conditions.After being extracted by CHCl₃ and THF, the crude product could be divided into two fractions with narrow molecular weight distribution(PDI≈2.0), CHCl₃-soluble but THF-insoluble fraction and THF-soluble fraction. The former contains high norbornene content(x_N＞90%) with higher molecular weight and the latter contains high β-pinene content with lower molecular weight, indicating that there exist two kinds of catalytic species in the copolymerization systems. The TGA analyses of the copolymers show that there are two thermal decomposition stages, and the loss of mass in the low thermal decomposition temperature stage decreases with an increase of norbornene content in the copolymer.

Key words: 2-Aminopyridine; Nickel(Ⅱ) complex; β-Pinene; Norborene; Copolymerization

TrendMD:

黄增芳, 高海洋, 伍青. 2-氨基吡啶镍配合物/MAO催化β-蒎烯与降冰片烯的共聚合反应. 高等学校化学学报, 2010, 31(6): 1257.

HUANG Zeng-Fang, GAO Hai-Yang, WU Qing*. Copolymerization of β-Pinene and Norbornene with 2-Aminopyridine Nickel(Ⅱ) Complexes/MAO Catalysts. Chem. J. Chinese Universities, 2010, 31(6): 1257.

参考文献

[1]GAO Hong-Yun(高红云), HA Cheng-Yong(哈成勇). Fine Chemicals(精细化工)[J], 2006, 23(11): 1135—1137
[2]Gozenbach C. T., Jordan M. A., Yunic R. P.. Encycl. Polym. Sci. Tech.[J], 1970, 13: 575—596
[3]Ruckel E. R., Arlt H. G., Wojcik R. T.. Adhesion Science and Technology[M], New York: Plenum Press, 1975: 395—400
[4]ZHUANG Jin-Shu(庄锦树), CHEN Hong-Xi(陈鸿熙). Chemistry and Industry of Forest Produce(林产化学与工业)[J], 1992, 12(2): 107—112
[5]Guine R. P. F., Castro J. A. A. M.. J. Appl. Polym. Sci.[J], 2001, 82: 2558—2565
[6]LI An-Long(李岸龙), LIANG Hui(梁晖), LU Jiang(卢江). Petrochemical Technology(石油化工)[J], 2004, 33(1): 82—86
[7]Martinez F., GaJardo I.. J. Polym. Sci., Part A: Polym. Chem.[J], 1981, 19(6): 1533—1538
[8]Martinez F., Florsheim R., Martinez H.. J. Polym. Sci., Part A: Polym. Chem.[J], 1882, 20(5): 1279—1285
[9]Snyder C., Mclver W., Sheffer H.. J. Appl. Polym. Sci.[J], 1977, 21(1): 131—139
[10]Li A. L., Wang Y., Liang H., Lu J.. J. Polym. Sci. Part A: Polym. Chem.[J], 2006, 44(8): 2376—2387
[11]Lu J., Kamigaito M., Sawamoto M., Higashimura T., Deng Y. X.. Macromolecules[J], 1997, 30(1): 22—26
[12]Lu J., Kamigaito M., Sawamoto M., Higashimura T., Deng Y. X.. Macromolecules[J], 1997, 30(1): 27—31
[13]DU Chuang(杜创), WANG Chun-Yu(王春雨), ZHANG Guo(张国), TANG Jun(汤钧). Chem. J. Chinese Universities(高等学校化学学报)[J], 2007, 28(10): 2018—2020
[14]WANG Yuan-Yuan(王媛媛), ZHU Fang-Ming(祝方明), LIN Shang-An(林尚安). Chem. J. Chinese Universities(高等学校化学学报)[J], 2008, 29(8): 1684—1688
[15]LU Ying-Ying(吕英莹), WU Qing(伍青), LU Ze-Jian(卢泽俭). Chem. J. Chinese Universities(高等学校化学学报)[J], 2001, 22(1): 160—162
[16]Huang Z. F., Song K. M., Liu F. S., Long J. M., Hu H., Gao H. Y., Wu Q.. J. Polym. Sci., Part A: Polym. Chem.[J], 2008, 46: 1618—1628
[17]Huang Z. F., Gao H. Y., Zhang L., Wu Q.. Chinese J. Polym. Sci.[J], 2008, 26: 567—573
[18]HUANG Zeng-Fang(黄增芳), GAO Hai-Yang(高海洋), WU Qing(伍青). Acta Polymerica Sinica(高分子学报)[J], 2009, (9): 874—878
[19]LU Jiang(卢江), LIANG Hui(梁晖), ZHANG Rong-Fu(张荣福). Chem. J. Chinese Universities(高等学校化学学报)[J], 2000, 21(12): 1932—1935
[20]Kennedy J. P., Liao T. P., Guhaniyogi S., Chang V. S. C.. J. Polym. Sci., Part A: Polym. Chem.[J], 1982, 20(11): 3229—3240
[21]SUN Zheng-Guang(孙争光). Vinyl Monomers Homo- and Co-Polymerization Catalyzed by Novel Diphosphinoamine Nickel(Ⅱ) Complexes and Characterization of Polymers(新型双膦胺镍催化烯类单体均聚合与共聚合及产物表征)[D], Guangzhou: Institute of Polymer Science, Sun Yat-sen University, 2006