Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

Citation: Xin-e Duan, Qi-feng Xing, Zhen-ming Dong, Jian-bin Chao, Sheng-di Bai, Dian-sheng Liu, Wen-hua Sun. Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2016, 34(3): 390-398. doi: 10.1007/s10118-016-1768-6 shu

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

1.
1. Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
2.
2. School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
3.
3. Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
4.
5.
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
6.
Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
7.
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
基金项目:
This work was financially supported by the National Natural Science Foundation of China (Nos. 21272142 and U1362204) and the Natural Science Foundation of Shanxi Province (No. 2015011015).

摘要: The trichlorozirconium 2-hydrazonides (R=H, A; R=CH3, B) were synthesized through the finely controlled stoichiometrical reactions of anhydrous zirconium tetrachloride with the lithium salt of either 1-(furan-2-ylmethylene)-2-phenylhydrazonide or 1-(furan-2-ylethylidene)-2-phenyl hydrazonide in the solvent tetrahydrofuran (THF), respectively. These complexes were highly sensitive to air and moisture due to solely using less bulky ligand of hydrazonides. The molecular structures of the title complexes, determined by means of single crystal X-ray diffraction, were found to be the distorted pentagonal bipyramid geometry around zirconium atom, with three chlorides and the hydrazonato ligand acting as the 2-coordination mode as well as two incorporated THF molecules. Upon activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), both complexes A and B exhibited catalytic activities toward ethylene polymerization, producing polyethylenes with ultra-high molecular weights.

关键词:

Titanium complexes
/ Phenylhydrazonide
/ Ethylene polymerization
/ Ultra-high molecular weight polyethylene

English

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

1.
1. Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
2.
2. School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
3.
3. Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
4.
5.
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
6.
Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
7.
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
Received Date: 21 November 2015
Revised Date: 21 December 2015
Available Online: 05 March 2016
Fund Project:
This work was financially supported by the National Natural Science Foundation of China (Nos. 21272142 and U1362204) and the Natural Science Foundation of Shanxi Province (No. 2015011015).

Abstract: The trichlorozirconium 2-hydrazonides (R=H, A; R=CH3, B) were synthesized through the finely controlled stoichiometrical reactions of anhydrous zirconium tetrachloride with the lithium salt of either 1-(furan-2-ylmethylene)-2-phenylhydrazonide or 1-(furan-2-ylethylidene)-2-phenyl hydrazonide in the solvent tetrahydrofuran (THF), respectively. These complexes were highly sensitive to air and moisture due to solely using less bulky ligand of hydrazonides. The molecular structures of the title complexes, determined by means of single crystal X-ray diffraction, were found to be the distorted pentagonal bipyramid geometry around zirconium atom, with three chlorides and the hydrazonato ligand acting as the 2-coordination mode as well as two incorporated THF molecules. Upon activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), both complexes A and B exhibited catalytic activities toward ethylene polymerization, producing polyethylenes with ultra-high molecular weights.

Key words:

Titanium complexes
/ Phenylhydrazonide
/ Ethylene polymerization
/ Ultra-high molecular weight polyethylene

1. [1]
  Makio, H., Terao, H., Iwashita, A. and Fujita, T., Chem. Rev., 2011, 111: 2363
2. [2]
  Wang, S., Sun, W.H. and Redshaw, C., J. Organomet. Chem., 2014, 751: 717
3. [3]
  Ma, J., Feng, C., Wang, S., Zhao, K.Q., Sun, W.H., Redshaw, C. and Solan, G.A. Inorg. Chem. Front., 2014, 1: 14
4. [4]
  Fan, M., Yang, Q.K., Tong, H.B., Yuan, S.F., Jia, B., Guo, D.L., Zhou, M.S. and Liu, D.S., RSC Adv., 2012, 2: 6599
5. [5]
  Bai, S.D., Guan, F., Hu, M., Yuan, S.F., Guo, J.P. and Liu, D.S., Dalton Trans., 2011, 40: 7686
6. [6]
  Tong, H.B., Li, M., Bai, S.D., Yuan, S.F., Chao, J.B., Huang, S.P. and Liu, D.S., Dalton Trans., 2011, 40: 4236
7. [7]
  Duan, X.E., Yuan, S.F., Tong, H.B., Bai, S.D., Wei, X.H. and Liu, D.S., Dalton Trans., 2012, 41: 9460
8. [8]
  Bai, S.D., Tong, H.B., Guo, J.P., Zhou, M.S., Liu, D.S. and Yuan, S.F., Polyhedron, 2010, 29: 262
9. [9]
  Bai, S.D., Tong, H.B., Guo, J.P., Zhou, M.S. and Liu, D.S., Inorg. Chim. Acta, 2009, 362: 1143
10. [10]
  Li, J.F., Huang, S.P., Weng, L.H. and Liu, D.S., J. Organomet. Chem., 2006, 691: 3003
11. [11]
  Li, J.F., Huang, S.P., Weng, L.H. and Liu, D.S., Eur. J. Inorg. Chem., 2003, 810
12. [12]
  Li, J.F., Weng, L.H., Wei, X.H. and Liu, D.S., J. Chem. Soc., Dalton Trans., 2002, 1401
13. [13]
  Yuan, S.F., Bai, S.D., Tong, H.B., Wei, X.H., Liu, D.S. and Sun, W.H., Inorg. Chim. Acta, 2011, 370: 215
14. [14]
  Yuan, S.F., Zhang, L.P., Liu, D.S. and Sun, W.H., Macromol. Res., 2010, 18: 690
15. [15]
  Zhou, M.S., Huang, S.P., Weng, L.H., Sun, W.H. and Liu, D.S., J. Organomet. Chem., 2003, 665: 237
16. [16]
  Chen, X., Guan, L.L., Eisen, M.S., Li, H.F., Tong, H.B., Zhang, L.P. and Liu, D.S., Eur. J. Inorg. Chem., 2009, 23: 3488
17. [17]
  Zhou, M.S., Tong, H.B., Wei, X.H. and Liu, D.S., J. Organomet. Chem., 2007, 692: 5195
18. [18]
  Zhou, M.S., Zhang, S., Tong, H.B., Sun, W.H. and Liu, D.S., Inorg. Chem. Commun., 2007, 10: 1262
19. [19]
  Yuan, S.F., Bai, S.D., Liu, D.S and Sun, W.H., Organometallics, 2010, 29: 2132
20. [20]
  Lappert, M.F. and Liu, D.S., J. Organomet. Chem., 1995, 500: 203
21. [21]
  Shakdofa, M.M.E., Shtaiwi, M.H., Morsy, N. and Abdel-rassel, T.M.A., Main Group Chem., 2014, 13: 187
22. [22]
  Chen, L.Y., Hou, J.X. and Sun, W.H., Appl. Cataly. A: General, 2003, 246: 11
23. [23]
  Hou, J.X., Sun, W.H., Zhang, D.H., Chen, L.Y., Li, W., Zhao, D.F. and Song, H.B., J. Mol. Catal. A: Chem., 2005, 231: 221
24. [24]
  Tabernero, V., Cuenca, T. and Herdtweck, E., J. Organomet. Chem., 2002, 663: 173
25. [25]
  Gambarotta, S., Floriani, C., Chiesi-Villa, A. and Guastini, C., Inorg. Chem., 1983, 22: 2029
26. [26]
  Hey, E., Lappert, M.F., Atwood, J.L. and Bott, S.G., Polyhedron, 1988, 7: 2083
27. [27]
  Kim, S.J., Yang, N., Kim, D.H., Kang, S.O. and Ko, J., Organometallics, 2000, 19: 4036
28. [28]
  Sheldrick, G.M., SHELXTL/PC. Version 6.10, Bruker AXS Inc., Madison, WI, 1999
29. [29]
  Kretschmer, W.P., Hessen, B., Noor, A., Scott, N.M. and Kempe, R., J. Organomet. Chem., 2007, 692: 4569
30. [30]
  Sanz, M., Mosquera, M.E.G., Cuenca, T., Arellano, C.R.de, Schormann, M. and Bochmann, M., Polyhedron, 2007, 26: 5339
31. [31]
  Alamo, R.G., Londono, J.D., Mandelkern, L., Stehling, F.C. and Wignall, G.D., Macromolecules, 1994, 27: 411
32. [32]
  Talja, M., Klinga, M., Polamo, M., Aitola, E. and Leskela, M., Inorg. Chim. Acta, 2005, 358: 1061
33. [33]
  Yuan, S.F., Wei, X.H., Tong, H.B., Zhang, L.P., Liu, D.S. and Sun, W.H., Organometallics, 2010, 29: 2085

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 1271
HTML全文浏览量: 45

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

English

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

English

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs