Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene

doi:10.6023/cjoc201701052

Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (5): 1284-1289.DOI: 10.6023/cjoc201701052 Previous Articles Next Articles

Notes

双核茂钛催化剂中苄基苯环的弱作用效应对乙烯聚合行为影响的研究

许胜, 梁春超, 吕中文, 朱玉玲, 张翠, 米普科

华东理工大学化学与分子工程学院上海 200237

收稿日期:2017-01-27 修回日期:2017-03-27 发布日期:2017-04-21
通讯作者: 许胜,米普科 E-mail:xusheng@ecust.edu.cn;pkm@ecust.edu.cn
基金资助:
国家自然科学基金（No.U1362111）资助项目.

Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene

Xu Sheng, Liang Chunchao, Lü Zhongwen, Zhu Yuling, Zhang Cui, Mi Puke

School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237

Received:2017-01-27 Revised:2017-03-27 Published:2017-04-21
Contact: 10.6023/cjoc201701052 E-mail:xusheng@ecust.edu.cn;pkm@ecust.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. U1362111).

1. Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene.PDF(542KB)

Abstract

In order to study the effect of the benzyl benzene ring on the catalytic behavior of binuclear metallocene, the binuclear metallocene [μ,μ-1,4-(CH₂)₂(C₆H₄)] [(η⁵-C₅H₅)TiCl₂(η⁵-(C₆H₅)C(Me)₂(C₅H₃)]₂ [(TiBz)₂] is synthesized and characterized by ¹H NMR, ¹³C NMR, mass spectra and elemental analysis. When combined with methylaluminoxane (MAO), the (TiBz)₂/MAO system catalyzed ethylene polymerization and the polymer with C(4) branch were obtained. It is suggested that the C(4) branch is from the ethylene trimerization by the weak effect between the benzyl and center metal. The (TiBz)₂/MAO system also showed great ability for ethylene copolymerization with 1-hexene and the incorporation of 1-hexene in polymer reached up to 13.7 mol%. The ¹³C NMR result of polymer showed that the polymer contained alternatively copolymerized HEHE fragment and the possible mechanism is presented for explaining the special catalytic behavior. It is the weak effect between the benzyl and center metal that led to the alternative insertion of ethylene and 1-hexene, and the narrow molecular weight distribution (PDI=2.23) meant that there could be a great synergistic effect between the two activate center metals in the polymerization process, which greatly increased the copolymerization capability.

Key words: benzyl, binuclear metallocene, weak effect, copolymerization ability, mechanism

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Xu Sheng, Liang Chunchao, Lü Zhongwen, Zhu Yuling, Zhang Cui, Mi Puke. Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene[J]. Chin. J. Org. Chem., 2017, 37(5): 1284-1289.

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[1] Saßmannshausen, J.; Powell, A. K.; Anson, C. E.; Wocadlo, S.; Bochmann, M. J. Organomet. Chem. 1999, 592, 84.
[2] Deckers, P. J. W.; van der Linden, A. J.; Meetsma, A.; Hessen B. Eur. J. Inorg. Chem. 2000, 929.
[3] Deckers, P. J. W.; Hessen, B.; Teuben, J. H. Angew. Chem., Int. Ed. 2001, 40(13), 2516.
[4] Deckers, P. J. W.; Hessen, B.; Teuben, J. H. Organometallics 2002, 21, 5122.
[5] de Bruin, T. J. M.; Magna, L.; Raybaud, P.; Toulhoat, H. Organometallics 2003, 22, 3404.
[6] Tobisch, S.; Ziegler, T. J. Am. Chem. Soc. 2004, 126, 9059.
[7] Hagen, H. Ind. Eng. Chem. Res. 2006, 45, 3544.
[8] Otten, E.; Batinas, A. A.; Meetsma, A.; Hessen, B. J. Am. Chem. Soc. 2009, 131, 5298.
[9] Wang, C.; Huang, J.-L. Chin. J. Chem. 2006, 24, 1397 (in Chinese). (王晨, 黄吉玲, 有机化学, 2006, 24, 1397.)
[10] Wu, T.-Z.; Qian, Y. L.; Huang, J.-L. J. Mol. Catal. A: Chem. 2004, 214, 227.
[11] Huang, J.-L.; Wu, T.-Z.; Qian, Y.-L. Chem. Commun. 2003, 2816.
[12] Suzuki, Y.; Kinoshita, S.; Shibahara, A.; Ishii, S.; Kawamura, K.; Inoue, Y.; Fujita, T. Organometallics 2010, 29, 2394.
[13] Stevens, J. C. In 11th International Congress on Catalysis-40th Anniversary, Eds.: Hightower, J. W.; Delgass, W. N.; Iglesia, E.; Bell, A. T., Elsevier, Amsterdam, 1996, pp. 11～20.
[14] Xu, S. 17th China Congress on Organometallic Chemistry, Beijing, 2012, p. 75 (in Chinese). (许胜, 第17届全国金属有机化学会议, 北京, 2012, p. 75.)
[15] Xu, S. 18th China Congress on Organometallic Chemistry, LanZhou, 2014, p. 251 (in Chinese). (许胜, 第18届全国金属有机化学会议, 兰州, 2014, p. 251.)
[16] Delferro, M.; Marks, T. J. Chem. Rev. 2011, 111, 2450.
[17] Weberski, M. P.; Chen, Jr. C.; Delferro, M.; Marks, T. J. Chem. Eur. J. 2012, 18, 10715.
[18] Motta, A.; Fragala, I. L.; Marks, T. J. J. Chem. Theory Comput. 2013, 9, 3491.
[19] Liu, S.; Motta, A.; Delferro, M.; Marks, T. J. J. Am. Chem. Soc. 2013, 135, 8830.
[20] McInnis, J. P.; Delferro, M.; Marks, T. J. Acc. Chem. Res. 2014, 47, 2545.
[21] Liu, S.; Motta, A.; Mouat, A. R.; Delferro, M.; Marks, T. J. J. Am. Chem. Soc. 2014, 136, 10460.
[22] Xu, S.; Jia, J.-J.; Huang, J.-L. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 4901.
[23] Xu, S.; Huang, J.-L. J. Appl. Polym. Sci. 2013, 2891.
[24] Mi, P.-K.; Xu, S.; Qu, L. D.; Zhang, D. S.; Qian, C.; Wang, S.-H. J. Appl. Polym. Sci. 2011, 121, 21.
[25] Xu, S. M.S. Thesis, East China University of Science and Tehnology, Shanghai, 2000 (in Chinese). (许胜, 硕士论文, 华东理工大学, 上海, 2000.)
[26] Sun, J.-Q.; Zhang, H.-Y.; Liu, X.-J.; Xiao, X.-H.; Lin, F. Eur. Polym. J. 2006, 42, 1259.
[27] Seger, M. R.; Maciel, G. E. Anal. Chem. 2004, 76, 5734.
[28] Liu, S.-F.; Motta, A.; Aidan, R. M.; Delferro, M.; Marks, T. J. J. Am. Chem. Soc. 2014, 136, 10460.

双核茂钛催化剂中苄基苯环的弱作用效应对乙烯聚合行为影响的研究

Study on the Influence of the Weak Effect of Benzyl Benzene Ring on the Polymerization Behavior of Ethylene

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