Citation: 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]. Chinese Journal of Organic Chemistry, ;2017, 37(5): 1284-1289. doi: 10.6023/cjoc201701052 shu

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

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

Corresponding author: Xu Sheng, xusheng@ecust.edu.cn Mi Puke, pkm@ecust.edu.cn
Received Date: 27 January 2017
Revised Date: 27 March 2017

Fund Project: Project supported by the National Natural Science Foundation of China U1362111

Figures(4)

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.
- benzyl,
- binuclear metallocene,
- weak effect,
- copolymerization ability,
- mechanism
1. [1]
  Saßmannshausen, J.; Powell, A. K.; Anson, C. E.; Wocadlo, S.; Bochmann, M. J. Organomet. Chem. 1999, 592, 84. doi: 10.1016/S0022-328X(99)00488-X
2. [2]
  Deckers, P. J. W.; van der Linden, A. J.; Meetsma, A.; Hessen B. Eur. J. Inorg. Chem. 2000, 929.
3. [3]
  Deckers, P. J. W.; Hessen, B.; Teuben, J. H. Angew. Chem., Int. Ed. 2001, 40(13), 2516. doi: 10.1002/(ISSN)1521-3773
4. [4]
  Deckers, P. J. W.; Hessen, B.; Teuben, J. H. Organometallics 2002, 21, 5122. doi: 10.1021/om020765a
5. [5]
  de Bruin, T. J. M.; Magna, L.; Raybaud, P.; Toulhoat, H. Organometallics 2003, 22, 3404. doi: 10.1021/om030255w
6. [6]
  Tobisch, S.; Ziegler, T. J. Am. Chem. Soc. 2004, 126, 9059. doi: 10.1021/ja048861l
7. [7]
  Hagen, H. Ind. Eng. Chem. Res. 2006, 45, 3544. doi: 10.1021/ie060133e
8. [8]
  Otten, E.; Batinas, A. A.; Meetsma, A.; Hessen, B. J. Am. Chem. Soc. 2009, 131, 5298. doi: 10.1021/ja810089f
9. [9]
  Wang, C.; Huang, J.-L. Chin. J. Chem. 2006, 24, 1397 (in Chinese).
10. [10]
  Wu, T.-Z.; Qian, Y. L.; Huang, J.-L. J. Mol. Catal. A: Chem. 2004, 214, 227. doi: 10.1016/j.molcata.2003.12.018
11. [11]
  Huang, J.-L.; Wu, T.-Z.; Qian, Y.-L. Chem. Commun. 2003, 2816.
12. [12]
  Suzuki, Y.; Kinoshita, S.; Shibahara, A.; Ishii, S.; Kawamura, K.; Inoue, Y.; Fujita, T. Organometallics 2010, 29, 2394. doi: 10.1021/om1003368
13. [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. [14]
  Xu, S. 17th China Congress on Organometallic Chemistry, Beijing, 2012, p. 75 (in Chinese).
15. [15]
  Xu, S. 18th China Congress on Organometallic Chemistry, LanZhou, 2014, p. 251 (in Chinese).
16. [16]
  Delferro, M.; Marks, T. J. Chem. Rev. 2011, 111, 2450. doi: 10.1021/cr1003634
17. [17]
  Weberski, M. P.; Chen, Jr. C.; Delferro, M.; Marks, T. J. Chem. Eur. J. 2012, 18, 10715.
18. [18]
  Motta, A.; Fragala, I. L.; Marks, T. J. J. Chem. Theory Comput. 2013, 9, 3491. doi: 10.1021/ct400259a
19. [19]
  Liu, S.; Motta, A.; Delferro, M.; Marks, T. J. J. Am. Chem. Soc. 2013, 135, 8830. doi: 10.1021/ja4039505
20. [20]
  McInnis, J. P.; Delferro, M.; Marks, T. J. Acc. Chem. Res. 2014, 47, 2545. doi: 10.1021/ar5001633
21. [21]
  Liu, S.; Motta, A.; Mouat, A. R.; Delferro, M.; Marks, T. J. J. Am. Chem. Soc. 2014, 136, 10460.
22. [22]
  Xu, S.; Jia, J.-J.; Huang, J.-L. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 4901. doi: 10.1002/pola.v45:21
23. [23]
  Xu, S.; Huang, J.-L. J. Appl. Polym. Sci. 2013, 2891.
24. [24]
  Mi, P.-K.; Xu, S.; Qu, L. D.; Zhang, D. S.; Qian, C.; Wang, S.-H. J. Appl. Polym. Sci. 2011, 121, 21. doi: 10.1002/app.v121.1
25. [25]
  Xu, S. M.S. Thesis, East China University of Science and Tehnology, Shanghai, 2000 (in Chinese).
26. [26]
  Sun, J.-Q.; Zhang, H.-Y.; Liu, X.-J.; Xiao, X.-H.; Lin, F. Eur. Polym. J. 2006, 42, 1259. doi: 10.1016/j.eurpolymj.2005.12.017
27. [27]
  Seger, M. R.; Maciel, G. E. Anal. Chem. 2004, 76, 5734. doi: 10.1021/ac040104i
28. [28]
  Liu, S.-F.; Motta, A.; Aidan, R. M.; Delferro, M.; Marks, T. J. J. Am. Chem. Soc. 2014, 136, 10460.
1. [1]
  Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce₄^ⅢCe₆^Ⅳ(μ₃-O)₄(μ₄-O)₄(acac)₁₄(CH₃O)₆]·2CH₃OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342
2. [2]
  Huijuan Liao , Yulin Xiao , Dong Xue , Mingyu Yang , Jianyang Dong . Synthesis of 1-Benzyl Isoquinoline via the Minisci Reaction. University Chemistry, 2025, 40(7): 294-299. doi: 10.12461/PKU.DXHX202409092
3. [3]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
4. [4]
  Hongling Yuan , Jialin Xie , Jiawei Wang , Jixiang Zhao , Jiayan Liu , Qing Feng , Wei Qi , Min Liu . Cyclic Olefin Copolymer (COC): The Agile Vanguard in the Realm of Materials. University Chemistry, 2024, 39(7): 294-298. doi: 10.12461/PKU.DXHX202311041
5. [5]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
6. [6]
  Chi Zhang , Yi Xu , Xiaopeng Guo , Zian Jie , Ling Li . 五彩斑斓的秘密——物质显色机理. University Chemistry, 2025, 40(6): 266-275. doi: 10.12461/PKU.DXHX202407061
7. [7]
  Xiaosong PU , Hangkai WU , Taohong LI , Huijuan LI , Shouqing LIU , Yuanbo HUANG , Xuemei LI . Adsorption performance and removal mechanism of Cd(Ⅱ) in water by magnesium modified carbon foam. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1537-1548. doi: 10.11862/CJIC.20240030
8. [8]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
9. [9]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
10. [10]
  Yuejiao An , Wenxuan Liu , Yanfeng Zhang , Jianjun Zhang , Zhansheng Lu . Revealing Photoinduced Charge Transfer Mechanism of SnO₂/BiOBr S-Scheme Heterostructure for CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(12): 2407021-. doi: 10.3866/PKU.WHXB202407021
11. [11]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
12. [12]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
13. [13]
  Zhen Yao , Bing Lin , Youping Tian , Tao Li , Wenhui Zhang , Xiongwei Liu , Wude Yang . Visible-Light-Mediated One-Pot Synthesis of Secondary Amines and Mechanistic Exploration. University Chemistry, 2024, 39(5): 201-208. doi: 10.3866/PKU.DXHX202311033
14. [14]
  Yi Li , Zhaoxiang Cao , Peng Liu , Xia Wu , Dongju Zhang . Revealing the Coloration and Color Change Mechanisms of the Eriochrome Black T Indicator through Computational Chemistry and UV-Visible Absorption Spectroscopy. University Chemistry, 2025, 40(3): 132-139. doi: 10.12461/PKU.DXHX202405154
15. [15]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
16. [16]
  Xudong Liu , Huili Fan , Junping Xiao , Min Yang , Yan Li . Teaching Approaches to the A_E + A_N Mechanism of Electrophilic Addition Reactions between Olefins and Inorganic Acids in Organic Chemistry. University Chemistry, 2025, 40(7): 367-372. doi: 10.12461/PKU.DXHX202409041
17. [17]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
18. [18]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
19. [19]
  Dongdong Yao , JunweiGu , Yi Yan , Junliang Zhang , Yaping Zheng . Teaching Phase Separation Mechanism in Polymer Blends Using Process Representation Teaching Method: A Teaching Design for Challenging Theoretical Concepts in “Polymer Structure and Properties” Course. University Chemistry, 2025, 40(4): 131-137. doi: 10.12461/PKU.DXHX202408125
20. [20]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(1018)
HTML views(142)

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