Copolymerization of ethylene with cycloolefins by titanium complexes containing tridentate [o−NSR] ligands |
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| Authors: | Ming‐Li Gao Xiu‐Li Sun Yue‐Feng Gu Xiao‐Li Yao Chuan‐Feng Li Ji‐Ye Bai Cong Wang Zhi Ma Yong Tang Zuowei Xie Shi‐Zheng Bu Changtao Qian |
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| Institution: | 1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China;2. Research Institute of Yangzi Petrochemical Co. Ltd., Dachang, Nanjing, 210048, China;3. Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China |
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| Abstract: | A family of titanium complexes of the general formula N‐(3,5‐di‐tert‐butylsalicylidene)‐2‐alkylsulfanylanilinato]Ti(IV)Cl3 5a – f was prepared from the reaction of TiCl4 with the potassium salts of the corresponding ligands. These complexes were fully characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 5b and 5e were further confirmed by single‐crystal X‐ray analyses. Complexes 5a – f (except for 5c ) exhibited good to high catalytic activities in ethylene copolymerization with cycloolefins such as norbornene, cyclopentene, dicyclopentadiene in the presence of modified methylaluminoxane. The reaction conditions and the steric hindrance of the alkyl substituents on sulfur atom in the precatalysts influenced strongly the copolymerization behaviors and the structures of the resultant copolymers. Complex 5c with bulky tert‐butylthio sidearm showed both low catalytic activity and comonomer incorporation ratio. The n‐alkylthio complexes 5a , 5d – f all exhibited good ethylene copolymerization capabilities with cycloolefins, which is superior to the corresponding phenylthio complex 5g . © 2008 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 46: 2807–2819, 2008 |
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| Keywords: | catalysis catalyst copolymerization polyolefins synthesis |
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