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考察了1-癸烯和不同结构的茂金属催化剂((η~5-C_5H_5)_2ZrC l_2,A;[μ,μ-(Me_2Si)_2(η~5-C_5H_3)_2][(η~5-C_5H_5)ZrC l_52)]2,B;[(C_6H_5)C(Me)_2(η~5-C_5H_4)]_2ZrC l_2,C;t BuN C(Me)_2(η-C_5H_4)ZrC l_2,D;(η-C_5H_4)C(C_5H_(10))(η~5-C_513H_8)ZrC l_2,E;(η~5-C_5H_4)C(Me)_2(η-C_(13)H_8)ZrC l_2,F;(η_5-C_5H_4)C(C_6H_5)_2(η~5-C_(13)H_8)ZrC l_2,G)/MAO的齐聚反应,并探讨了茂金属F的用量,聚合温度和Al/Zr比对聚合反应和齐聚物性能的影响.实验结果表明,由于其不同的位阻效应和电子效应,不同结构的茂金属对1-癸烯的催化活性和齐聚物组分分布影响显著.其中,Cp_2ZrCl_2,双核硅桥联的茂金属B和大位阻的茂金属C主要合成低粘度的齐聚物(100℃Kv:2~3 cS t,二聚体含量约为60%);限制构型的茂金属D因为有更加开放的配位结构呈现出高的催化活性,齐聚物的粘度也略高(100℃Kv:3~4 cS t);Cs-对称型茂金属E,F,G都有较高的催化活性,合成的齐聚物粘度也较高(100℃Kv>20cS t),主要归因于茂金属的特殊结构和聚合机理.GC-MS结果表明茂金属催化1-癸烯合成的齐聚物异构化较少,主要由二聚体到五聚体的混合物组成.茂金属F催化1-癸烯较优的齐聚条件是催化剂用量10μmol,聚合温度80℃,Al/Zr比300∶1.
The effects of 1-decene and different metallocene catalysts (η 5-C 5 H 5) 2 ZrCl 2, A, [μ, μ- (Me 2 Si) 2 (η 5-C 5 H 3) 2] C_5H_5) ZrCl_52)] 2, B; [(C_6H_5) C (Me) _2 (η_5_C_5H_4)] _2ZrC__2, C; t BuN C (Me) _2 (η_C_5H_4) ZrCl_2, D; (η_5_C_5H_4) C (Me) _2 (η_C_ (13) H_8) ZrC__2, F; (η_5_C_5H_4) C (C_5H_ (10)) (η_5-C_5H_4) C (C_6H_5) _2 (η ~ 5-C_ (13) H_8) ZrCl 2, G) / MAO was investigated. The effects of metallocene F content, polymerization temperature and Al / Zr ratio on the polymerization Reaction and oligomer properties.The experimental results show that due to different steric hindrance and electronic effect, the catalytic activity of 1-decene and the distribution of oligomer components of metallocene with different structures are significantly affected.Among them, Cp_2ZrCl_2 , Binuclear silicon bridged metallocene B and sterically hindered metallocene C mainly synthesize low-viscosity oligomers (100 ° C Kv: 2-3 cS t, dimer content about 60%); Metallocene D has a higher catalytic activity due to a more open coordination structure, and the viscosity of the oligomer is also slightly higher (100 ° C Kv: 3-4 cS t); Cs-symmetric metallocenes E, F, G A higher catalytic activity, the synthesis of oligomers also higher viscosity (100 ℃ Kv> 20cS t), which is mainly attributed to the special structure and polymerization mechanism of metallocene.GC-MS results show that metallocene-catalyzed oligomerization of 1-decene is less isomerization, To pentamers.More preferable oligomerization conditions of metallocene F for catalysis of 1-decene are catalyst dosage 10μmol, polymerization temperature 80 ℃ and Al / Zr ratio 300:1.