Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands  

作　　者：Vladislav A.Tuskaev Kasim F.Magomedov Svetlana Ch.Gagieva Dmitry A.Kurmaev Yulia V.Nelyubina Evgenii K.Golubev Maria D.Evseeva Viktor G.Vasil'ev Galina G.Nikiforova Mikhail I.Buzin Vyacheslav S.Bogdanov Boris M.Bulychev 

机构地区：[1]Department of Chemistry,M.V.Lomonosov Moscow State University,Moscow 119992,Russian Federation [2]A.N.Nesmeyanov Institute of Organoelement Compounds,Russian Academy of Sciences,Moscow119991,Russian Federation [3]Enikolopov Institute of Synthetic Polymer Materials,Russian Academy of Sciences,Moscow 117393,Russian Federation

出　　处：《Chinese Journal of Polymer Science》2024年第1期52-62,I0007,共12页高分子科学（英文版）

基　　金：supported by the Russian Science Foundation (No.22-23-00578);the financial support from the Ministry of Science and Higher Education of the Russian Federation using the equipment of Center for molecular composition studies of INEOS RAS (No.075-00697-22-00);the financial support of the Ministry of Science and Higher Education of the Russian Federation employing the equipment of Center for molecular composition studies of INEOS RAS。

摘　　要：A series of Ti(Ⅳ) dichloride and dialkoxide com plexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been synthesized.The molecular structures of complexes 1 and 4 were established by single-crystal X-ray diffraction studies.The complexes adopt a distorted octahedral coordination structure around the titanium atom and two oxygen atoms are situated in trans position while two nitrogen atoms and two outgoing ligands(Cl or iPrO) are situated in cis position.Effect of activators(MMAO-12 and combinations Et_nAICl_(3-n)+Bu_(2)Mg) and outgoing ligand(Cl or iPrO) nature on the catalytic activity and properties of the resulting polymers was studied.The Ti complexes,despite the nature of the outgoing ligands(Cl or iPrO) in the presence of Al/Mg activators,was found to display a high ethylene polymerization activity in the range 1600-3830 kg_(polymer)·mol_(Ti)^(-1)·h^(-1)·atm^(-1) with a viscosity average molecular weight(M_v) value in the range 1.1×10~6-7.1×10~6 Dalton(Da).The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented films.The rheological characteristics of a polymer melt have been studied.The absence of a cross-over point did not allow to compare the values of the molecular weight distribution of polymers obtained on fluorinated and non-fluorinated pre-catalysts,however,the estimation of the entanglement density is in good agreement with the mechanical characteristics of oriented film s.Upon activation with methylalumoxane,the activity of the com plexes decreased very significantly;however,a polymer with a molecular weight of about 12 million Da was obtained.In the process of ethylene/octene-1 copolymerization,fluorine-containing precatalysts showed a clear advantage over non-fluorinated analogues both in activity and in comonomer content.

关 键 词：FI catalysts Titanium(IV) (Co)polymerization Al/Mg co-catalyst Ultra-high molecular weight polyethylene 

分 类 号：O641.4[理学—物理化学]