Supported metallocene catalyst and preparation and application thereof

Abstract

The invention relates to a supported metallocene catalyst and a preparation and application thereof. Activated SiO2 reacts with halogenosilane containing double bond to obtain functional SiO2 solid; the adding amount of unsaturated double bond halogenosilane is calculated according to the content of surface hydroxyls of the activated SiO2; the mol ratio of halogenosilane to surface hydroxyls of SiO2 is (10000:1)-(1:10000); the functional SiO2 reacts with aluminiferous organic metal compound; then the solution of a metallocene compound is added into the reaction system to react to obtain the solid catalyst by solution removing, washing and decompressing and extracting after reaction. Central atoms Ti, Zr or Hf of the metallocene compound accounts for 0.01-50% of carrier weight by weight percent. The catalyst is suitable for gas phase method, solution method, slurry packing method and bulk polymerization process, is not adhered to the kettle and has good stability when used for synthesizing homopolymers and copolymers of polyethylene.

Description

technical field [0001] The invention relates to a supported metallocene catalyst and its preparation and application. Background technique [0002] Metallocene catalyst support means that the metallocene catalyst is supported on SiO by physical or chemical methods. 2 , MgCl 2 , molecular sieve, clay, Al 2 o 3 and other inorganic carriers, or supported on organic carriers such as styrene polymers. At present, the most widely used and industrialized supported metallocene catalyst is SiO 2 Supported metallocene catalysts. SiO 2 There are three loading methods for supported metallocene catalysts: the first loading method is to directly load metallocene compounds on SiO 2 (WKaminsky, Makromol.Chem.Rapid Commun., 1993, 14:239, WO9632423), but because the metallocene ligand can react with the hydroxyl on the carrier to make the ligand fall off, resulting in a reduction in catalyst activity and a complication of the reaction ; The second loading method is the indirect loadin...

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Problems solved by technology

SiO 2 There are three loading methods for supported metallocene catalysts: the first loading method is to directly load metallocene compounds on SiO 2 (WKaminsky, Makromol.Chem.Rapid Commun., 1993, 14:239, WO9632423), but because the metallocene ligand can react with the hydroxyl on the carrier to make the ligand fall off, resulting in a reduction in catalyst activity and a complication of the reaction ; The second loading method is the indirect loading of metallocene compounds on SiO through MAO or alkylaluminum 2 (US6153551, US5240894, US4937217, US4912075, US4935937, etc.), the advantages of this type of catalyst are high activity, the nature of the carrier has little influence on the metallocene, the carrier generally has no regulatory effect on the microstructure of the polymer, and during polymerization It can reduce the amount of MAO, which is a more commonly used loading method; the third method is to synthesize metallocene complexes in situ on the carrier, and the preparation and loading of metallocenes are carried out at the same time. Typical patents such as EP708116 describe that gasified Zirconium tetrachloride (ZrCl 4 ) at a temperature of 160 ~ 450 ° C to contact and load the carrier, and then the loaded ZrCl 4 React with the lithium salt of the ligand, and finally cooperate with the co-catalyst for polymerization. This loading process requires high temperature and high vacuum and is not suitable for industrial production.

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