TH54092A - Supporting polymerization catalyst - Google Patents

Abstract

DC60 (05/10/44) Supported charged metallocene catalyst systems can be prepared by a method that includes the following steps: (i) mixing the following compounds in a suitable solvent: (a) organometallic compounds, and (b) charged catalysts consisting of cations and anions; (ii) adding the mixture from step (i) to the supporter; (iii) adding the metallocene complex to the suitable solvent; (iv) adding further organometallic compounds to the suitable solvent; and (v) removing the solvent. Commonly preferred supported catalysts are those with stressed molecular structures, such as, for example, (t-butylamido) (tetramethyl--5-cyclopentadienne) dimethyl silane titanium--4-1,3-pentadiene and is particularly suitable for the polymerization of ethylene or the copolymerization of ethylene and alpha-olefins with 3 to 10 carbon atoms in the gaseous phase. The supported metallocene catalyst of this invention shows improved yield compared to conventional supported charged metallocene catalyst systems, especially when used in the gaseous phase. Supported charged metallocene catalyst systems can be prepared by methods in which The process involves the following steps: (i) mixing the following compounds in a suitable solvent: (a) organometallic compounds, and (b) charged catalysts containing both cations and anions; (ii) adding the mixture from step (i) to the supporter; (iii) adding the metallocene complex to the suitable solvent; (iv) adding further organometallic compounds to the suitable solvent; and (v) removing the solvent. The preferred supported catalysts are often stressed metallocene complexes, such as (t-butylamido)(tetramethyl-5-cyclopentadienne)dimethyl silane titanium-4-1,3-pentadiene, which are particularly suitable for polyphenolic production. The morization of ethylene, or the copolymerization of ethylene and alpha-olephine with 3 to 10 carbon atoms in the gaseous phase, is performed using this invention's supported metallocene catalyst, which exhibits improved yield compared to conventional supported charged metallocene catalyst systems, particularly when used in the gaseous phase.

Claims (18)

1. A method for preparing a supported metallocene catalytic system, which includes the following steps: (i) mixing the following compounds in a suitable solvent: (a) organometallic compounds, and (b) charged catalysts containing both cations and anions; (ii) adding the mixture from step (i) to the support; (iii) adding the metallocene complex to the suitable solvent; (iv) adding additional organometallic compounds to the suitable solvent; and (v) removing the solvent. 2. The method to comply with claim 1, where the organometallic compounds used in step (i) are organoaluminum compounds. 3. The method to fulfill claim number 2, where the organoaluminum compound is a trialkyl aluminum compound. 4. A method for fulfilling any one of the preceding claims where the charged cation of the catalyst consists of hydrocarbil substituted ammonium salt and the anion consists of aryl substituted borate. 5. A method pursuant to one of the preceding claims whereby a charged activator shall consist of a cation and an anion, whereby the anion shall contain at least one substituent group which includes a molecular group containing a reactive hydrogen. 6. The method under claim number 5, where the charged catalyst is alkylaluminum tris(pentafluorophenyl)4-(hydroxyphenyl)borate. 7. The method under claim number 6, where the charged catalyst is bis-(hydrogenated tallow alkyl)methyl ammonium tris(pentafluorophenyl)(4-hydroxyphenyl) borate. 8. The method under claim 1, where the supporting substance is an inorganic oxide. 9. The method under claim number 8, where the inorganic oxide is silica. 10. The method under claim 9, where the silica has been pretreated with organometallic compounds. 11. The method under claim 1, where the metallocene complex is a complex with a stressed molecular structure. 12. According to claim 1, the metallocene complex has the general formula: (chemical formula) where R' is an independent group chosen from hydrogen, hydrocarbil, silyl, germyl, halo, cyano groups and their combinations, with R' containing up to 20 non-hydrogen atoms, and in some cases two R' groups (where R' is not hydrogen, halo, or cyano) are combined in the form of a derivative with two valences of the groups connected at adjacent positions of the cyclopentadienyl ring to form a fused molecular structure. X is a diene group connected at the 4th bond at the center containing up to 30 non-hydrogen atoms, which will result in It is a complex compound with metal M; Y is -O-, -S-, -NR*-, -PR*-, M is titanium or zirconium under normal oxidation conditions -2-: Z* is Sir*2, CR*2, SiR*2, SiR*2, CR*2, CR*2, CR* = CR*, 2SiR*, or GeR*2, where the R* group formation is independent of each other, being hydrogen or a selected member from hydrocarbil, silyl, halogenated alkyl, halogenated aryl groups, and combinations of those groups. R* can have up to 10 non-hydrogen atoms, and in some cases, two R* groups from Z* (when R* is not hydrogen) or an R* group from Z* and an R* group from Y will form a ring system. 13. The method under claim number 12, where metal M is titanium. 14. The method pursuant to claim No. 13, whereby the metallocene complex is (t-butylamido)(tetramethyl-5-cyclopentadienne)dimethylsilane titanium-4-1,3-pentadienne 15. The method under any of the preceding claims, where the molar ratio of the complex to the charged catalyst is in the range of 1:10,000 to 100:1. 16. The method under claim 15, where the Mylar ratio is in the range of 1:10 to 10:1. 17. A procedure for the polymerization of ethylene or the copolymerization of ethylene and alpha-ilefins with 3 to 10 carbon atoms, which is carried out under polymerization conditions with the participation of a metallocene-supported catalytic system prepared according to one of the prior claims. 18. The procedures under claim 17 were implemented in the gas phase.