Preparation of Supported Silyl-Capped Silica-Bound Anion Activators and Associated Catalysts

Abstract

A method for the preparation of olefin polymerization catalysts that are the reaction products of the catalytic reaction of surface hydroxyls of a support with a trialkyl silane to afford hydrogen and the corresponding surface bound alkyl silyl ether and at the same time with a strong Lewis acid which support is converted to a silica bound anion that in a second step is fully converted by reaction with QM 2 to the desired catalyst. Catalyst compositions are disclosed herein. Processes disclosed herein include processes for the polymerization of olefinically unsaturated monomers comprising contacting a plurality of one or more of the monomers with the catalyst.

1 . A supported catalyst formed by a method comprising:
 reacting a metal oxide support selected from the group consisting of: silicas, fumed silicas, alumina, silica-alumina, magnesia, titania, zirconia, montmorillonites, phyllosilicates, zeolites, talc, clays, silica-chromium, silica-titania, aerogels, spherulites, and mixtures thereof, with at least one silane compound having the general formula: H x Si(R) 4−x , wherein x is at least 1; and R is a hydrido, alkyl, aryl, heteroalkyl, or heteroaryl ligand, in the presence of a first Lewis acid, thereby generating a silyl capped support;   reacting said silyl capped support with a second Lewis acid, which may be the same or different as said first Lewis acid, and an amine, thereby forming a supported silyl-capped silica-bound anion activator; and   reacting said supported silyl-capped silica-bound anion activator with at least one catalyst precursor, thereby forming said supported catalyst.   
     
     
         2 . The supported catalyst according to  claim 1 , wherein the reaction of said metal oxide support with said silane is catalyzed at a temperature in the range between 0 to 120° C. for a time period in the range between 0.1 to 10 hours. 
     
     
         3 . The supported catalyst according to  claim 1 , wherein the reaction of said metal oxide support with said silane is conducted in the presence of a solvent. 
     
     
         4 . The supported catalyst according to  claim 1 , wherein x is 2, 3, or 4. 
     
     
         5 . The supported catalyst according to  claim 1 , wherein said silane compound is trialkylsilane. 
     
     
         6 . The supported catalyst according to  claim 1 , wherein said silyl capped support comprises a trialkylsilyl content of between 1 to 99% of the available surface hydroxyl groups. 
     
     
         7 . The supported catalyst according to  claim 1 , wherein the reaction of said silyl capped support with a Lewis acid and said amine is conducted at temperature in the range between −80 to 150° C. for a time period in the range between 5 minutes to 24 hours. 
     
     
         8 . The supported catalyst according to  claim 1 , wherein the reaction of said silyl capped support with a Lewis acid and said amine is conducted in the presence of a solvent. 
     
     
         9 . The supported catalyst according to  claim 1 , wherein said first and/or second Lewis acid is an acid having the general formula:
   R x B(ArHal) 3−x,      
       where x can equal 0, 1, 2, or 3; R is a monoanionic ligand; B is boron; and ArHal is a halogenated C 6  aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly in which two or more rings or fused ring systems are joined directly to one another or together. 
     
     
         10 . The supported catalyst according to  claim 1 , wherein said amine is any amine that deprotonates a surface hydroxyl. 
     
     
         11 . The supported catalyst according to  claim 1 , wherein said supported silyl-capped silica-bound anion activator is a trialkylsilyl-capped silica-bound anion. 
     
     
         12 . The supported catalyst according to  claim 1 , wherein said metal oxide support is silica. 
     
     
         13 . The supported catalyst according to  claim 1 , wherein said catalyst precursor is chosen from any olefin polymerization catalyst precursor. 
     
     
         14 . The supported catalyst according to  claim 1 , wherein said support is chosen from: silica, fumed silica, alumina, silica-alumina, magnesia, titania, zirconia, silica-chromium, silica-titania, and mixtures thereof 
     
     
         15 .- 16 . (canceled) 
     
     
         17 . A method for the preparation of a supported silyl-capped silica-bound anion activator comprising:
 reacting a metal oxide support with at least one silane compound in the presence of a first Lewis acid, thereby generating a silyl capped support; and   reacting said silyl capped support with a second Lewis acid, which may be the same or different as said first Lewis acid, and an amine, thereby forming said supported silyl-capped silica-bound anion activator.   
     
     
         18 . The method according to  claim 17 , wherein said amine is any amine that deprotonates a surface hydroxyl. 
     
     
         19 . The method according to  claim 17 , wherein said supported silyl-capped silica-bound anion activator is trialkylsilyl-capped silica-bound anion. 
     
     
         20 . The supported catalyst according to  claim 1 , wherein all reactions are conducted in a single reaction vessel. 
     
     
         21 .- 22 . (canceled) 
     
     
         23 . The method according to  claim 17 , wherein all reactions are conducted in a single reaction vessel. 
     
     
         24 . The supported catalyst of  claim 1 , wherein the silane is selected from the group consisting of: methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, propylsilane, di(n-propyl)silane, tri(n-propyl)silane, phenylsilane, diphenylsilane, triphenylsilane, diethylphenylsilane, ethyldiphenylsilane, diethylperfluorophenylsilane, and trisperfluorophenylsilane. 
     
     
         25 . The supported catalyst of  claim 1 , wherein the catalyst precursor is selected from the group consisting of rac-dimethylsilyl-bis(indenyl)hafniumdimethyl,
 rac-dimethylsilyl-bis(indenyl)zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl) zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-benzindenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-benzindenyl) zirconiumdimethyl,   rac-dimethylsilyl-bis-(2-methyl-indenyl) zirconiumdimethyl,   rac-dimethylsilyl-bis-(2-methyl-indenyl) hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-naphthyl-indenyl) zirconiumdimethyl,   rac-ethylene-bis(indenyl)hafniumdimethyl,   rac-ethylene-bis(indenyl)zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(2′-methyl-phenyl)-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(2′-methyl-phenyl)-indenyl)zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(4′-methyl-phenyl)-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(4′-methyl-phenyl)-indenyl)zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl -phenyl)-indenyl)zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4-(4′-tert-butyl -phenyl)-indenyl)zirconiumdimethyl,   rac-dimethylsilyl-(2-methyl-4-(4′-tert-butyl-phenyl)-indenyl)(2-isoprpyl-4-(4′-tert-butyl-phenyl)-indenyl)hafniumdimethyl,   rac-dimethylsilyl-(2-methyl-4-(4′-tert-butyl -phenyl)-indenyl)(2-isoprpyl-4-(4′-tert-butyl-phenyl)-indenyl)zirconiumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)hafniumdimethyl,   rac-dimethylsilyl-bis(2-methyl-4,6-diisopropyl-indenyl)zirconiumdimethyl,   Bis(cyclopentadienyl)zirconiumdimethyl,   Bis(pentamethylcyclopentadienyl)zirconiumdimethyl,   Bis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,   Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl,   Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl,   Bis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide,   Bis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl,   Bis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl,   Bis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl,   Bis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl,   Bis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdimethyl,   Bis(1,3-dimethylcyclopentadienyl)zirconiumdimethyl,   Bis(n-propylcyclopentadienyl)zirconiumdimethyl,   Bis(n-propylcyclopentadienyl)zirconiumdiamide,   Bis(n-propylcyclopentadienyl)zirconiumdibenzyl,   Bis(n-propylcyclopentadienyl)hafniumdimethyl,   Bis(n-propylcyclopentadienyl)hafniumdiamide,   Bis(n-propylcyclopentadienyl)hafniumdibenzyl,   Bis(n-propylcyclopentadienyl)hafniumdimethoxide,   Bis(n-butylcyclopentadienyl)zirconiumdimethyl,   Bis(tert-butylcyclopentadienyl)zirconiumdimethyl,   Bis(benzylcyclopentadienyl)zirconiumdimethyl,   Bis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,   Bis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,   Bis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdimethyl,   Bis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl, Bis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(cyclopentadienyl)zirconiumdiamide,   Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdiamide,   Dimethylsilylbis(pentamethylcyclopentadienyl)zirconiumdibenzyl,   Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdiamide,   Dimethylsilylbis(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdibenzyl,   Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdiamide,   Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdimethoxide,   Dimethylsilylbis(1-methyl,4-butylcyclopentadienyl)zirconiumdibenzyl,   Dimethylsilylbis(1-methyl,4-ethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(1-methyl,4-benzylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(1-methyl,3-butylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(1-methyl,3-n-propylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(1-methyl,3-iso-propylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(1,3-dimethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(n-propylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(tert-butylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(benzylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(benzylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(propylcyclopentadienyl)(pentamethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconiumdimethyl,   Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(pentamethylcyclopentadienyl)-zirconiumdimethyl, and   Dimethylsilylbis(tetramethyl,propylcyclopentadienyl)(cyclopentadienyl)zirconiumdimethyl.   
     
     
         26 . The supported catalyst of  claim 1 , wherein the catalyst precursor is selected from the group consisting of: rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl)hafniumdimethyl, and rac-dimethylsilyl-bis(2-methyl-4-phenyl-indenyl) zirconiumdimethyl. 
     
     
         27 . The supported catalyst according to  claim 1 , wherein said amine is chosen from analine-type structures. 
     
     
         28 . The supported catalyst according to  claim 1 , wherein said amine is diethylanaline. 
     
     
         29 . The method of  claim 17 , wherein the metal oxide support is selected from the group consisting of: silica, fumed silica, alumina, silica-alumina, magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, silica-chromium, silica-titania, aerogels, spherulites, and mixtures thereof, and the silane compound has the general formula: H x Si(R) 4−x , wherein x is at least 1; and R is a hydrido, alkyl, aryl, heteroalkyl, or heteroaryl ligand. 
     
     
         30 . The method according to  claim 17 , wherein the reaction of said metal oxide support with said silane is catalyzed at a temperature in the range between 0 to 120° C. for a time period in the range between 0.1 to 10 hours. 
     
     
         31 . The method according to  claim 17 , wherein the reaction of said metal oxide support with said silane is conducted in the presence of a solvent. 
     
     
         32 . The method according to  claim 29 , wherein x is 2, 3, or 4. 
     
     
         33 . The method according to  claim 17 , wherein said silane compound is trialkylsilane. 
     
     
         34 . The method according to  claim 17 , wherein said silyl capped support comprises a trialkylsilyl content of between 1 to 99% of the available surface hydroxyl groups. 
     
     
         35 . The method according to  claim 17 , wherein the reaction of said silyl capped support with a Lewis acid and said amine is conducted at temperature in the range between −80 to 150° C. for a time period in the range between 5 minutes to 24 hours. 
     
     
         36 . The method according to  claim 17 , wherein the reaction of said silyl capped support with a Lewis acid and said amine is conducted in the presence of a solvent. 
     
     
         37 . The method according to  claim 17 , wherein said first and/or second Lewis acid is an acid having the general formula:
   R x B(ArHal) 3−x ,   
       where x can equal 0, 1, 2, or 3; R is a monoanionic ligand; B is boron; and ArHal is a halogenated C 6  aromatic or higher carbon number polycyclic aromatic hydrocarbon or aromatic ring assembly in which two or more rings or fused ring systems are joined directly to one another or together. 
     
     
         38 . The method according to  claim 17 , wherein said metal oxide support is silica. 
     
     
         39 . The method of  claim 17 , wherein the silane is selected from the group consisting of: methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, propylsilane, di(n-propyl)silane, tri(n-propyl)silane, phenylsilane, diphenylsilane, triphenylsilane, diethylphenylsilane, ethyldiphenylsilane, diethylperfluorophenylsilane, and trisperfluorophenylsilane.