Silica supported transition metal catalysts

Claim 2

A supported transition metal catalyst component which comprises an inert liquid medium having slurried therein a composition comprising the unwashed. undecanted product resulting from contacting (1) a porous solid inorganic oxide support material selected from the group consisting of silica, alumina, or a combination of silica and alumina, said support material containing not greater than about 5 millimoles of hydroxyl groups per gram of support material and a particle size not greater than about 10 microns and a surface area of from about 50 to about 800 m 2 /g; (2) an organomagnesium alkoxide or dialkoxide represented by the formula R x Mg(OR) y wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms: x+y=2; and 0.5≦y≦2; (3) a titanium compound; optionally (4) a vanadium compound; and (5) a Group IIIA metal alkyl halide: and wherein the components are employed in amounts which provide the following atomic ratios: Si+Al (from the inorganic oxide support):Mg of from about 1:1 to about 50:1; Mg:IIIA metal of from about 0.01:1 to about 100:1; Mg:Ti of from about 0.05:1 to about 40:1; Mg:V, when present, of from about 0.1:1 to about 40:1; V:Ti of from about 0:1 to about 10:1.

Claim 3

A catalyst of claim 1 wherein (a) said solid support material contains not greater than about 4 millimoles of hydroxyl groups per gram of support material, has a particle size of from about 0.1 to about 10 microns and a surface area of from about 50 to about 800 m 2 /g; (b) said transition metal catalyst contains an atomic ratio of Si+Al (from the inorganic support):Mg of from about 2:1 to about 40:1; (c) said transition metal catalyst contains an atomic ratio of Mg:Ti of from about 0.1:1 to about 20:1; (d) said transition metal catalyst contains an atomic ratio of Mg:V of from about 0.1:1 to about 20:1; (e) said transition metal catalyst contains an atomic ratio of Mg:IIIA metal of from about 0.05:1 to about 10:1; and (f) said transition metal catalyst contains an atomic ratio of V:Ti of from about 0.1:1 to about 10:1.

Claim 4

A catalyst of claim 1 wherein (a) said solid support material contains not greater than about 3 millimoles of hydroxyl groups per gram of support material, has a particle size of from about 1 to about 8 and a surface area of from about 150 to about 600 m 2 /g; (b) said transition metal catalyst contains an atomic ratio of Si+Al:Mg of from about 4:1 to about 20:1; (c) said transition metal catalyst contains an atomic ratio of Mg:Ti of from about 0.2:1 to about 10:1; (d) said transition metal catalyst contains an atomic ratio of Mg:V of from about 0.2:1 to about 10:1; (e) said transition metal catalyst contains an atomic ratio of Mg:IIIA metal of from about 0.1:1 to about 5:1; and (f) said transition metal catalyst contains an atomic ratio of V:Ti of from about 0.2:1 to about 5:1.

Claim 5

A catalyst of claim 1, 2 or 3 wherein (a) said solid support material is silica; (b) said titanium compound is a compound represented by the formula TiX 4-a (OR') a wherein each R' is independently an alkyl group having from 1 to about 20 carbon atoms, X is a halogen atom, and a has a value from zero to 4; (c) said vanadium compound, when present, is a compound represented by the formulas VX 4 or wherein each R' is independently an alkyl group having from 1 to about 20 carbon atoms, X is a halogen atom, and a has a value from zero to 4; and (d) said Group IIIA metal alkyl halide is a compound represented by the formula R' y MX z wherein M is a metal from Group IIIA of the Periodic Table of the Elements, each R' is independently an alkyl group having from 1 to about 20 carbon atoms; X is a halogen atom, y and z each independently have a value from 1 to a value equal to the valence of M minus 1 and y+z has a value equal to the valence of M.

Claim 6

A catalyst of claim 1, 2 or 3 wherein (a) said solid support material is silica; (b) said magnesium compound is ethylmagnesium ethoxide, butylmagnesium ethoxide, octylmagnesium ethoxide, butylmagnesium butoxide, ethylmagnesium butoxide, butylmagnesium octoxide, s-butylmagnesium octoxide or any combination of such compounds; ( c) said titanium compound is titanium tetrachloride, titanium tetraisopropoxide, or any combination of such compounds; (d) said vanadium compound, when present, is vanadium tetrachloride, vanadium oxytrichloride, or any combination of such compounds; and (e) said Group IIIA metal alkyl halide is ethylaluminum dichloride, i-butylaluminum dichloride, ethylaluminum sesquichloride or any combination thereof.

Claim 7

A process for preparing a supported transition metal catalyst component slurried in an inert liquid medium, which process comprises (A) forming in an inert atmosphere which excludes oxygen and moisture a slurry of (1) a porous inorganic oxide support material selected from the group consisting of silica, alumina, or a combination of silica and alumina, said support material containing not greater than about 5 millimoles of hydroxyl groups per gram of support material and a particle size not greater than about 10 microns and a surface area of from about 50 to about 800 m 2 /g in an inert organic liquid medium; (B) mixing said slurry with (2) a hydrocarbon soluble organomagnesium alkoxide or hydrocarbon soluble magnesium dialkoxide represented by the formula R x Mg(OR) y wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; x+y=2; and 0.5≦y≦2 and stirring the resultant mixture at a temperature of from about -20° C. to about 120° C. for a time sufficient to saturate the surface of the support material; (C) mixing the product from (B) with (3) a titanium compound or a combination of a titanium compound and (4) a vanadium compound or adding the titanium compound and the vanadium compound separately and stirring the resultant mixture at a temperature of from about -20° C. to about 120° C. for a time sufficient to allow complete reaction of the titanium compound and the vanadium compound with the organomagnesium moieties remaining on the solid support; (D) mixing the product from (C) with an inert organic solution of (5) a Group IIIA metal alkyl halide at a temperature of from about -20° C. to about 120° C. for a time sufficient to complete the reduction of the titanium and vanadium, if present, compounds to their final oxidation state.

Claim 8

A process for preparing a supported transition metal catalyst component slurried in an inert liquid medium, which process comprises (A) forming in an inert atmosphere which excludes oxygen and moisture a slurry of (1) a porous inorganic oxide support material selected from the group consisting of silica, alumina, or a combination of silica and alumina, said support material containing not greater than about 5 millimoles of hydroxyl groups per gram of support material and a particle size not greater than about 10 microns and a surface area of from about 50 to about 800 m 2 /g in an inert organic liquid medium; (B) mixing said slurry with (2) a hydrocarbon soluble organomagnesium alkoxide or hydrocarbon soluble magnesium dialkoxide represented by the formula R x Mg(OR) y wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; x+y=2; and 0.5≦y≦2 and stirring the resultant mixture at a temperature of from about -20° C. to about 120° C. for a time sufficient to saturate the surface of the support material; (C) mixing the product from (B) with (3) a titanium compound or a combination of a titanium compound and (4) a vanadium compound or adding the titanium compound and the vanadium compound separately and stirring the resultant mixture at a temperature of from about -20° C. to about 120° C. for a time sufficient to allow complete reaction of the titanium compound and the vanadium compound with the organomagnesium moieties remaining on the solid support; (D) mixing the product from (C) with an inert organic solution of (5) a Group IIIA metal alkyl halide at a temperature of from about -20° C. to about 120° C. for a time sufficient to complete the reduction of the titanium and vanadium, if present, compounds to their final oxidation state.

Claim 9

A process of claim 6 wherein (a) step A is conducted at a temperature of from about 0° C. to about 100° C.; (b) step B is conducted at a temperature of from about 0° C. to about 100° C.; (c) step C is conducted at a temperature of from about 0° C. to about 100° C.; (d) step D is conducted at a temperature of from about 0° C. to about 100° C.; (e) said solid support material contains not greater than about 4 millimoles of hydroxyl groups per gram of support material, a particle size of from about to about 8 microns and a surface area of from about 150 to about 600 m 2 /g; (f) said transition metal catalyst contains an atomic ratio of Si+Al (from the inorganic support):Mg of from about 2:1 to about 40:1; (g) said transition metal catalyst contains an atomic ratio of Mg:Ti of from about 0.1:1 to about 40:1; (h) said transition metal catalyst contains an atomic ratio of Mg:V, when present, of from about 0.1:1 to about 40:1; (i) said transition metal catalyst contains an atomic ratio of Mg:IIIA metal of from about 0.01:1 to about 100:1; and (j) said transition metal catalyst contains an atomic ratio of V:Ti of from about 0:1 to about 10:1.

Claim 10

A process of claim 6 wherein (a) step A is conducted at a temperature of from about 20° C. to about 70° C.; (b) step B is conducted at a temperature of from about 20° C. to about 70° C.; (c) step C is conducted at a temperature of from about 20° C. to about 70° C.; (d) step D is conducted at a temperature of from about 20° C. to about 70° C.; (e) said solid support material contains not greater than about 3 millimoles of hydroxyl groups per gram of support material, a particle size of from about 2 to about 8 microns and a surface area of from about 300 to about 500 m 2 /g; (f) said transition metal catalyst contains an atomic ratio of Si+Al (from the inorganic oxide support):Mg of from about 4:1 to about 20:1; (g) said transition metal catalyst contains an atomic ratio of Mg:Ti of from about 0.5:1 to about 10:1; (h) said transition metal catalyst contains an atomic ratio of Mg:V, if present, of from about 0.5:1 to about 10:1; (i) said transition metal catalyst contains an atomic ratio of Mg:IIIA metal of from about 0.1:1 to about 5:1; and (j) said transition metal catalyst contains an atomic ratio of V:Ti of from about 0:1 to about 1:1.

Claim 11

A process of claim 6, 7 or 8 wherein (a) said solid support material is silica; (b) said titanium compound is a compound represented by the formula TiX 4-a (OR') a wherein each R' is independently an alkyl group having from 1 to about 20 carbon atoms, X is a halogen atom, and a has a value from zero to 4; (c) said vanadium compound, when present, is a compound represented by the formula VX 4-a (OR) a wherein each R' is independently an alkyl group having from 1 to about 20 carbon atoms, X is a halogen atom, and a has a value from zero to 4; and (d) said Group IIIA metal alkyl halide is a compound represented by the formula R' y MX z wherein M is a metal from Group IIIA of the Periodic Table of the Elements, each R' is independently an alkyl group having from 1 to about 20 carbon atoms; X is a halogen atom, y and z each independently have a value from 1 to a value equal to the valence of M minus 1 and y+z has a value equal to the valence of M.

Claim 12

A process of claim 6, 7 or 8 wherein (a) said magnesium compound is ethylmagnesium ethoxide, butylmagnesium ethoxide, octylmagnesium ethoxide, butylmagnesium butoxide, ethylmagnesium butoxide, butylmagnesium octoxide, s-butylmagnesium octoxide or any combination of such compounds; (b) said titanium compound is titanium tetrachloride, titanium tetraisopropoxide, or any combination of such compounds; (c) said vanadium compound, when present is vanadium tetrachloride, vanadium oxytrichloride, or any combination of such compounds; and (d) said Group IIIA metal alkyl halide is ethylaluminum dichloride, i-butylaluminum dichloride, ethylaluminum sesquichloride or any combination of such compounds.