Process for polymerizing olefins employing a catalyst prepared from organomagnesium compound; oxygen- or nitrogen- containing compound; halide source; transition metal compound and reducing agent

Claim 2

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble product resulting from the admixture of: (I) the reaction product of (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof such components represented by the formula MgR 2 .xMeR' x' , wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R 1 is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms Me is Al, Zn or B, x has a value of from zero to 10 and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently a hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4, Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined above; z-n has a value from zero up to the valence of Tm in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (III) a suitable reducing agent or mixture of reducing agents represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is independently a halogen, a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms each; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; with the proviso that when component (I-B), the halide source, contains a sufficient quantity of transition metal to satisfy the Mg:Tm ratio, then component (II) may be omitted.

Claim 3

The process of claim 1 wherein in component (A-1) each R and R' group is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms; Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates, glycols, alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; the halide source is represented by the formulas AlR 3-a X a or TmY n X z-n ; in component (II) Y is OR"; the reducing agent is represented by the formula AlR 3 3-m X m ; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1; and wherein said cocatalyst contains aluminum.

Claim 4

The process of claim 2 wherein R and R' and the value of x are such that the organo magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; the halide source is TiCl 4 ; component (II) is omitted; in the formula for the reducing agent each R 3 is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing agent is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 5

The process of claim 3 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 6

The process of claim 4 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination.

Claim 7

The process of claim 5 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol.

Claim 8

The process of claim 1 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 9

The process of claim 7 wherein component (A-2) is ammonia or an amine.

Claim 10

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble reaction product of: (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, x' has a value equal to the valence of Me, and (2) a transition metal free oxygen-containing and/or a transition metal free nitrogen-containing compound in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a ; wherein R 3 is independently hydrogen or the same definition as R above, X is defined above and a has a value of from 1 to less than 3; said halide being employed in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide atom and such that the R 3 :Tm ratio is from about 1:1 to about 50:1; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B or VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1.

Claim 11

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble reaction product of: (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, x' has a value equal to the valence of Me, and (2) a transition metal free oxygen-containing and/or a transition metal free nitrogen-containing compound in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a ; wherein R 3 is independently hydrogen or the same definition as R above, X is defined above and a has a value of from 1 to less than 3; said halide being employed in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide atom and such that the R 3 :Tm ratio is from about 1:1 to about 50:1; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B or VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1.

Claim 12

The process of claim 9 wherein in component (A-1), each R and R' group is independently an aliphatic hydrocarbon having from 1 to about 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from, acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates and glycols, alcohols, aldehydes, ketones, carboxylic acids, or mixture thereof in any combination; in component (C), Y is OR"; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing halide is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1; and wherein said cocatalyst contains aluminum.

Claim 13

The process of claim 10 wherein R and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; the halide source is diethylaluminum chloride or ethylaluminum dichloride; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value of from zero to 2; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing halide is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 14

The process of claim 11 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 15

The process of claim 12 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixtures thereof.

Claim 16

The process of claim 13 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol.

Claim 17

The process of claim 9 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 18

The process of claim 15 wherein component (A-2) is ammonia, an amine, an isocyanate or mixture thereof in any combination.

Claim 19

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst; the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture of complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10; and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4; Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) recovering the resultant hydrocarbon insoluble product, washing said product with fresh inert diluent; and (III) mixing, in fresh inert diluent, the product from (II) with (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined as above; z-n has a value of from zero up to the valence of Tm; in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; (IV) reacting the product from (III) with (D) a suitable reducing agent or mixture of reducing agents selected from compounds represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is a halogen or a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; and (V) recovering and washing with fresh inert diluent the resultant solid hydrocarbon insoluble catalyst produced in step IV.

Claim 20

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst; the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture of complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10; and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4; Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) recovering the resultant hydrocarbon insoluble product, washing said product with fresh inert diluent; and (III) mixing, in fresh inert diluent, the product from (II) with (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined as above; z-n has a value of from zero up to the valence of Tm; in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; (IV) reacting the product from (III) with (D) a suitable reducing agent or mixture of reducing agents selected from compounds represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is a halogen or a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; and (V) recovering and washing with fresh inert diluent the resultant solid hydrocarbon insoluble catalyst produced in step IV.

Claim 21

The process of claim 17 wherein in component (A-1), each R and R' group is independently an aliphatic hydrocarbon having from 1 to about 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from, acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; the halide source is represented by the formulas AlR 3-a X a or TmY n X z-n ; in component (C) Y is OR"; the reducing agent is represented by the formula AlR 3 3-m X m ; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1; and wherein said cocatalyst contains aluminum.

Claim 22

The process of claim 18 wherein R, R' and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, and carboxylic acids or mixture thereof in any combination; the halide source is represented by the formula TiCl 4 ; component (C) is TiCl 4 in the formula for the reducing agent each R 3 is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing agent is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 23

The process of claim 19 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; the component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 24

The process of claim 20 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination.

Claim 25

The process of claim 21 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or mixture thereof in any combination.

Claim 26

The process of claim 17 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 27

The process of claim 23 wherein component (A-2) is ammonia or an amine.

Claim 28

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10 and x' has a value equal to the valence of Me; with (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of 25° C.; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a wherein each X is independently a halogen atom; R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and a has a value of from 1 to less than 3; said halide being employed in a quantity such that the R 3 :Tm ratio is from about 1:1 to about 50:1 and to provide a sufficient amount of halogen atoms to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (II) recovering and washing with fresh inert diluent the resultant solid, hydrocarbon insoluble catalyst.

Claim 29

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10 and x' has a value equal to the valence of Me; with (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of 25° C.; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a wherein each X is independently a halogen atom; R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and a has a value of from 1 to less than 3; said halide being employed in a quantity such that the R 3 :Tm ratio is from about 1:1 to about 50:1 and to provide a sufficient amount of halogen atoms to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (II) recovering and washing with fresh inert diluent the resultant solid, hydrocarbon insoluble catalyst.

Claim 30

The process of claim 25 wherein in component (A-1), each R and R' group is independently an aliphatic hydrocarbon having from 1 to about 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from, acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; in component (C), Y is OR"; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing halide is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1.

Claim 31

The process of claim 26 wherein R and R' and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, and carboxylic acids or mixture thereof in any combination; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value of from zero to 2; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing halide is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 32

The process of claim 27 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 33

The process of claim 28 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination.

Claim 34

The process of claim 31 wherein said alcohol is selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or mixture thereof in any combination.

Claim 35

The process of claim 25 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 36

The process of claim 31 wherein component (A-2) is ammonia or an amine.

Claim 37

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble product resulting from the admixture of: (I) the reaction product of (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof such components represented by the formula MgR 2 .xMeR' x' , wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms Me is Al, Zn or B, x has a value of from zero to 10 and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (II); Y is oxygen, OR" or NR" 2 , each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component II, atomic ratio is from 0.01:1 to about 0.5:1; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently a hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4, Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined above; z-n has a value from zero up to the valence of Tm in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (III) a suitable reducing agent or mixture of reducing agents represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is independently a halogen, a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms each; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; with the proviso that when component (I-B), the halide source, contains a sufficient quantity of transition metal to satisfy the Mg:Tm ratio, then component (II) may be omitted.

Claim 38

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble product resulting from the admixture of: (I) the reaction product of (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof such components represented by the formula MgR 2 .xMeR' x' , wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms Me is Al, Zn or B, x has a value of from zero to 10 and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (II); Y is oxygen, OR" or NR" 2 , each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component II, atomic ratio is from 0.01:1 to about 0.5:1; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently a hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; each R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4, Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined above; z-n has a value from zero up to the valence of Tm in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (III) a suitable reducing agent or mixture of reducing agents represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is independently a halogen, a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms each; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; with the proviso that when component (I-B), the halide source, contains a sufficient quantity of transition metal to satisfy the Mg:Tm ratio, then component (II) may be omitted.

Claim 39

The process of claim 33 wherein in component (A-1) each R and R' group is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms; Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates, glycols, alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; in component (A-2) Tm' is Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine and the atomic ratio of Tm':Tm is from about 0.02:1 to about 0.2:1; the halide source is represented by the formulas AlR 3-a X a or TmY n X z-n ; in component (II) Y is OR"; the reducing agent is represented by the formula AlR 3 3-m X m ; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1; and wherein said cocatalyst contains aluminum.

Claim 40

The process of claim 34 wherein R and R' and the value of x are such that the organo magnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones and carboxylic acids or mixture thereof in any combination; said transition metal compound represented by the formula Tm'Y n X z-n is NiCl 2 , NiCl 2 .6H 2 O, FeCl 3 , FeCl 3 .6H 2 O, CrCl 3 , CrCl 2 , CrCl 3 .6H 2 O, MoCl 5 , WCl 6 , ZrCl 4 , Zr(O-iC 3 H 7 ) 4 , VOCl 3 or mixture thereof in any combination; the halide source is TiCl 4 ; component (II) is omitted; in the formula for the reducing agent each R 3 is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing agent is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 41

The process of claim 35 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 42

The process of claim 36 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination.

Claim 43

The process of claim 37 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol.

Claim 44

The process of claim 33 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 45

The process of claim 39 wherein component (A-2) is ammonia or an amine.

Claim 46

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 of mixtures thereof wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble reaction product of: (A) The reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing and/or a transition metal free nitrogen-containing compound in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component (C), atomic ratio is from 0.01:1 to about 0.5:1; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a ; wherein R 3 is independently hydrogen or the same definition as R above, X is as defined above and a has a value of from 1 to less than 3; said halide being employed in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide atom and such that the R 3 :Tm ratio is from about 1:1 to about 50:1; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B or VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1.

Claim 47

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 of mixtures thereof wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the inert diluent washed hydrocarbon insoluble reaction product of: (A) The reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value from zero to 10, x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing and/or a transition metal free nitrogen-containing compound in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component (C), atomic ratio is from 0.01:1 to about 0.5:1; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a ; wherein R 3 is independently hydrogen or the same definition as R above, X is as defined above and a has a value of from 1 to less than 3; said halide being employed in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide atom and such that the R 3 :Tm ratio is from about 1:1 to about 50:1; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B or VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1.

Claim 48

The process of claim 41 wherein in component (A-1), each R and R' group is independently an aliphatic hydrocarbon having from 1 to about 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from, acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates and glycols, alcohols, aldehydes, ketones, carboxylic acids, or mixture thereof in any combination; in component (A-2) Tm' is Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine and the atomic ratio of Tm':Tm is from about 0.02:1 to about 0.2:1; in component (C), Y is OR"; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing halide is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1, and wherein said cocatalyst contains aluminum.

Claim 49

The process of claim 42 wherein R and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; said transition metal compound represented by the formula Tm'Y n X z-n is NiCl 2 , NiCl 2 .6H 2 O, FeCl 3 , FeCl 3 .6H 2 O, CrCl 3 , CrCl 2 , CrCl 3 .6H 2 O, MoCl 5 , WCl 6 , ZrCl 4 , Zr(O-iC 3 H 7 ) 4 , VOCl 3 or mixture thereof in any combination; the halide source is diethylaluminum chloride or ethylaluminum dichloride; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value of from zero to 2; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing halide is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 50

The process of claim 43 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 51

The process of claim 44 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixtures thereof.

Claim 52

The process of claim 45 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol or n-butyl alcohol.

Claim 53

The process of claim 41 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 54

The process of claim 47 wherein component (A-2) is ammonia, an amine, an isocyanate or mixture thereof in any combination.

Claim 55

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst; the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10; and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component (C), atomic ratio is from 0.01:1 to about 0.5:1; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4; Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) recovering the resultant hydrocarbon insoluble product, washing said product with fresh inert diluent; and (III) mixing, in fresh inert diluent, the product from (II) with (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined as above; z-n has a value of from zero up to the valence of Tm; in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; (IV) reacting the product from (III) with (D) a suitable reducing agent or mixture of reducing agents selected from compounds represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is a halogen or a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; (V) recovering and washing with fresh inert diluent the resultant solid hydrocarbon insoluble catalyst produced in step IV.

Claim 56

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst; the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10; and x' has a value equal to the valence of Me; and (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of about 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component (C), atomic ratio is from 0.01:1 to about 0.5:1; and (B) a suitable halide source or mixture thereof represented by the formulas AlR 3-a X a , SiR 4-b X b , SnR 4-b X b , POX 3 , PX 3 , PX 5 , SO 2 X 2 , GeX 4 , R 4 (CO)X, TmY n X z-n and R 4 X wherein each R is independently hydrogen, a hydrocarbyl or a hydrocarbyloxy group having from 1 to about 20 carbon atoms; R 4 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; each X is a halogen atom; a has a value of from 1 to 3; b has a value of from 1 to 4; Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; z has a value equal to the valence of said transition metal, n has a value of from zero to 5 with the value of z-n being from at least 1 up to a value equal to the valence of the transition metal; said halide source being present in a quantity sufficient to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; (II) recovering the resultant hydrocarbon insoluble product, washing said product with fresh inert diluent; and (III) mixing, in fresh inert diluent, the product from (II) with (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm, Y, X, z and n are as defined as above; z-n has a value of from zero up to the valence of Tm; in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; (IV) reacting the product from (III) with (D) a suitable reducing agent or mixture of reducing agents selected from compounds represented by the formulas B(R 3 ) 3-m X m , Al(R 3 ) 3-m X m , ZnR 3 X, ZnR 3 2 , MgR 3 X or MgR 3 2 wherein each X is a halogen or a hydrocarbyloxy group having from 1 to about 20 carbon atoms or an NR 3 2 group; each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; m has a value from zero to 2; said reducing agent being employed in a quantity so as to provide an R 3 :Tm ratio of from about 1:1 to about 50:1; (V) recovering and washing with fresh inert diluent the resultant solid hydrocarbon insoluble catalyst produced in step IV.

Claim 57

The process of claim 49 wherein in component (A-1), each R and R' group is independently an aliphatic hydrocarbon having from 1 to about 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from, acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; in component (A-2) Tm' is Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine and the atomic ratio of Tm':Tm is from about B 0.02:1 to about 0.2:1; the halide source is represented by the formulas AlR 3-a X a or TmY n X z-n ; in component (C) Y is OR"; the reducing agent is represented by the formula AlR 3 3-m X m ; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing agent is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1; and wherein said cocatalyst contains aluminum.

Claim 58

The process of claim 50 wherein R, R' and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, and carboxylic acids or mixture thereof in any combination; said transition metal compound represented by the formula Tm'Y n X z-n is NiCl 2 , NiCl 2 .6H 2 O, FeCl 3 , FeCl 3 .6H 2 O, CrCl 3 , CrCl 2 , CrCl 3 .6H 2 O, MoCl 5 , WCl 6 , ZrCl 4 , Zr(O-iC 3 H 7 ) 4 , VOCl 3 or mixture thereof in any combination; the halide source is represented by the formula TiCl 4 ; component (C) is TiCl 4 in the formula for the reducing agent each R 3 is independently an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms, each X is chlorine, m has a value of zero or 1; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing agent is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 59

The process of claim 51 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; the component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 60

The process of claim 52 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination.

Claim 61

The process of claim 53 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or mixture thereof in any combination.

Claim 62

The process of claim 49 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 63

The process of claim 55 wherein component (A-2) is ammonia or an amine.

Claim 64

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10 and x' has a value equal to the valence of Me; with (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component (C), atomic ratio is from 0.01:1 to about 0.5:1; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a wherein each X is independently a halogen atom; R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and a has a value of from 1 to less than 3; said halide being employed in a quantity such that the R 3 :Tm ratio is from about 1:1 to about 50:1 and to provide a sufficient amount of halogen atoms to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (II) recovering and washing with fresh inert diluent the resultant solid, hydrocarbon insoluble catalyst.

Claim 65

In a process for the polymerization of one or more polymerizable ethylenically unsaturated monomers containing one or more polymerizable α-olefins under Ziegler polymerization conditions wherein the polymerization is conducted in the presence of a transition metal-containing catalyst and at least one cocatalyst represented by the formulas Al(R 3 ) 3-a X a , B(R 3 ) 3-a X a , MgR 3 2 , MgR 3 X, ZnR 3 2 wherein each R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms and X is halogen; the improvement which comprises employing as the transition metal-containing catalyst the hydrocarbon insoluble catalyst prepared by a process which comprises: (I) reacting in an inert diluent (A) the reaction product of (1) an organomagnesium component or a mixture or complex thereof represented by the formula MgR 2 .xMeR' x' wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms, each R' is independently hydrogen, a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, Me is Al, Zn or B, x has a value of from zero to about 10 and x' has a value equal to the valence of Me; with (2) a transition metal free oxygen-containing compound, a transition metal free nitrogen-containing compound or mixture of such compounds in a quantity sufficient to lower the amount of hydrocarbyl groups present in component (A-1) such that the resultant product does not substantially reduce TiCl 4 at a temperature of 25° C.; one or more transition metal compound(s) represented by the formula Tm'Y n X z-n wherein Tm' is a transition metal selected from groups I-B, IV-B V-B, VI-B VII-B or VIII of the Periodic Table of the Elements and is not the same element as that represented by Tm in component (C); Y is oxygen, OR" or NR" 2 ; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen atom; z has a value corresponding to the valence of the transition metal Tm'; n has a value of from zero to 5; the value of z-n is from zero up to the valence of the transition metal Tm'; and wherein said transition metal compound is present in a quantity such that the Tm':Tm, from component (C), atomic ratio is from 0.01:1 to about 0.5:1; (B) a suitable reducing halide source represented by the formulas Al(R 3 ) 3-a X a wherein each X is independently a halogen atom; R 3 is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; and a has a value of from 1 to less than 3; said halide being employed in a quantity such that the R 3 :Tm ratio is from about 1:1 to about 50:1 and to provide a sufficient amount of halogen atoms to convert essentially all of the groups attached to a magnesium atom in component (A) to a halide group; and (C) a transition metal compound represented by the formula TmY n X z-n wherein Tm is a metal selected from groups IV-B, V-B and VI-B of the Periodic Table of Elements; Y is oxygen, OR" or NR" 2 ; X is a halogen; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; n has a value from zero to 5 with z-n being from one up to a value equal to the valence of the transition metal in a quantity so as to provide a Mg:Tm atomic ratio of from about 0.05:1 to about 50:1; and (II) recovering and washing with fresh inert diluent the resultant solid, hydrocarbon insoluble catalyst.

Claim 66

The process of claim 57 wherein in component (A-1), each R and R' group is independently an aliphatic hydrocarbon having from 1 to about 10 carbon atoms, Me is Al and x' has a value of 3; component (A-2) is water, carbon monoxide, carbon dioxide, sulfur dioxide, an organic oxygen-containing compound selected from, acetals, ketals, esters of carboxylic acids, orthoesters of carboxylic acids, halides of carboxylic acids, carboxylic acid anhydrides, carbonates, glycols, alcohols, aldehydes, ketones, carboxylic acids or mixture thereof in any combination; in component (A-2) Tm' is Co, Cr, Fe, Mo, Ni, V, W or Zr; R" has from 1 to about 10 carbon atoms; X is chlorine or bromine and the atomic ratio of Tm':Tm is from about 0.02:1 to about 0.2:1; in component (C), Y is OR"; the Mg:Tm atomic ratio is from about 0.1:1 to about 5:1; and the reducing halide is present in a quantity so as to provide a R 3 :Tm ratio of from about 1:1 to about 10:1.

Claim 67

The process of claim 58 wherein R and R' and the value of x are such that the organomagnesium component is hydrocarbon soluble; component (A-2) is carbon dioxide, an organic oxygen-containing compound selected from alcohols, aldehydes, ketones, and carboxylic acids or mixture thereof in any combination; said transition metal compound represented by the formula Tm'Y n X z-n is NiCl 2 , NiCl 2 .6H 2 O, FeCl 3 , FeCl 3 .6H 2 O, CrCl 3 , CrCl 2 , CrCl 3 .6H 2 O, MoCl 5 , WCl 6 , ZrCl 4 , Zr(O-iC 3 H 7 ) 4 , VOCl 3 or mixture thereof in any combination; in the formula for component (C), each X is chlorine, Tm is titanium, each R" is an aliphatic hydrocarbon group having from 1 to about 10 carbon atoms and n has a value of from zero to 2; the atomic ratio of Mg:Ti is from about 0.2:1 to about 1:1 and the reducing halide is employed in a quantity so as to provide an R 3 :Ti ratio of from about 1:1 to about 3:1.

Claim 68

The process of claim 59 wherein the value of x and each R and R' is such that the reaction product (A) is hydrocarbon soluble; component (A-2) is an alcohol or mixture of alcohols having from 1 to about 20 carbon atoms; and said cocatalyst contains triisobutylaluminum, triethylaluminum, trimethylaluminum, isoprenylaluminum or a mixture thereof in any combination.

Claim 69

The process of claim 60 wherein said alcohol is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, octadecyl alcohol, phenol, 2,6-di-tert-butyl-4-methylphenol, or mixture thereof in any combination.

Claim 70

The process of claim 61 wherein said alcohol is selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol or mixture thereof in any combination.

Claim 71

The process of claim 57 wherein component (A-2) is ammonia, an amine, a nitrile, an amide, an oxime, an imide, an isocyanate or a mixture thereof in any combination.

Claim 72

The process of claim 63 wherein component (A-2) is ammonia or an amine.

Claim 73

The process of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, or 64 wherein ethylene or a mixture of ethylene and one or more α-olefins having from 3 to about 10 carbon atoms are polymerized under slurry polymerization conditions.

Claim 74

The process of claim 65 wherein a mixture of ethylene and one or more of butene-1, hexene-1 or octene-1 are polymerized.

Claim 75

The process of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, or 64 wherein ethylene or a mixture of ethylene and one or more α-olefins having from 3 to about 10 carbon atoms are polymerized under solution polymerization conditions.

Claim 76

The process of claim 67 wherein a mixture of ethylene and one or more of butene-1, hexene-1 or octene-1 are polymerized.