Process for polymerizing alpha-olefins

Claim 2

A process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst which is a catalytic reaction product of (A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (a) at least one transition metal compound represented by the empirical formulae Tm(OR) y or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; x has a value equal to the valence of Tm and y has a value equal to the valence of Tm; and (b) at least one oxygen-containing compound; and (2) at least one non-reducing alkylating agent represented by the empirical formulae ZnR 2 or RZnX wherein X is a halogen; each R is independently an alkyl group having from 1 to about 20 carbon atoms; (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR" 2 .xMR" y wherein M is aluminum or zinc, each R" is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (a) an active non-metallic halide, said non-metallic halide corresponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst and X is halogen or (b) a metallic halide corresponding to the empirical formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlR y' X y" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and wherein the components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; the non-metallic oxygen-containing component is employed in quantities so as to provide an atomic ratio of O:Tm of from about 0.1:1 to about 4:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 5:1.

Claim 3

A process of claim 1 wherein (a) in component (A-1), Tm is titanium, each R is independently a hydrocarbyl group having from 1 to about 10 carbon atoms and said oxygen-containing component is an alcohol, water, acetone or mixture thereof; (b) in component (A-2), said alkylating agent is represented by the empirical formula ZnR 2 wherein R is a hydrocarbyl group having from 1 to about 10 carbon atoms; (c) in component (B-1), M is aluminum and R" is a hydrocarbyl group having from 1 to about 10 carbon atoms and x has a value of from about zero to about 5; (d) in component (B-2-a), R' is hydrogen or a tertiary butyl group and X is chlorine; (e) in component (B-2-b), M is a metal from Groups IIIA or IVA, y-a is zero, 1 or 2 and X is chlorine; (f) in component (C), the aluminum compound is a trialkyl aluminum compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (g) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 2:1 to about 100:1; Zn:Ti from about 0.25:1 to about 5:1; O:Ti of from about 0.25:1 to about 3:1; Al:Ti of from about 0.5:1 to about 100:1 and excess X:Al of from about 0.002:1 to about 2:1.

Claim 4

A process of claim 2 wherein (a) in component (A-1), R is a saturated aliphatic hydrocarbyl group; (b) in component (B-1), x has a value of from about 0.001 to about 2.5; and (c) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 5:1 to about 75:1; Zn:Ti of from about 0.5:1 to about 2:1; O:Ti of from about 0.5:1 to about 2:1; and excess X:Al of from about 0.01:1 to about 1.4:1.

Claim 5

A process of claim 3 wherein (a) component (A-1-a) is titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra-(2-ethylhexoxide) or a mixture thereof; (b) component (A-1-b) is n-butanol, sec-butanol, n-propanol, isopropanol, water, acetone or a mixture thereof; (c) component (A-2) is dimethyl zinc, diethyl zinc, diphenyl zinc or a mixture thereof; (d) component (B-1) is a dialkyl magnesium compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (e) component (B-2) is substantially anhydrous hydrogen chloride, ethyl aluminum dichloride or tin tetrachloride.

Claim 6

A process of claims 1, 2, 3 or 4 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 7

A process of claim 5 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 8

A process of claim 6 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 9

A process of claims 1, 2, 3 or 4 wherein the components of said catalytic reaction product are added in the order (B-1), (B-2), (C) if employed and (A).

Claim 10

A process of claim 8 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 11

A process of claim 9 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 12

A process of claim 10 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 13

A process of claims 1, 2, 3 or 4 wherein the components of said catalytic reaction product are added in the order (B-1), (B-2), (A) and (C) if employed, and provided that the halide source, (B-2), is not a tin compound.

Claim 14

A process of claim 12 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 15

A process of claim 13 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 16

A process of claim 14 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 17

A process of claims 1, 2, 3 or 4 wherein the components of said catalytic reaction product are added in the order (B-2), (C) if employed, (B-1) and (A).

Claim 18

A process of claim 16 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 19

A process of claim 17 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 20

A process of claim 18 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 21

A process of claims 1, 2, 3 or 4 wherein the components of said catalytic reaction product are added in the order (B-2), (C) if employed, (A) and (B-1).

Claim 22

A process of claim 20 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 23

A process of claim 21 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 24

A process of claim 22 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 25

An improvement in a process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst composition comprising a magnesium halide, a transition metal compound represented by the empirical formula Tm(OR) y or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; x has a value equal to the valence of Tm and y has a value equal to the valence of Tm and a zinc compound, said composition having an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 10:1; wherein the improvement comprises forming a reaction product or complex of (1) a mixture of the transition metal compound and an oxygen-containing compound in quantities so as to provide an atomic ratio of O:Tm of from about 0.1:1 to about 4:1; and (2) the zinc compound prior to preparation of the catalyst therefrom.

Claim 26

An improvement in a process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst composition comprising a magnesium halide, a transition metal compound represented by the empirical formula Tm(OR) y or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; x has a value equal to the valence of Tm and y has a value equal to the valence of Tm and a zinc compound, said composition having an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 10:1; wherein the improvement comprises forming a reaction product or complex of (1) a mixture of the transition metal compound and an oxygen-containing compound in quantities so as to provide an atomic ratio of O:Tm of from about 0.1:1 to about 4:1; and (2) the zinc compound prior to preparation of the catalyst therefrom.

Claim 27

A process of claim 24 wherein the atomic ratios of the elements are Mg:Tm of from about 2:1 to about 100:1; Zn:Tm of from about 0.25:1 to about 5:1; O:Tm of from about 0.25:1 to about 3:1; Al:Tm of from about 0.5:1 to about 100:1 and excess X:Al of from about 0.002:1 to about 2:1.

Claim 28

A process of claim 25 wherein the atomic ratios of the elements are Mg:Tm of from about 5:1 to about 75:1; Zn:Tm of from about 0.5:1 to about 2:1; O:Tm of from about 0.5:1 to about 2:1; Al:Tm of from about 1:1 to about 75:1 and excess X:Al of from about 0.01:1 to about 1.4:1.

Claim 29

A process of claims 24, 25 or 26 wherein said transition metal compound is a titanium compound and said zinc compound is a dialkyl zinc wherein each alkyl group independently has from 1 to about 10 carbon atoms.

Claim 30

A process of claim 27 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 31

A process of claim 28 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 32

A process of claim 29 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 33

A process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst which is a catalytic reaction product of (A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (a) at least one transition metal compound represented by the empirical formulae TM(OR) y X x-y , TmOX x-2 or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; each X is independently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (b) at least one oxygen-containing compound selected from the group consisting of molecular oxygen, ketones, aldehydes, carboxylic acids, esters of carboxylic acids, peroxides and water; and (2) at least one non-reducing alkylating agent represented by the empirical formulae ZnR 2 or RZnX wherein X is a halogen; each R is independently an alkyl group having from 1 to about 20 carbon atoms; (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR" 2 .xMR" y wherein M is aluminum or zinc, each R" is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (a) an active non-metallic halide, said non-metallic halide corresponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst and X is halogen or (b) a metallic halide corresponding to the empirical formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlR y' X y" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and wherein the components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; the non-metallic oxygen-containing component is employed in quantities so as to provide an atomic ratio of O:Tm of from about about 0.1:1 to about 4:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 5:1.

Claim 34

A process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst which is a catalytic reaction product of (A) a reaction product or complex formed from the admixture of (1) a reaction product or complex formed by mixing (a) at least one transition metal compound represented by the empirical formulae TM(OR) y X x-y , TmOX x-2 or Tm(OR) x-2 O wherein Tm is a transition metal selected from groups IVB, VB or VIB; each R is independently a hydrocarbyl group, having from 1 to about 20 carbon atoms; each X is independently a halogen; x has a value equal to the valence of Tm and y has a value from 1 to the valence of Tm; and (b) at least one oxygen-containing compound selected from the group consisting of molecular oxygen, ketones, aldehydes, carboxylic acids, esters of carboxylic acids, peroxides and water; and (2) at least one non-reducing alkylating agent represented by the empirical formulae ZnR 2 or RZnX wherein X is a halogen; each R is independently an alkyl group having from 1 to about 20 carbon atoms; (B) a magnesium halide resulting from the reaction of (1) an organomagnesium compound represented by the empirical formula MgR" 2 .xMR" y wherein M is aluminum or zinc, each R" is independently a hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms, x has a value from zero to 10 and y has a value corresponding to the valence of M; with (2) a halide source selected from (a) an active non-metallic halide, said non-metallic halide corresponding to the empirical formula R'X wherein R' is hydrogen or a hydrocarbyl group such that the hydrocarbyl halide is at least as active as sec-butyl chloride and does not poison the catalyst and X is halogen or (b) a metallic halide corresponding to the empirical formula MR y-a X a wherein M is a metal of Group IIIA or IVA of Mendeleev's Periodic Table of Elements, R is a monovalent hydrocarbyl radical, X is halogen, y is a number corresponding to the valence of M and a is a number of 1 to y; and (C) when the organomagnesium component and/or the halide source provides insufficient quantities of aluminum, an aluminum compound is added which is represented by the empirical formula AlR y' X y" wherein R and X are as defined above and y' and y" each have a value of from zero to three with the sum of y' and y" being three; and wherein the components are employed in quantities which provide an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; the non-metallic oxygen-containing component is employed in quantities so as to provide an atomic ratio of O:Tm of from about about 0.1:1 to about 4:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 5:1.

Claim 35

A process of claim 31 wherein (a) in component (A-1), Tm is titanium, each R is independently a hydrocarbyl group having from 1 to about 10 carbon atoms and X is chlorine or bromine and said oxygen-containing component is water, acetone or mixture thereof; (b) in component (A-2), said alkylating agent is represented by the empirical formula ZnR 2 wherein R is a hydrocarbyl group having from 1 to about 10 carbon atoms; (c) in component (B-1), M is aluminum and R" is a hydrocarbyl group having from 1 to about 10 carbon atoms and x has a value of from about zero to about 5; (d) in component (B-2-a), R' is hydrogen or a tertiary butyl group and X is chlorine; (e) in component (B-2-b), M is a metal from Groups IIIA or IVA, y-a is zero, 1 or 2 and X is chlorine; (f) in component (C), the aluminum compound is a trialkyl aluminum compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (g) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 2:1 to about 100:1; Zn:Ti from about 0.25:1 to about 5:1; O:Ti of from about 0.25:1 to about 3:1; Al:Ti of from about 0.5:1 to about 100:1 and excess X:Al of from about 0.002:1 to about 2:1.

Claim 36

A process of claim 32 wherein (a) in component (A-1), R is a saturated aliphatic hydrocarbyl group; (b) in component (B-1), x has a value of from about 0.001 to about 2.5; and (c) the components are employed in quantities so as to provide atomic ratios of Mg:Ti of from about 5:1 to about 75:1; Zn:Ti of from about 0.5:1 to about 2:1; O:Ti of from about 0.5:1 to about 2:1; and excess X:Al of from about 0.01:1 to about 1.4:1.

Claim 37

A process of claim 33 wherein (a) component (A-1-a) is titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra-(2-ethylhexoxide) or a mixture thereof; (b) component (A-2) is dimethyl zinc, diethyl zinc, diphenyl zinc or a mixture thereof; (c) component (B-1) is a dialkyl magnesium compound wherein the alkyl groups independently have from 1 to about 10 carbon atoms; and (d) component (B-2) is substantially anhydrous hydrogen chloride, ethyl aluminum dichloride or tin tetrachloride.

Claim 38

A process of claims 31, 32, 33 or 34 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 39

A process of claim 35 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 40

A process of claim 36 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 41

A process of claims 31, 32, 33 or 34 wherein the components of said catalytic reaction product are added in the order (B-1), (B-2), (C) if employed and (A).

Claim 42

A process of claim 38 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 43

A process of claim 39 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 44

A process of claim 40 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 45

A process of claims 31, 32, 33 or 34 wherein the components of said catalytic reaction product are added in the order (B-1), (B-2), (A) and (C) if employed, and provided that the halide source, (B-2), is not a tin compound.

Claim 46

A process of claim 42 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 47

A process of claim 43 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 48

A process of claim 44 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 49

A process of claims 31, 32, 33 or 34 wherein the components of said catalytic reaction product are added in the order (B-2), (C) if employed, (B-1) and (A).

Claim 50

A process of claim 46 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerizaton conditions.

Claim 51

A process of claim 47 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 52

A process of claim 48 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 53

A process of claims 31, 32, 33 or 34 wherein the components of said catalytic reaction product are added in the order (B-2), (C) if employed, (A) and (B-1).

Claim 54

A process of claim 50 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 55

A process of claim 51 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 56

A process of claim 52 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.

Claim 57

An improvement in a process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst composition comprising a magnesium halide, a transition metal compound and a zinc compound, said composition having an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 10:1; wherein the improvement comprises forming a reaction product or complex of (1) a mixture of the transition metal compound and an oxygen-containing compound selected from the group consisting of molecular oxygen, ketones, aldehydes, carboxylic acids, esters of carboxylic acids, peroxides and water in quantities so as to provide an atomic ratio of O:Tm of from about 0.1:1 to about 4:1; and (2) the zinc compound prior to preparation of the catalyst therefrom.

Claim 58

An improvement in a process for polymerizing one or more polymerizable α-olefins which process comprises conducting the polymerization under Ziegler polymerization conditions in the presence of a catalyst composition comprising a magnesium halide, a transition metal compound and a zinc compound, said composition having an atomic ratio of the elements Mg:Tm of from about 1:1 to about 200:1; Zn:Tm of from about 0.1:1 to about 10:1; Al:Tm of from about 0.1:1 to about 200:1 and an excess X:Al of from about 0.0005:1 to about 10:1; wherein the improvement comprises forming a reaction product or complex of (1) a mixture of the transition metal compound and an oxygen-containing compound selected from the group consisting of molecular oxygen, ketones, aldehydes, carboxylic acids, esters of carboxylic acids, peroxides and water in quantities so as to provide an atomic ratio of O:Tm of from about 0.1:1 to about 4:1; and (2) the zinc compound prior to preparation of the catalyst therefrom.

Claim 59

A process of claim 54 wherein the atomic ratios of the elements are Mg:Tm of from about 2:1 to about 100:1; Zn:Tm of from about 0.25:1 to about 5:1; O:Tm of from about 0.25:1 to about 3:1; Al:Tm of from about 0.5:1 to about 100:1 and excess X:Al of from about 0.002:1 to about 2:1.

Claim 60

A process of claim 55 wherein the atomic ratios of the elements are Mg:Tm of from about 5:1 to about 75:1; Zn:Tm of from about 0.5:1 to about 2:1; O:Tm of from about 0.5:1 to about 2:1; Al:Tm of from about 1:1 to about 75:1 and excess X:Al of from about 0.01:1 to about 1.4:1.

Claim 61

A process of claims 54, 55 or 56 wherein said transition metal compound is a titanium compound and said zinc compound is a dialkyl zinc wherein each alkyl group independently has from 1 to about 10 carbon atoms.

Claim 62

A process of claim 57 wherein ethylene and at least one higher α-olefin are polymerized under solution polymerization conditions.

Claim 63

A process of claim 58 wherein said higher α-olefin has from 3 to about 10 carbon atoms.

Claim 64

A process of claim 59 wherein said higher α-olefin is selected from butene-1, hexene-1 and octene-1.