US4833111A
Expired / Lapsed
US
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Catalyst composition for polymerizing alpha-olefin polymers of narrow molecular weight distribution
Assignee: Mobil Oil AS
•
Filing: 1988-01-14
•
Granted: 1989-05-23
•
Expires: 2008-01-14
Abstract
Abstract A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a hydroxyl group-containing compound, e.g., an alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) contacting the slurry of step (3) with a halogenated alkyl aluminum compound, e.g., ethyl aluminum dichloride, and, (5) activating the product of step (5) with trimethylaluminum. The resulting catalyst composition is extremely active in polymerizing C 2 -C 10 alpha-olefins and exhibits very good higher (C 3 -C 10 ) alpha-olefins incorporation properties.
Inventors
- 👤 Thomas E. Nowlin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 01:31
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 68
Claim 1
Independent Claim
186 words
A process for preparing a supported alpha-olefin polymerization catalyst composition which comprises the steps of: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry of step (i) with at least one compound of the formula R.sup.2 --OH (II) where R 2 is a C 1 -C 10 alkyl group or a C 1 -C 10 halogenated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; (iv) contacting the slurry of step (iii) with at least one halogenated alkyl aluminum compound of the formula R.sub.y.sup.3 AlX.sub.(3-y) (III) where R 3 is a C 1 -C 10 alkyl group, X is Cl, Br or I and y is 1 or 2; and (v) combining the product of step (iv) with trimethylaluminum.
Claim 2
Dependent Claim
186 words
A process for preparing a supported alpha-olefin polymerization catalyst composition which comprises the steps of: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry of step (i) with at least one compound of the formula R.sup.2 --OH (II) where R 2 is a C 1 -C 10 alkyl group or a C 1 -C 10 halogenated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; (iv) contacting the slurry of step (iii) with at least one halogenated alkyl aluminum compound of the formula R.sub.y.sup.3 AlX.sub.(3-y) (III) where R 3 is a C 1 -C 10 alkyl group, X is Cl, Br or I and y is 1 or 2; and (v) combining the product of step (iv) with trimethylaluminum.
Claim 3
Dependent Claim
16 words
A process of claim 1 wherein R and R' are C 4 -C 10 alkyl groups.
Claim 4
Dependent Claim
16 words
A process of claim 2 wherein R and R' are C 4 -C 8 alkyl groups.
Claim 5
Dependent Claim
20 words
A process of claim 3 wherein R and R' are each butyl groups, m is 1 and n is 1.
Claim 6
Dependent Claim
19 words
A process of claim 4 wherein the non-polar solvent is a hydrocarbon which is a liquid at ambient conditions.
Claim 7
Dependent Claim
16 words
A process of claim 5 wherein R 2 is a C 1 -C 8 alkyl group.
Claim 8
Dependent Claim
16 words
A process of claim 6 wherein R 2 is a methyl, ethyl, propyl or butyl group.
Claim 9
Dependent Claim
17 words
A process of claim 7 wherein the transition metal compound is a compound of titanium or vanadium.
Claim 10
Dependent Claim
13 words
A process of claim 8 wherein the transition metal compound is titanium halide.
Claim 11
Dependent Claim
12 words
A process of claim 9 wherein the titanium halide is titanium tetrahalide.
Claim 12
Dependent Claim
13 words
A process of claim 10 wherein the titanium tetrahalide is TiCl 4 .
Claim 13
Dependent Claim
33 words
A process of claim 10 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 1 to about 3.
Claim 14
Dependent Claim
33 words
A process of claim 12 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar raio of Mg to Ti is about 2 to about 3.
Claim 15
Dependent Claim
13 words
A process of claim 13 wherein the solid, porous carrier contains OH groups.
Claim 16
Dependent Claim
31 words
A process of claim 14 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 1:1 to about 6:1.
Claim 17
Dependent Claim
31 words
A process of claim 15 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 2:1 to about 4:1.
Claim 18
Dependent Claim
31 words
A process of claim 16 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 2.5:1 to about 3.5:1.
Claim 19
Dependent Claim
28 words
A process of claim 17 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio of Mg:OH is about 3:1.
Claim 20
Dependent Claim
35 words
A process of claim 18 wherein the solid, porous carrier is silica which, prior to contact thereof with the solvent in said step (i), is heated at a temperature of at least about 600° C.
Claim 21
Dependent Claim
17 words
A process of claim 19 wherein the silica is heated at a temperature of about 600° C.
Claim 22
Dependent Claim
37 words
A process of claim 20 wherein the silica has, after the heating, surface hydroxyl group concentration of about 0.5 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 23
Dependent Claim
20 words
A process of claim 21 wherein R 3 is a C 1 -C 4 alkyl group and X is Cl.
Claim 24
Dependent Claim
15 words
A process of claim 22 wherein the compound of the formula (III) is diethylaluminum chloride.
Claim 25
Dependent Claim
15 words
A process of claim 22 wherein the compound of the formula (III) is ethylaluminum dichloride.
Claim 26
Dependent Claim
179 words
A supported alpha-olefin polymerization catalyst composition prepared by: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each, 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry of step (i) with at least one compound of the formula R.sup.2 --OH (II) where R 2 is a C 1 -C 10 alkyl group or a C 1 -C 10 halogenated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; (iv) contacting the slurry of step (iii) with at least one halogenated alkyl aluminum compound of the formula R.sub.y.sup.3 AlX.sub.(3-y) (III) where R 3 is a C 1 -C 10 alkyl group, X is Cl, Br or I and y is 1 or 2; and (v) combining the product of step (iv) with trimethylaluminum.
Claim 27
Dependent Claim
179 words
A supported alpha-olefin polymerization catalyst composition prepared by: (i) contacting a slurry of a solid, porous carrier and a non-polar solvent with at least one organomagnesium composition having the formula R.sub.m MgR.sub.n ' (I) where R and R' are the same or different C 4 -C 12 alkyl groups, m and n are each, 0, 1 or 2, provided that m+n is equal to the valence of Mg; (ii) contacting the slurry of step (i) with at least one compound of the formula R.sup.2 --OH (II) where R 2 is a C 1 -C 10 alkyl group or a C 1 -C 10 halogenated alkyl group; (iii) contacting the slurry of step (ii) with at least one transition metal compound soluble in the non-polar solvent; (iv) contacting the slurry of step (iii) with at least one halogenated alkyl aluminum compound of the formula R.sub.y.sup.3 AlX.sub.(3-y) (III) where R 3 is a C 1 -C 10 alkyl group, X is Cl, Br or I and y is 1 or 2; and (v) combining the product of step (iv) with trimethylaluminum.
Claim 28
Dependent Claim
17 words
A catalyst composition of claim 25 wherein R and R' are C 4 -C 10 alkyl groups.
Claim 29
Dependent Claim
17 words
A catalyst composition of claim 26 wherein R and R' are C 4 -C 8 alkyl groups.
Claim 30
Dependent Claim
21 words
A catalyst composition of claim 27 wherein R and R' are each butyl groups, m is 1 and n is 1.
Claim 31
Dependent Claim
20 words
A catalyst composition of claim 28 wherein the non-polar solvent is a hydrocarbon which is a liquid at ambient conditions.
Claim 32
Dependent Claim
17 words
A catalyst composition of claim 29 wherein R 2 is a C 1 -C 8 alkyl group.
Claim 33
Dependent Claim
17 words
A catalyst composition of claim 30 wherein R 2 is a methyl, ethyl, propyl or butyl group.
Claim 34
Dependent Claim
18 words
A catalyst composition of claim 29 wherein the transition metal compound is a compound of titanium or vanadium.
Claim 35
Dependent Claim
14 words
A catalyst composition of claim 32 wherein the transition metal compound is titanium halide.
Claim 36
Dependent Claim
13 words
A catalyst composition of claim 33 wherein the titanium halide is titanium tetrahalide.
Claim 37
Dependent Claim
14 words
A catalyst composition of claim 34 wherein the titanium tetrahalide is TiCl 4 .
Claim 38
Dependent Claim
34 words
A catalyst composition of claim 35 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 1 to about 3.
Claim 39
Dependent Claim
34 words
A catalyst composition of claim 36 wherein the amount of the TiCl 4 present in said step (iii) is such that the molar ratio of Mg to Ti is about 2 to about 3.
Claim 40
Dependent Claim
14 words
A catalyst composition of claim 37 wherein the solid, porous carrier contains OH groups.
Claim 41
Dependent Claim
31 words
A catalyst composition of claim 38 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio Mg:OH is about 1:1 to about 6:1.
Claim 42
Dependent Claim
31 words
A catalyst composition of claim 39 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio Mg:OH is about 2:1 to about 4:1.
Claim 43
Dependent Claim
31 words
A catalyst composition of claim 40 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ratio Mg:OH is about 2.5:1 to about 3.5:1.
Claim 44
Dependent Claim
28 words
A catalyst composition of claim 41 wherein the amount of the organomagnesium composition used in said step (i) is such that the molar ration Mg:OH is about 3:1.
Claim 45
Dependent Claim
36 words
A catalyst composition of claim 42 wherein the solid, porous carrier is silica which, prior to contact thereof with the solvent in said step (i), is heated at a temperature of at least about 600° C.
Claim 46
Dependent Claim
18 words
A catalyst composition of claim 43 wherein the silica is heated at a temperature of about 600° C.
Claim 47
Dependent Claim
38 words
A catalyst composition of claim 44 wherein the silica has, after the heating, surface hydroxyl groups concentration of about 0.5 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 48
Dependent Claim
22 words
A catalyst composition of claim 45 wherein R 3 is a C 1 14 C 4 alkyl group and X is Cl.
Claim 49
Dependent Claim
15 words
A catalyst composition of claim 46 wherein the compound of formula (III) is diethylaluminum chloride.
Claim 50
Dependent Claim
15 words
A catalyst composition of claim 46 wherein the compound of formula (III) is ethylaluminum dichloride.
Claim 51
Dependent Claim
148 words
A process of claim 1 wherein in said step (i) only such an amount of the organomagnesium composition is used which will be deposited onto the carrier; in said step (ii) only such an amount of the compound of the formula (II) is used which is sufficient to convert substantially all of the magnesium alkyl groups on the carrier to magnesium-alkoxy groups, so that substantially no excess of the formula (II) compound is present in the non-polar solvent after substantially all of the magnesium groups are converted to the magnesium alkoxy groups; in said step (iii) such an amount of the transition metal compound is used which is not greater than that which can be deposited on the carrier; and in said step (iv) such an amount of the halogenated alkyl aluminum compound is used which is not greater than that which can be deposited onto the carrier.
Claim 52
Dependent Claim
36 words
A process of claim 8 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1 to about 3.
Claim 53
Dependent Claim
36 words
A process of claim 50 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 2 to about 3.
Claim 54
Dependent Claim
37 words
A process of claim 22 wherein the amount of the halogenated alkyl aluminum compound in said step (iv) is such that the molar ratio of Al:transition metal in the catalyst composition is about 0.1 to about 10.
Claim 55
Dependent Claim
37 words
A process of claim 52 wherein the amount of the halogenated alkyl aluminum compound in said step (iv) is such that the molar ratio of Al:transition metal in the catalyst composition is about 0.5 to about 5.
Claim 56
Dependent Claim
37 words
A process of claim 53 wherein the amount of the halogenated alkyl aluminum compound in said step (iv) is such that the molar ratio of Al:transition metal in the catalyst composition is about 1.0 to about 2.0.
Claim 57
Dependent Claim
27 words
A process of claim 54 wherein the product of said step (iv), prior to conducting said step (v), is dried at about 40° to about 65° C.
Claim 58
Dependent Claim
27 words
A process of claim 55 wherein the product of said step (iv), prior to conducting said step (v), is dried at about 45° to about 55° C.
Claim 59
Dependent Claim
24 words
A process of claim 56 wherein the product of said step (iv), prior to conducting said step (v), is dried at about 55° C.
Claim 60
Dependent Claim
149 words
A catalyst composition of claim 25 wherein in said step (i) only such an amount of the organomagnesium composition is used which will be deposited onto the carrier; in said step (ii) only such an amount of the compound of the formula (II) is used which is sufficient to convert substantially all of the magnesium alkyl groups on the carrier to magnesium-alkoxy groups, so that substantially no excess of the formula (II) compound is present in the non-polar solvent after substantially all of the magnesium groups are converted to the magnesium alkoxy groups; in said step (iii) such an amount of the transition metal compound is used which is not greater than that which can be deposited on the carrier; and in said step (iv) such an amount of the halogenated alkyl aluminum compound is used which is not greater than that which can be deposited onto the carrier.
Claim 61
Dependent Claim
37 words
A catalyst composition of claim 32 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 1 to about 3.
Claim 62
Dependent Claim
37 words
A catalyst composition of claim 59 wherein the amount of the transition metal compound present in said step (iii) is such that the molar ratio of Mg to the transition metal is about 2 to about 3.
Claim 63
Dependent Claim
38 words
A catalyst composition of claim 46 wherein the amount of the halogenated alkyl aluminum compound in said step (iv) is such that the molar ratio of Al:transition metal in the catalyst composition is about 0.1 to about 10.
Claim 64
Dependent Claim
38 words
A catalyst composition of claim 61 wherein the amount of the halogenated alkyl aluminum compound in said step (iv) is such that the molar ratio of Al:transition metal in the catalyst composition is about 0.5 to about 5.
Claim 65
Dependent Claim
38 words
A catalyst composition of claim 62 wherein the amount of the halogenated alkyl aluminum compound in said step (iv) is such that the molar ratio of Al:transition metal in the catalyst composition is about 1.0 to about 2.0.
Claim 66
Dependent Claim
28 words
A catalyst composition of claim 63 wherein the product of said step (iv), prior to conducting said step (v), is dried at about 40° to about 65° C.
Claim 67
Dependent Claim
28 words
A catalyst composition of claim 64 wherein the product of said step (iv), prior to conducting said step (v), is dried at about 45° to about 55° C.
Claim 68
Dependent Claim
25 words
A catalyst composition of claim 65 wherein the product of said step (iv), prior to conducting said step (v), is dried at about 55° C.
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