US4668650A
Expired / Lapsed
US
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Catalyst composition for polymerizing alpha-olefin polymers of relatively narrow molecular weight distribution
Assignee: Mobil Oil AS
•
Filing: 1986-01-03
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Granted: 1987-05-26
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Expires: 2006-01-03
Abstract
Abstract A catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier containing OH groups with a liquid solution containing an excess of an organomagnesium composition with respect to the OH groups and contacting the thus-formed magnesium-containing carrier with a hydrocarbyl alcohol and at least one transition metal compound. Prior to contacting the magnesium-containing carrier with the alcohol, most of the liquid must be removed therefrom, so that it comprises not more than about 6% of the liquid. The amount of the transition metal compound is such that the molar ratio thereof to magnesium in the reaction mixture is about 0.3 to about 0.9. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalyst of the invention.
Inventors
- 👤 Frederick Y. Lo
- 👤 Thomas E. Nowlin
- 👤 Margaret M. Wu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 07:19
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 64
Claim 1
Independent Claim
292 words
A process for preparing a supported catalyst composition for use in alpha-olefin polymerization reactions comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be a halogen and n is 0, 1, or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier, whereby said organomagnesium composition is reacted with said OH groups on said carrier; (ii) removing said liquid, whereby a supported magnesium (Mg) composition in the form of a solid powder is formed; (iii) drying said solid powder, without washing, rinsing or decantantation thereof, until it comprises not more than about 6% by weight of the liquid; (iv) contacting the product of step (iii) with at least one hydrocarbyl alcohol of the formula R"OH wherein R" is a C 1 -C 10 alkyl, alkenyl, aryl, alkaryl or aralkyl group; (v) contacting the product of step (iv) with at least one transition metal compound soluble in a non-polar solvent, the number of moles of said transition metal compound being such that the molar ratio of the transition metal to magnesium (Mg) is about 0.3 to about 0.9, both the transition metal and Mg being calculated as elemental metals, said supported magnesium composition being substantially insoluble in said non-polar solvent, whereby a reacted form of transition metal which is insoluble in said non-polar solvent becomes supported on said carrier; and (vi) removing said non-polar solvent without washing, rinsing or decantation of the product of step (v).
Claim 2
Dependent Claim
292 words
A process for preparing a supported catalyst composition for use in alpha-olefin polymerization reactions comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be a halogen and n is 0, 1, or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier, whereby said organomagnesium composition is reacted with said OH groups on said carrier; (ii) removing said liquid, whereby a supported magnesium (Mg) composition in the form of a solid powder is formed; (iii) drying said solid powder, without washing, rinsing or decantantation thereof, until it comprises not more than about 6% by weight of the liquid; (iv) contacting the product of step (iii) with at least one hydrocarbyl alcohol of the formula R"OH wherein R" is a C 1 -C 10 alkyl, alkenyl, aryl, alkaryl or aralkyl group; (v) contacting the product of step (iv) with at least one transition metal compound soluble in a non-polar solvent, the number of moles of said transition metal compound being such that the molar ratio of the transition metal to magnesium (Mg) is about 0.3 to about 0.9, both the transition metal and Mg being calculated as elemental metals, said supported magnesium composition being substantially insoluble in said non-polar solvent, whereby a reacted form of transition metal which is insoluble in said non-polar solvent becomes supported on said carrier; and (vi) removing said non-polar solvent without washing, rinsing or decantation of the product of step (v).
Claim 3
Dependent Claim
27 words
A process of claim 1 wherein the drying in step (iii) is conducted until the solid powder comprises less than about 5% by weight of the liquid.
Claim 4
Dependent Claim
25 words
A process of claim 2 wherein the drying is conducted until the solid powder comprises about 2% to about 5% by weight of the liquid.
Claim 5
Dependent Claim
24 words
A process of claim 3 wherein the molar ratio of the transition metal to Mg in step (iv) is about 0.4 to about 0.8.
Claim 6
Dependent Claim
24 words
A process of claim 4 wherein the molar ratio of the transition metal to Mg in step (iv) is about 0.5 to about 0.8.
Claim 7
Dependent Claim
17 words
A process of claim 5 wherein R" is a C 1 -C 10 alkyl or alkenyl group.
Claim 8
Dependent Claim
15 words
A process of claim 6 wherein R" is a C 1 -C 10 alkyl group.
Claim 9
Dependent Claim
14 words
A process of claim 7 wherein the alcohol is methanol, ethanol, propanol or isopropanol.
Claim 10
Dependent Claim
10 words
A process of claim 8 wherein the alcohol is ethanol.
Claim 11
Dependent Claim
9 words
A process of claim 9 wherein n is 1.
Claim 12
Dependent Claim
39 words
A process of claim 10 wherein step (i) comprises: (a) slurrying the carrier in a non-Lewis base liquid; and (b) adding to the slurry resulting from step (a) the organomagnesium composition in the form of an ether solution thereof.
Claim 13
Dependent Claim
10 words
A process of claim 11 wherein the ether is tetrahydrofuran.
Claim 14
Dependent Claim
16 words
A process of claim 12 wherein the porous, solid carrier is silica, alumina or combinations thereof.
Claim 15
Dependent Claim
12 words
A process of claim 13 wherein the porous, solid carrier is silica.
Claim 16
Dependent Claim
15 words
A process of claim 14 wherein the transition metal compound is a tetravalent titanium compound.
Claim 17
Dependent Claim
14 words
A process of claim 15 wherein the tetravalent titanium compound is TiCl 4 .
Claim 18
Dependent Claim
39 words
A process of claim 16 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.1 to about 3.5.
Claim 19
Dependent Claim
38 words
A process of claim 17 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.5 to 3.5.
Claim 20
Dependent Claim
39 words
A process of claim 18 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 2.0 to about 3.5.
Claim 21
Dependent Claim
27 words
A process of claim 19 wherein the tetrahydrofuran is evaporated in step (ii) at about 75° to about 90° C. for about 12 to about 20 hours.
Claim 22
Dependent Claim
26 words
A process of claim 20 wherein the tetrahydrofuran is evaporated at about 80° to about 85° C. for about 16 hours in a dry nitrogen atmosphere.
Claim 23
Dependent Claim
48 words
A process of claim 21 wherein said steps (iv) and (v) are conducted by, in step (iv), slurrying the product of step (iii) in a non-polar solvent and contacting the resulting slurry with said hydrocarbyl alcohol, and, in step (v), contacting the slurry with said transition metal compound.
Claim 24
Dependent Claim
32 words
A process of claim 22 wherein, in said step (vi), said non-polar solvent is removed by evaporating it at about 75° to about 90° C. for about 12 to about 20 hours.
Claim 25
Dependent Claim
27 words
A process of claim 23 wherein said non-polar solvent is evaporated at about 80° to about 85° C. for about 16 hours in a dry nitrogen atmosphere.
Claim 26
Dependent Claim
19 words
A process of claim 24 wherein said non-polar solvent is an alkane, cycloalkane, aromatics, halogenated aromatics or hydrogenated aromatics.
Claim 27
Dependent Claim
11 words
A process of claim 25 wherein said non-polar solvent is hexane.
Claim 28
Dependent Claim
33 words
A process of claim 26 wherein, prior to contacting the silica in step (i), it is heated at a temperature of about 750° C. to about 850° C. for at least four hours.
Claim 29
Dependent Claim
12 words
A process of claim 27 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 30
Dependent Claim
289 words
A supported catalyst composition for use in alpha-olefin polymerization reactions, prepared by a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different C 1 -C 12 hydrocarbyl groups, provided that R' may also be a halogen and n is 0, 1, or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier, whereby said organomagnesium composition is reacted with said OH groups on said carrier; (ii) removing said liquid, whereby a supported magnesium (Mg) composition in the form of a solid powder is formed; (iii) drying said solid powder, without washing, rinsing or decantation thereof, until it comprises not more than about 6% by weight of the liquid; (iv) contacting the product of step (iii) with at least one hydrocarbyl alcohol of the formula R"OH wherein R" is a C 1 -C 10 alkyl, alkenyl, aryl, alkaryl or aralkyl group; (v) contacting the product of step (iv) with at least one transition metal compound soluble in a non-polar solvent, the number of moles of said transition metal compound being such that the molar ratio of the transition metal to magnesium (Mg) is about 0.3 to about 0.9, both the transition metal and Mg being calculated as elemental metals, said supported magnesium composition being substantially insoluble in said non-polar solvent, whereby a reacted form of transition metal which is insoluble in said non-polar solvent becomes supported on said carrier; and (vi) removing said non-polar solvent without washing, rinsing or decantation of the product of step (v).
Claim 31
Dependent Claim
289 words
A supported catalyst composition for use in alpha-olefin polymerization reactions, prepared by a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different C 1 -C 12 hydrocarbyl groups, provided that R' may also be a halogen and n is 0, 1, or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier, whereby said organomagnesium composition is reacted with said OH groups on said carrier; (ii) removing said liquid, whereby a supported magnesium (Mg) composition in the form of a solid powder is formed; (iii) drying said solid powder, without washing, rinsing or decantation thereof, until it comprises not more than about 6% by weight of the liquid; (iv) contacting the product of step (iii) with at least one hydrocarbyl alcohol of the formula R"OH wherein R" is a C 1 -C 10 alkyl, alkenyl, aryl, alkaryl or aralkyl group; (v) contacting the product of step (iv) with at least one transition metal compound soluble in a non-polar solvent, the number of moles of said transition metal compound being such that the molar ratio of the transition metal to magnesium (Mg) is about 0.3 to about 0.9, both the transition metal and Mg being calculated as elemental metals, said supported magnesium composition being substantially insoluble in said non-polar solvent, whereby a reacted form of transition metal which is insoluble in said non-polar solvent becomes supported on said carrier; and (vi) removing said non-polar solvent without washing, rinsing or decantation of the product of step (v).
Claim 32
Dependent Claim
27 words
A catalyst composition of claim 29 wherein the drying in step (iii) is conducted until the powder comprises less than about 5% by weight of the liquid.
Claim 33
Dependent Claim
25 words
A catalyst composition of claim 30 wherein the drying is conducted until the powder comprises about 2% to about 5% by weight of the liquid.
Claim 34
Dependent Claim
25 words
A catalyst composition of claim 31 wherein the molar ratio of the transition metal to Mg in step (iv) is about 0.4 to about 0.8.
Claim 35
Dependent Claim
25 words
A catalyst composition of claim 32 wherein the molar ratio of the transition metal to Mg in step (iv) is about 0.5 to about 0.8.
Claim 36
Dependent Claim
18 words
A catalyst composition of claim 33 wherein R" is a C 1 -C 10 alkyl or alkenyl group.
Claim 37
Dependent Claim
16 words
A catalyst composition of claim 34 wherein R" is a C 1 -C 10 alkyl group.
Claim 38
Dependent Claim
15 words
A catalyst composition of claim 35 wherein the alcohol is methanol, ethanol, propanol or isopropanol.
Claim 39
Dependent Claim
11 words
A catalyst composition of claim 36 wherein the alcohol is ethanol.
Claim 40
Dependent Claim
10 words
A catalyst composition of claim 37 wherein n is 1.
Claim 41
Dependent Claim
40 words
A catalyst composition of claim 38 wherein step (i) comprises: (a) slurrying the carrier in a non-Lewis base liquid; and (b) adding to the slurry resulting from step (a) the organomagnesium composition in the form of an ether solution thereof.
Claim 42
Dependent Claim
11 words
A catalyst composition of claim 39 wherein the ether is tetrahydrofuran.
Claim 43
Dependent Claim
17 words
A catalyst composition of claim 40 wherein the porous, solid carrier is silica, alumina or combinations thereof.
Claim 44
Dependent Claim
13 words
A catalyst composition of claim 41 wherein the porous, solid carrier is silica.
Claim 45
Dependent Claim
16 words
A catalyst composition of claim 42 wherein the transition metal compound is a tetravalent titanium compound.
Claim 46
Dependent Claim
15 words
A catalyst composition of claim 43 wherein the tetravalent titanium compound is TiCl 4 .
Claim 47
Dependent Claim
40 words
A catalyst composition of claim 44 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.1 to about 3.5.
Claim 48
Dependent Claim
40 words
A catalyst composition of claim 45 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.5 to about 3.5.
Claim 49
Dependent Claim
40 words
A catalyst composition of claim 46 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 2.0 to about 3.5.
Claim 50
Dependent Claim
28 words
A catalyst composition of claim 47 wherein the tetrahydrofuran is evaporated in step (ii) at about 75° to about 90° C. for about 12 to about 20 hours.
Claim 51
Dependent Claim
27 words
A catalyst composition of claim 48 wherein the tetrahydrofuran is evaporated at about 80° to about 85° C. for about 16 hours in a dry nitrogen atmosphere.
Claim 52
Dependent Claim
49 words
A catalyst composition of claim 49 wherein said steps (iv) and (v) are conducted by, in step (iv), slurrying the product of step (iii) in a non-polar solvent and contacting the resulting slurry with said hydrocarbyl alcohol, and, in step (v), contacting the slurry with said transition metal compound.
Claim 53
Dependent Claim
33 words
A catalyst composition of claim 50 wherein, in said step (vi), said non-polar solvent is removed by evaporating it at about 75° to about 90° C. for about 12 to about 20 hours.
Claim 54
Dependent Claim
28 words
A catalyst composition of claim 51 wherein said non-polar solvent is evaporated at about 80° to about 85° C. for about 16 hours in a dry nitrogen atmosphere.
Claim 55
Dependent Claim
20 words
A catalyst composition of claim 52 wherein said non-polar solvent is an alkane, cycloalkane, aromatics, halogenated aromatics or hydrogenated aromatics.
Claim 56
Dependent Claim
12 words
A catalyst composition of claim 53 wherein said non-polar solvent is hexane.
Claim 57
Dependent Claim
30 words
A catalyst composition of claim 54 wherein, prior to contacting the silica in step (i), it is heated at a temperature of about 750° C. for at least four hours.
Claim 58
Dependent Claim
34 words
A catalyst composition of claim 55 wherein, prior to contacting the silica in step (i), it is heated at a temperature of about 750° C. to about 850° C. for at least four hours.
Claim 59
Dependent Claim
23 words
A process of claim 28 wherein said liquid is removed in step (ii) by evaporation at about the boiling point of the liquid.
Claim 60
Dependent Claim
25 words
A process of claim 57 wherein, in said step (vi), said non-polar solvent is removed by evaporation at about the boiling point of the solvent.
Claim 61
Dependent Claim
20 words
A process of claim 58 wherein the molar ratio of the transition metal to Mg in step (iv) is 0.7.
Claim 62
Dependent Claim
24 words
A catalyst composition of claim 56 wherein said liquid is removed in step (ii) by evaporation at about the boiling point of the liquid.
Claim 63
Dependent Claim
26 words
A catalyst composition of claim 60 wherein, in said step (vi), said non-polar solvent is removed by evaporation at about the boiling point of the solvent.
Claim 64
Dependent Claim
21 words
A catalyst composition of claim 61 wherein the molar ratio of the transition metal to Mg in step (iv) is 0.7.
References Cited (Backward Citations)
US4063009A
Cited
US4076698B1
Cited
US4076698A
Cited
US3135809A
Cited
US3787384A
Cited
US4148754A
Cited
US4173547A
Cited
US4302566A
Cited
US4378304A
Cited
CA1195792A
Cited
US4481301A
Cited
US4558024A
Cited
US4558025A
Cited
US4579834A
Cited
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1990-05-25 | 1990-11-24 | 1991-05-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-05-25 | 1994-11-24 | 1995-05-26 | $3760.00 | Window Closed / Lapsed |
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