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US4277370A
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Alpha-olefin polymerization catalyst
Assignee: BP Corp North America Inc
•
Filing: 1980-01-21
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Granted: 1981-07-07
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Expires: 2000-01-21
Abstract
Abstract Catalyst for the stereospecific polymerization of alpha-olefins of 3 or more carbon atoms comprising an organoaluminum compound and a component prepared from halogen-containing compound of titanium(IV), organic electron donor, and a pretreatment product of components comprising magnesium alcoholate, Group II or IIIA metal alkyl, and optionally, one or more pretreatment modifiers such as a mineral acid or anhydride of sulfur, organometallic chalcogenide derivative of hydrogen sulfide, organic acid or organic acid ester. Preferably, the product obtained from such materials is contacted with liquid Lewis acid and mechanically activated prior to polymerization use.
Inventors
- 👤 Nicholas M. Karayannis
- 👤 John S. Skryantz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 06:42
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64
Claims Analysis
Total Claims: 82
Claim 1
Independent Claim
142 words
A catalyst for the polymerization of alpha-olefins of at least 3 carbon atoms comprising (A) an organoaluminum component, and (B) a solid component which is the reaction product of components comprising (1) at least one titanium(IV) halide or haloalcoholate; (2) at least one organic electron donor containing at least one of oxygen, nitrogen, sulfur and phosphorus; and (3) at least one hydrocarbon-insoluble, magnesium-containing pretreatment product of components comprising (a) at least one magnesium alcoholate; and (b) at least one Group II or IIIA metal alkyl; wherein the atomic ratio of metal in (3)(b) to metal in (3)(a) ranges from about 0.001:1 to about 1:1, the atomic ratio of titanium in (1) to metal in (3)(a) is at least about 0.5:1, and (2) is employed in an amount ranging from about 0.001 to about 1 mole per gram-atom of titanium contained in (1).
Claim 2
Dependent Claim
142 words
A catalyst for the polymerization of alpha-olefins of at least 3 carbon atoms comprising (A) an organoaluminum component, and (B) a solid component which is the reaction product of components comprising (1) at least one titanium(IV) halide or haloalcoholate; (2) at least one organic electron donor containing at least one of oxygen, nitrogen, sulfur and phosphorus; and (3) at least one hydrocarbon-insoluble, magnesium-containing pretreatment product of components comprising (a) at least one magnesium alcoholate; and (b) at least one Group II or IIIA metal alkyl; wherein the atomic ratio of metal in (3)(b) to metal in (3)(a) ranges from about 0.001:1 to about 1:1, the atomic ratio of titanium in (1) to metal in (3)(a) is at least about 0.5:1, and (2) is employed in an amount ranging from about 0.001 to about 1 mole per gram-atom of titanium contained in (1).
Claim 3
Dependent Claim
39 words
The catalyst of claim 1 wherein component (2) comprises a C 1-6 alkyl ester of an aromatic monocarboxylic acid or of an aromatic monocarboxylic acid substituted with at least one of halogen, hydroxyl, oxo, alkyl, alkoxy, aryl or aryloxy.
Claim 4
Dependent Claim
47 words
The catalyst of claim 1 wherein component (3)(b) comprises a compound of the formula MR 3 m wherein M is aluminum, magnesium, or zinc, each R 3 is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.
Claim 5
Dependent Claim
49 words
The catalyst of claim 1 wherein component (3)(a) comprises a compound of the formula Mg(OR 1 ) n (OR 2 ) 2-n , wherein R 1 and R 2 are identical or different hydrocarbyl radicals of 1 to about 20 carbon atoms, and n ranges from 0 to 2.
Claim 6
Dependent Claim
13 words
The catalyst of claim 1 wherein the solid component (B) is mechanically activated.
Claim 7
Dependent Claim
18 words
The catalyst of claim 1 wherein component (3) is prepared in the presence of at least one alpha-olefin.
Claim 8
Dependent Claim
38 words
The catalyst of claim 1 further characterized in that the solid component (B) is treated with at least one liquid Lewis acid having a high enough Lewis acidity to remove impurities from the surface of said solid component.
Claim 9
Dependent Claim
16 words
The catalyst of claim 7 further characterized in that said Lewis acid-treated solid is mechanically activated.
Claim 10
Dependent Claim
11 words
The catalyst of claim 1 wherein component (1) comprises titanium tetrachloride.
Claim 11
Dependent Claim
29 words
The catalyst of claim 9 wherein component (2) comprises an alkyl ester of benzoic acid or a halobenzoic acid, said alkyl radical containing 1 to about 6 carbon atoms.
Claim 12
Dependent Claim
47 words
The catalyst of claim 10 wherein component (3)(b) comprises a compound of the formula MR 3 m wherein M is aluminum, magnesium, or zinc, each R 3 is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.
Claim 13
Dependent Claim
48 words
The catalyst of claim 11 wherein component (3)(a) comprises a compound of the formula Mg(OR 1 ) n (OR 2 ) 2-n wherein R 1 and R 2 are identical or different hydrocarbyl radicals of 1 to about 20 carbon atoms and n ranges from 0 to 2.
Claim 14
Dependent Claim
41 words
The catalyst of claim 12 further characterized in that said solid component (B) is treated with at least one Lewis acid selected from the Group III-V metal halides which are in the liquid state at temperatures up to about 170° C.
Claim 15
Dependent Claim
21 words
The catalyst of claim 13 wherein component (3)(b) comprises a trialkylaluminum containing 1 to about 6 carbon atoms per alkyl radical.
Claim 16
Dependent Claim
11 words
The catalyst of claim 14 wherein component (2) comprises ethyl benzoate.
Claim 17
Dependent Claim
10 words
The catalyst of claim 15 wherein component (3)(b) comprises triethylaluminum.
Claim 18
Dependent Claim
55 words
The catalyst of claim 16 wherein component (3)(a) comprises a compound of the formula Mg(OR 1 ) 2 wherein R 1 is an alkyl radical of 1 to about 6 carbon atoms, an aryl radical of 6 to about 12 carbon atoms or an alkaryl or aralkyl radical of 6 to about 12 carbon atoms.
Claim 19
Dependent Claim
16 words
The catalyst of claim 17 further characterized in that said solid component (B) is ball milled.
Claim 20
Dependent Claim
41 words
The catalyst of claim 17 further characterized in that the solid component (B) is treated with liquid Lewis acid selected from the group consisting of titanium tetrachloride and silicon tetrachloride at a temperature ranging from about 0° to about 170° C.
Claim 21
Dependent Claim
23 words
The catalyst of claim 19 further characterized in that said solid component (B) is ball milled subsequent to treatment with said Lewis acid.
Claim 22
Dependent Claim
23 words
The catalyst of claim 1 wherein the organoaluminum compound (A) comprises a trialkylaluminum containing 2 to about 12 carbon atoms per alkyl radical.
Claim 23
Dependent Claim
17 words
The catalyst of claim 21 further characterized in that said catalyst comprises at least one crystallinity promoter.
Claim 24
Dependent Claim
12 words
The catalyst of claim 22 wherein the organoaluminum compound (A) comprises triethylaluminum.
Claim 25
Dependent Claim
118 words
The catalyst of claim 1 wherein the components in (3) comprise (c) at least one pretreatment modifier selected from the group consisting of mineral acids and anhydrides of sulfur, organometallic chalcogenide derivatives of hydrogen sulfide in which each hydrogen is replaced by an organosilicon, organogermanium or organotin group wherein the organic radicals are selected from the group consisting of phenyl, alkyl-substituted phenyl, phenyl-substituted alkyl and alkyl radicals, said alkyl radicals containing 1 to about 6 carbon atoms, organic acids containing 1 to about 20 carbon atoms and 1 to about 4 carboxyl groups and C 1 to about C 12 alkyl and haloalkyl and C 6 to about C 10 aryl and haloaryl esters of said organic acids.
Claim 26
Dependent Claim
29 words
The catalyst of claim 24 wherein component (2) comprises an alkyl ester of benzoic acid or a halobenzoic acid, said alkyl radical containing 1 to about 6 carbon atoms.
Claim 27
Dependent Claim
47 words
The catalyst of claim 24 wherein component (3)(b) comprises a compound of the formula MR 3 m wherein M is aluminum, magnesium, or zinc, each R 3 is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.
Claim 28
Dependent Claim
48 words
The catalyst of claim 24 wherein component (3)(a) comprises a compound of the formula Mg(OR 1 ) n (OR 2 ) 2-n wherein R 1 and R 2 are identical or different hydrocarbyl radicals of 1 to about 20 carbon atoms and n ranges from 0 to 2.
Claim 29
Dependent Claim
13 words
The catalyst of claim 24 wherein the solid component (B) is mechanically activated.
Claim 30
Dependent Claim
38 words
The catalyst of claim 24 further characterized in that the solid component (B) is treated with at least one liquid Lewis acid having a high enough Lewis acidity to remove impurities from the surface of said solid component.
Claim 31
Dependent Claim
16 words
The catalyst of claim 29 further characterized in that said Lewis acid-treated solid is mechanically activated.
Claim 32
Dependent Claim
11 words
The catalyst of claim 24 wherein component (1) comprises titanium tetrachloride.
Claim 33
Dependent Claim
29 words
The catalyst of claim 31 wherein component (2) comprises an alkyl ester of benzoic acid or a halobenzoic acid, said alkyl radical containing 1 to about 6 carbon atoms.
Claim 34
Dependent Claim
47 words
The catalyst of claim 32 wherein component (3)(b) comprises a compound of the formula MR 3 m wherein M is aluminum, magnesium, or zinc, each R 3 is independently an alkyl radical of 1 to about 20 carbon atoms, and m corresponds to the valence of M.
Claim 35
Dependent Claim
35 words
The catalyst of claim 33 wherein component (3)(c) comprises sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, hydrogen sulfide, benzoic acid, a C 1 to about C 6 alkyl benzoate or halobenzoate, or a mixture thereof.
Claim 36
Dependent Claim
48 words
The catalyst of claim 34 wherein component (3)(a) comprises a compound of the formula Mg(OR 1 ) n (OR 2 ) 2-n wherein R 1 and R 2 are identical or different hydrocarbyl radicals of 1 to about 20 carbon atoms, and n ranges from 0 to 2.
Claim 37
Dependent Claim
41 words
The catalyst of claim 35 further characterized in that said solid component (B) is treated with at least one Lewis acid selected from the Group III-V metal halides which are in the liquid state at temperatures up to about 170° C.
Claim 38
Dependent Claim
11 words
The catalyst of claim 36 wherein component (2) comprises ethyl benzoate.
Claim 39
Dependent Claim
21 words
The catalyst of claim 37 wherein component (3)(b) comprises a trialkylaluminum containing 1 to about 6 carbon atoms per alkyl radical.
Claim 40
Dependent Claim
55 words
The catalyst of claim 38 wherein component (3)(a) comprises a compound of the formula Mg(OR 1 ) 2 wherein R 1 is an alkyl radical of 1 to about 6 carbon atoms, an aryl radical of 6 to about 12 carbon atoms or an alkaryl or aralkyl radical of 6 to about 12 carbon atoms.
Claim 41
Dependent Claim
14 words
The catalyst of claim 39 wherein component (3)(c) comprises chlorosulfonic acid and methyl benzoate.
Claim 42
Dependent Claim
10 words
The catalyst of claim 40 wherein component (3)(b) comprises triethylaluminum.
Claim 43
Dependent Claim
18 words
The catalyst of claim 41 wherein component (3) is prepared in the presence of at least one alpha-olefin.
Claim 44
Dependent Claim
10 words
The catalyst of claim 42 wherein the alphaolefin is propylene.
Claim 45
Dependent Claim
13 words
The catalyst of claim 42 wherein the solid component (B) is ball milled.
Claim 46
Dependent Claim
41 words
The catalyst of claim 42 further characterized in that the solid component (B) is treated with liquid Lewis acid selected from the group consisting of titanium tetrachloride and silicon tetrachloride at a temperature ranging from about 0° to about 170° C.
Claim 47
Dependent Claim
23 words
The catalyst of claim 45 further characterized in that said solid component (B) is ball milled subsequent to treatment with said Lewis acid.
Claim 48
Dependent Claim
16 words
The catalyst of claim 41 further characterized in that said solid component (B) is ball milled.
Claim 49
Dependent Claim
41 words
The catalyst of claim 41 further characterized in that the solid component (B) is treated with liquid Lewis acid selected from the group consisting of titanium tetrachloride and silicon tetrachloride at a temperature ranging from about 0° to about 170° C.
Claim 50
Dependent Claim
23 words
The catalyst of claim 48 further characterized in that said solid component (B) is ball milled subsequent to treatment with said Lewis acid.
Claim 51
Dependent Claim
18 words
The catalyst of claim 24 wherein component (3) is prepared in the presence of at least one alpha-olefin.
Claim 52
Dependent Claim
10 words
The catalyst of claim 50 wherein the alpha-olefin is propylene.
Claim 53
Dependent Claim
23 words
The catalyst of claim 24 wherein the organoaluminum compound (A) comprises a trialkylaluminum containing 2 to about 12 carbon atoms per alkyl radical.
Claim 54
Dependent Claim
17 words
The catalyst of claim 52 further characterized in that said catalyst comprises at least one crystallinity promoter.
Claim 55
Dependent Claim
12 words
The catalyst of claim 53 wherein the organoaluminum compound (A) comprises triethylaluminum.
Claim 56
Dependent Claim
141 words
A catalyst for the stereospecific polymerization of alpha-olefins of at least 3 carbon atoms comprising (A) triethylaluminum, triisobutylaluminum or a mixture thereof and (B) a solid component which is the reaction product of components comprising (1) titanium tetrachloride; (2) ethyl benzoate; and (3) a hydrocarbon-insoluble, magnesium-containing pretreatment product of components comprising (a) magnesium ethoxide; (b) triethylaluminum; (c) chlorosulfonic acid; and (d) methyl benzoate; wherein the atomic ratio of aluminum in (3)(b) to magnesium in (3)(a) ranges from about 0.005:1 to about 0.5:1, the molar ratio of component (3)(c) plus (3)(d) to component (3)(b) ranges from about 0.001:1 to about 2:1, the atomic ratio of titanium in component (1) to magnesium in component (3)(a) ranges from about 0.5:1 to about 20:1, and the ratio of component (2) to titanium in component (1) ranges from about 0.005 to about 0.6 mole per gram-atom.
Claim 57
Dependent Claim
141 words
A catalyst for the stereospecific polymerization of alpha-olefins of at least 3 carbon atoms comprising (A) triethylaluminum, triisobutylaluminum or a mixture thereof and (B) a solid component which is the reaction product of components comprising (1) titanium tetrachloride; (2) ethyl benzoate; and (3) a hydrocarbon-insoluble, magnesium-containing pretreatment product of components comprising (a) magnesium ethoxide; (b) triethylaluminum; (c) chlorosulfonic acid; and (d) methyl benzoate; wherein the atomic ratio of aluminum in (3)(b) to magnesium in (3)(a) ranges from about 0.005:1 to about 0.5:1, the molar ratio of component (3)(c) plus (3)(d) to component (3)(b) ranges from about 0.001:1 to about 2:1, the atomic ratio of titanium in component (1) to magnesium in component (3)(a) ranges from about 0.5:1 to about 20:1, and the ratio of component (2) to titanium in component (1) ranges from about 0.005 to about 0.6 mole per gram-atom.
Claim 58
Dependent Claim
18 words
The catalyst of claim 55 further characterized in that component (B) is prepared in the presence of propylene.
Claim 59
Dependent Claim
16 words
The catalyst of claim 55 further characterized in that the solid component (B) is ball milled.
Claim 60
Dependent Claim
24 words
The catalyst of claim 55 further characterized in that the solid component (B) is treated with titanium tetrachloride at 20° to about 135° C.
Claim 61
Dependent Claim
23 words
The catalyst of claim 58 further characterized in that the solid component (B) is ball milled subsequent to treatment with said titanium tetrachloride.
Claim 62
Dependent Claim
17 words
The catalyst of claim 59 further characterized in that said catalyst comprises at least one crystallinity promoter.
Claim 63
Dependent Claim
17 words
The catalyst of claim 55 further characterized in that said catalyst comprises at least one crystallinity promoter.
Claim 64
Dependent Claim
162 words
A process for preparing a catalyst component useful in the stereospecific polymerization of alpha-olefins having at least 3 carbon atoms comprising (A) contacting components comprising (1) at least one magnesium alcoholate, and (2) at least one Group II or IIIA metal alkyl in amounts such that the atomic ratio of metal in (2) to metal in (1) ranges from about 0.001:1 to about 1:1; (B) removing unreacted Group II or IIIA metal component from the product of (A) to form a solid, hydrocarbon-insoluble, magnesium-containing pretreatment product; and (C) contacting said pretreatment product with components comprising at least one titanium(IV) halide or haloalcoholate and at least one organic electron donor containing at least one of oxygen, nitrogen, sulfur and phosphorus, in amounts such that the atomic ratio of titanium to metal in (A)(1) is at least about 0.5:1 and the ratio of organic electron donor to titanium ranges from about 0.001 to about 1 mole per gram-atom, to form a solid catalyst component.
Claim 65
Dependent Claim
162 words
A process for preparing a catalyst component useful in the stereospecific polymerization of alpha-olefins having at least 3 carbon atoms comprising (A) contacting components comprising (1) at least one magnesium alcoholate, and (2) at least one Group II or IIIA metal alkyl in amounts such that the atomic ratio of metal in (2) to metal in (1) ranges from about 0.001:1 to about 1:1; (B) removing unreacted Group II or IIIA metal component from the product of (A) to form a solid, hydrocarbon-insoluble, magnesium-containing pretreatment product; and (C) contacting said pretreatment product with components comprising at least one titanium(IV) halide or haloalcoholate and at least one organic electron donor containing at least one of oxygen, nitrogen, sulfur and phosphorus, in amounts such that the atomic ratio of titanium to metal in (A)(1) is at least about 0.5:1 and the ratio of organic electron donor to titanium ranges from about 0.001 to about 1 mole per gram-atom, to form a solid catalyst component.
Claim 66
Dependent Claim
20 words
The process of claim 62 further characterized in that (A) is conducted in the presence of at least one alpha-olefin.
Claim 67
Dependent Claim
37 words
The process of claim 62 further characterized in that said solid catalyst component is contacted with at least one liquid Lewis acid having a high enough Lewis acidity to remove impurities from the surface of said solid.
Claim 68
Dependent Claim
21 words
The process of claim 64 further characterized in that said solid is mechanically activated subsequent to treatment with said Lewis acid.
Claim 69
Dependent Claim
16 words
The process of claim 62 further characterized in that said solid catalyst component is mechanically activated.
Claim 70
Dependent Claim
121 words
The process of claim 62 further characterized in that the components in (A) further comprise (3) at least one modifier selected from the group consisting of mineral acids and anhydrides of sulfur, organometallic chalcogenide derivatives of hydrogen sulfide in which each hydrogen is replaced by an organosilicon, organogermanium or organotin group wherein the organic radicals are selected from the group consisting of phenyl, alkyl-substituted phenyl, phenyl-substituted alkyl and alkyl radicals, said alkyl radicals containing 1 to about 6 carbon atoms, organic acids containing 1 to about 20 carbon atoms and 1 to about 4 carboxyl groups and C 1 to about C 12 alkyl and haloalkyl and C 6 to about C 10 aryl and haloaryl esters of said organic acids.
Claim 71
Dependent Claim
17 words
The process of claim 67 wherein (A) is conducted in the presence of at least one alpha-olefin.
Claim 72
Dependent Claim
37 words
The process of claim 67 further characterized in that said solid catalyst component is contacted with at least one liquid Lewis acid having a high enough Lewis acidity to remove impurities from the surface of said solid.
Claim 73
Dependent Claim
21 words
The process of claim 69 further characterized in that said solid is mechanically activated subsequent to treatment with said Lewis acid.
Claim 74
Dependent Claim
16 words
The process of claim 67 further characterized in that said solid catalyst component is mechanically activated.
Claim 75
Dependent Claim
40 words
The process of claim 67 wherein component (1) comprises magnesium ethoxide, component (2) comprises triethylaluminum, the titanium(IV) component comprises titanium tetrachloride, the organic electron donor component comprises ethyl benzoate, and the modifier component (3) comprises chlorosulfonic acid and methyl benzoate.
Claim 76
Dependent Claim
22 words
The process of claim 72 wherein the solid catalyst component is contacted with titanium tetrachloride at about 20° to about 135° C.
Claim 77
Dependent Claim
20 words
The process of claim 73 wherein the solid catalyst component is ball milled subsequent to treatment with said titanium tetrachloride.
Claim 78
Dependent Claim
13 words
The process of claim 72 wherein the solid catalyst component is ball milled.
Claim 79
Dependent Claim
14 words
The process of claim 72 wherein (A) is conducted in the presence of propylene.
Claim 80
Dependent Claim
22 words
The process of claim 76 wherein the solid catalyst component is contacted with titanium tetrachloride at about 20° to about 135° C.
Claim 81
Dependent Claim
20 words
The process of claim 77 wherein the solid catalyst component is ball milled subsequent to treatment with said titanium tetrachloride.
Claim 82
Dependent Claim
13 words
The process of claim 76 wherein the solid catalyst component is ball milled.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-07-06 | 1985-01-05 | 1985-07-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-07-06 | 1989-01-05 | 1989-07-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-07-06 | 1993-01-05 | 1993-07-07 | $7700.00 | Window Closed / Lapsed |