Patent US4530913A successfully refreshed from Google Patents.
US4530913A
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Polymerization catalyst and method
Assignee: Enron Chemical Co
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Filing: 1980-01-16
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Granted: 1985-07-23
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Expires: 2000-01-16
Abstract
Abstract A catalyst and method in which the catalyst is used with an aluminum cocatalyst in the polymerization and copolymerization of 1-olefins and is prepared by reacting a monofunctional organic silicon compound with silica, alumina, or the like followed by reacting the product of this reaction with a Group IIA organometallic compound or complex, then reacting this product with a halide or alkoxide of a metal of Group IVB or Group VB or mixtures thereof. If desired, the halide or alkoxide may be first reacted with the silicon compound reaction product before the reacting with the organometallic compound or complex.
Inventors
- 👤 Thomas J. Pullukat
- 👤 Raymond E. Hoff
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 17:41
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 50
Claim 1
Independent Claim
146 words
A solid catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins, and prepared by: (1) reacting a halogen free monofunctional organic silicon compound with silica or alumina having surface hydroxyl groups or a mixture thereof, said silicon compound being reactive with said surface hydroxyl groups; (2) reacting the product of (1) with a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures of these; or (2') reacting the product of (1) with an alkyl aluminum halide and a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium prior to (3); or (1') reacting the product of (1) with the halide or alkoxide of (3) prior to (2).
Claim 2
Dependent Claim
146 words
A solid catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins, and prepared by: (1) reacting a halogen free monofunctional organic silicon compound with silica or alumina having surface hydroxyl groups or a mixture thereof, said silicon compound being reactive with said surface hydroxyl groups; (2) reacting the product of (1) with a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures of these; or (2') reacting the product of (1) with an alkyl aluminum halide and a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium prior to (3); or (1') reacting the product of (1) with the halide or alkoxide of (3) prior to (2).
Claim 3
Dependent Claim
24 words
The catalyst of claim 1 wherein the metal of step (3) is in a concentration of about 0.1-20 weight percent of said solid product.
Claim 4
Dependent Claim
25 words
The catalyst of claim 1 wherein said Group IIA compound or complex of (2) comprises an alkyl or aryl of magnesium or a magnesium complex.
Claim 5
Dependent Claim
26 words
The catalyst of claim 1 wherein the weight ratio of the Group IIA metal compound to the Group IVB or VB metal compound is from 0.1-100.
Claim 6
Dependent Claim
12 words
The catalyst of claim 4 wherein said weight ratio is about 0.1-20.
Claim 7
Dependent Claim
22 words
The catalyst of claim 1 wherein one or more of said organometallic compounds contains a halide in addition to the organic moiety.
Claim 8
Dependent Claim
33 words
The catalyst of claim 1 wherein said reaction of (1) is with silica which has been predried at about 100°-200° C. for a time sufficient to remove surface water prior to said reaction.
Claim 9
Dependent Claim
27 words
The catalyst of claim 1 wherein said organic silicon compound in (1) is in stoichiometric excess thereby facilitating a complete reaction, and said excess is later removed.
Claim 10
Dependent Claim
21 words
The catalyst of claim 1 wherein the product of (1) is separated from any unreacted organic silicon compound and reaction by-products.
Claim 11
Dependent Claim
12 words
The catalyst of claim 9 wherein said separation is by vacuum suction.
Claim 12
Dependent Claim
20 words
The catalyst of claim 9 wherein said separation is by purging with a gas inert to the product of (1).
Claim 13
Dependent Claim
17 words
The catalyst of claim 9 wherein said separation is at a temperature between ambient and 200° C.
Claim 14
Dependent Claim
20 words
The catalyst of claim 1 wherein said cocatalyst is a trialkyl aluminum, an alkyl aluminum hydride or a mixture thereof.
Claim 15
Dependent Claim
34 words
The catalyst of claim 13 wherein said cocatalyst is an alkyl aluminum and the alkyl groups comprise hydrocarbon chains that are straight or branched and each chain contains about 1 to 10 carbon atoms.
Claim 16
Dependent Claim
13 words
The catalyst of claim 1 wherein said cocatalyst comprises an aryl aluminum compound.
Claim 17
Dependent Claim
21 words
The catalyst of claim 1 wherein said aluminum compound comprises an alkyl aluminum, an alkyl aluminum halide or a mixture thereof.
Claim 18
Dependent Claim
18 words
The catalyst of claim 1 wherein said aluminum compound comprises a trialkyl aluminum or an alkyl aluminum hydride.
Claim 19
Dependent Claim
25 words
The catalyst of claim 1 wherein the cocatalyst aluminum compound is in a molar ratio with the product of (3) of from 0.1-100 to 1.
Claim 20
Dependent Claim
14 words
The catalyst of claim 18 wherein said ratio is from about 1-20 to 1.
Claim 21
Independent Claim
148 words
The method of making a solid catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins by: (1) reacting a halogen free monofunctional organic silicon compound with silica or alumina having surface hydroxyl groups or a mixture thereof, said silicon compound being reactive with said surface hydroxyl groups; (2) reacting the product of (1) with a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures of these; or (2') reacting the product of (1) with an alkyl aluminum halide and a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium prior to (3); or (1') reacting the product of (1) with the halide or alkoxide of (3) prior to (2).
Claim 22
Independent Claim
148 words
The method of making a solid catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins by: (1) reacting a halogen free monofunctional organic silicon compound with silica or alumina having surface hydroxyl groups or a mixture thereof, said silicon compound being reactive with said surface hydroxyl groups; (2) reacting the product of (1) with a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures of these; or (2') reacting the product of (1) with an alkyl aluminum halide and a Group IIA organometallic compound, or complex of an alkyl aluminum compound, of magnesium or calcium prior to (3); or (1') reacting the product of (1) with the halide or alkoxide of (3) prior to (2).
Claim 23
Dependent Claim
24 words
The method of claim 20 wherein the metal of step (3) is in a concentration of about 0.1-20 weight percent of said solid product.
Claim 24
Dependent Claim
25 words
The method of claim 20 wherein said Group IIA compound or complex of (2) comprises an alkyl or aryl of magnesium or a magnesium complex.
Claim 25
Dependent Claim
26 words
The method of claim 20 wherein the weight ratio of the Group IIA metal compound to the Group IVB or VB metal compound is from 0.1-100.
Claim 26
Dependent Claim
12 words
The method of claim 23 wherein said weight ratio is about 0.1-20.
Claim 27
Dependent Claim
22 words
The method of claim 20 wherein one or more of said organometallic compounds contains a halide in addition to the organic moiety.
Claim 28
Dependent Claim
33 words
The method of claim 20 wherein said reaction of (1) is with silica which has been predried at about 100°-200° C. for a time sufficient to remove surface water prior to said reaction.
Claim 29
Dependent Claim
27 words
The method of claim 20 wherein said organic silicon compound in (1) is in stoichiometric excess thereby facilitating a complete reaction, and said excess is later removed.
Claim 30
Dependent Claim
21 words
The method of claim 20 wherein the product of (1) is separated from any unreacted organic silicon compound and reaction by-products.
Claim 31
Dependent Claim
12 words
The method of claim 28 wherein said separation is by vacuum suction.
Claim 32
Dependent Claim
20 words
The method of claim 28 wherein said separation is by purging with a gas inert to the product of (1).
Claim 33
Dependent Claim
17 words
The method of claim 28 wherein said separation is at a temperature between ambient and 200° C.
Claim 34
Dependent Claim
20 words
The method of claim 20 wherein said cocatalyst is a trialkyl aluminum, an alkyl aluminum hydride or a mixture thereof.
Claim 35
Dependent Claim
34 words
The method of claim 32 wherein said cocatalyst is an alkyl aluminum and the alkyl groups comprise hydrocarbon chains that are straight or branched and each chain contains about 1 to 10 carbon atoms.
Claim 36
Dependent Claim
13 words
The method of claim 20 wherein said cocatalyst comprises an aryl aluminum compound.
Claim 37
Dependent Claim
21 words
The method of claim 20 wherein said aluminum compound comprises an alkyl aluminum, an alkyl aluminum halide or a mixture thereof.
Claim 38
Dependent Claim
18 words
The method of claim 20 wherein said aluminum compound comprises a trialkyl aluminum or an alkyl aluminum hydride.
Claim 39
Dependent Claim
25 words
The method of claim 20 wherein the cocatalyst aluminum compound is in a molar ratio with the product of (3) of from 0.1-100 to 1.
Claim 40
Dependent Claim
14 words
The method of claim 37 wherein said ratio is from about 1-20 to 1.
Claim 41
Dependent Claim
23 words
The catalyst of claim 1 wherein the Group IIA metal of (2) comprises magnesium and the reaction of (3) is performed with titanium.
Claim 42
Dependent Claim
23 words
The method of claim 20 wherein the Group IIA metal of (2) comprises magnesium and the reaction of (3) is performed with titanium.
Claim 43
Dependent Claim
82 words
A catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins, and prepared by: (1) reacting a halogen free monofunctional organic silicon compound with silica or alumina or a mixture thereof; (2) reacting the product of (1) with a Group IIA organometallic compound or complex of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures thereof to produce a solid catalyst product.
Claim 44
Dependent Claim
82 words
A catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins, and prepared by: (1) reacting a halogen free monofunctional organic silicon compound with silica or alumina or a mixture thereof; (2) reacting the product of (1) with a Group IIA organometallic compound or complex of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures thereof to produce a solid catalyst product.
Claim 45
Independent Claim
84 words
The method of making a catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins by: (1) reacting a halogen free organic monofunctional silicon compound with silica of alumina or a mixture thereof; (2) reacting the product of (1) with a Group IIA organometallic compound or complex of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures thereof to produce a solid catalyst product.
Claim 46
Independent Claim
84 words
The method of making a catalyst for use with an alkyl or aryl aluminum compound cocatalyst in the polymerization and copolymerization of 1-olefins by: (1) reacting a halogen free organic monofunctional silicon compound with silica of alumina or a mixture thereof; (2) reacting the product of (1) with a Group IIA organometallic compound or complex of magnesium or calcium; and (3) reacting the product of (2) with a halide or alkoxide of titanium, vanadium, zirconium or mixtures thereof to produce a solid catalyst product.
Claim 47
Dependent Claim
59 words
A solid polymerization catalyst component prepared by mixing: (a) a support obtained by reacting silica having surface hydroxyl groups with a halogen free monofunctional silylating compound which is reactive with said surface hydroxyl groups, with (b) an organomagnesium compound including a component of the formula MgR 2 where R is a hydrocarbon radical, and (c) a tetravalent titanium compound.
Claim 48
Dependent Claim
59 words
A solid polymerization catalyst component prepared by mixing: (a) a support obtained by reacting silica having surface hydroxyl groups with a halogen free monofunctional silylating compound which is reactive with said surface hydroxyl groups, with (b) an organomagnesium compound including a component of the formula MgR 2 where R is a hydrocarbon radical, and (c) a tetravalent titanium compound.
Claim 49
Independent Claim
65 words
A method of making a solid polymerization catalyst component by the steps of mixing (a) a support obtained by reacting silica having surface hydroxyl groups with a halogen free monofunctional silylating compound which is reactive with said surface hydroxyl groups, with (b) an organomagnesium compound including a component of the formula MgR 2 wherein R is a hydrocarbon radical, and (c) a tetravalent titanium compound.
Claim 50
Independent Claim
65 words
A method of making a solid polymerization catalyst component by the steps of mixing (a) a support obtained by reacting silica having surface hydroxyl groups with a halogen free monofunctional silylating compound which is reactive with said surface hydroxyl groups, with (b) an organomagnesium compound including a component of the formula MgR 2 wherein R is a hydrocarbon radical, and (c) a tetravalent titanium compound.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-07-22 | 1989-01-21 | 1989-07-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-07-22 | 1993-01-21 | 1993-07-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-07-22 | 1997-01-21 | 1997-07-23 | $7700.00 | Window Closed / Lapsed |