US4268418A
Expired / Lapsed
US
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Polymerization catalyst
Assignee: Enron Chemical Co
•
Filing: 1979-11-19
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Granted: 1981-05-19
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Expires: 1999-11-19
Abstract
Abstract A novel olefin polymerization and copolymerization catalyst and method is provided wherein the catalyst is prepared by mixing an alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, preferably of 1-6 carbon atoms, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer whereby a reaction product is formed on the particles, and evaporating the solvent. The catalyst is active in the presence of an organometallic co-catalyst.
Inventors
- 👤 Raymond E. Hoff
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 19:06
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
146 words
A supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst prepared by mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic and polycyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 2
Dependent Claim
146 words
A supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst prepared by mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic and polycyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 3
Dependent Claim
26 words
The catalyst of claim 1 wherein less than about 5% by weight of the total of said reaction product and said organic polymer particles comprises titanium.
Claim 4
Dependent Claim
24 words
The catalyst of claim 1 wherein about 0.1-10% by weight of the total of said reaction product and said organic polymer particles comprises titanium.
Claim 5
Dependent Claim
32 words
The catalyst of claim 1 wherein said lower alkyl aluminum halide is chosen from the group consisting essentially of di-lower alkyl aluminum halides, lower alkyl aluminum sesquihalides and lower alkyl aluminum dihalides.
Claim 6
Dependent Claim
15 words
The catalyst of claim 4 wherein said lower alkyl aluminum halide comprises ethyl aluminum sesquichloride.
Claim 7
Dependent Claim
13 words
The catalyst of claim 1 wherein said dialkyl magnesium compound comprises dibutyl magnesium.
Claim 8
Dependent Claim
13 words
The catalyst of claim 1 wherein said dialkyl magnesium compound comprises di-n-hexyl magnesium.
Claim 9
Dependent Claim
14 words
The catalyst of claim 1 wherein said dialkyl magnesium compound comprises butyl ethyl magnesium.
Claim 10
Dependent Claim
17 words
The catalyst of claim 1 wherein said dialkyl magnesium compound comprises a magnesium complex of trialkyl aluminum.
Claim 11
Dependent Claim
12 words
The catalyst of claim 1 wherein said titanium compound comprises titanium tetraisopropoxide.
Claim 12
Dependent Claim
12 words
The catalyst of claim 1 wherein said titanium compound comprises titanium tetrachloride.
Claim 13
Dependent Claim
14 words
The catalyst of claim 1 wherein said titanium compound comprises a titanium dialkoxy dihalide.
Claim 14
Dependent Claim
14 words
The catalyst of claim 12 wherein said titanium dialkoxy dihalide comprises titanium diisopropoxide dichloride.
Claim 15
Dependent Claim
41 words
The catalyst of claim 1 wherein said reactive materials are present in amounts to produce a quantity of said reaction product which is less than about 30 percent of the total weight of said reaction product and said organic polymer particles.
Claim 16
Dependent Claim
129 words
A supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic cocatalyst prepared by mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer consisting essentially of high density polyethylene which has chemically bonded to it between about 0.05 and about 30 weight percent of an organic carboxylic acid or acid anhydride to form a reaction product supported on said particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 17
Dependent Claim
129 words
A supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic cocatalyst prepared by mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer consisting essentially of high density polyethylene which has chemically bonded to it between about 0.05 and about 30 weight percent of an organic carboxylic acid or acid anhydride to form a reaction product supported on said particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 18
Dependent Claim
17 words
The catalyst of claim 15 wherein said organic polymer is an X-methyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride grafted polyethylene.
Claim 19
Dependent Claim
179 words
A supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst prepared by mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, said reactive materials being present in amounts to produce a quantity of said reaction product which is less than about 30 percent of the total weight of said reaction product and said organic polymer particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 20
Dependent Claim
179 words
A supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst prepared by mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, said reactive materials being present in amounts to produce a quantity of said reaction product which is less than about 30 percent of the total weight of said reaction product and said organic polymer particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 21
Independent Claim
149 words
The method of preparing a supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst comprising mixing reactive materials comprising a lower alkyl aluinum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic and polycyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 22
Independent Claim
149 words
The method of preparing a supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst comprising mixing reactive materials comprising a lower alkyl aluinum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic and polycyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 23
Dependent Claim
28 words
The catalyst preparation method of claim 18 wherein less than about 5% by weight of the total of said reaction product and said organic polymer particles comprises titanium.
Claim 24
Dependent Claim
26 words
The catalyst preparation method of claim 18 wherein about 0.1-10% by weight of the total of said reaction product and said organic polymer particles comprises titanium.
Claim 25
Dependent Claim
34 words
The catalyst preparation method of claim 18 wherein said lower alkyl aluminum halide is chosen from the group consisting essentially of di-lower alkyl aluminum halides, lower alkyl aluminum sesquihalides and lower alkyl aluminum dihalides.
Claim 26
Dependent Claim
17 words
The catalyst preparation method of claim 21 wherein said lower alkyl aluminum halide comprises ethyl aluminum sesquichloride.
Claim 27
Dependent Claim
15 words
The catalyst preparation method of claim 18 wherein said dialkyl magnesium compound comprises dibutyl magnesium.
Claim 28
Dependent Claim
15 words
The catalyst preparation method of claim 18 wherein said dialkyl magnesium compound comprises di-n-hexyl magnesium.
Claim 29
Dependent Claim
16 words
The catalyst preparation method of claim 18 wherein said dialkyl magnesium compound comprises butyl ethyl magnesium.
Claim 30
Dependent Claim
19 words
The catalyst preparation method of claim 18 wherein said dialkyl magnesium compound comprises a magnesium complex of trialkyl aluminum.
Claim 31
Dependent Claim
14 words
The catalyst preparation method of claim 18 wherein said titanium compound comprises titanium tetraisopropoxide.
Claim 32
Dependent Claim
14 words
The catalyst preparation method of claim 18 wherein said titanium compound comprises titanium tetrachloride.
Claim 33
Dependent Claim
16 words
The catalyst preparation method of claim 18 wherein said titanium compound comprises a titanium dialkoxy dihalide.
Claim 34
Dependent Claim
16 words
The catalyst preparation method of claim 29 wherein said titanium dialkoxy dihalide comprises titanium diisopropoxide dichloride.
Claim 35
Dependent Claim
42 words
The method of claim 18 wherein the quantities of said reactive materials and said organic polymer are regulated such that said reaction product is less than about 30 percent of the total weight of said reaction product and said organic polymer particles.
Claim 36
Independent Claim
133 words
The method of preparing a supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst comprising mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer consisting essentially of a high density polyethylene which has chemically bonded to it between about 0.05 and about 30 weight percent of an organic carboxylic acid or acid anhydride to form a reaction product supported on said particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 37
Independent Claim
133 words
The method of preparing a supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst comprising mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer consisting essentially of a high density polyethylene which has chemically bonded to it between about 0.05 and about 30 weight percent of an organic carboxylic acid or acid anhydride to form a reaction product supported on said particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 38
Dependent Claim
19 words
The catalyst preparation method of claim 32 wherein said organic polymer is an X-methyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride grafted polyethylene.
Claim 39
Independent Claim
184 words
The method of preparing a supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst comprising mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic and polycyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, regulating the quantities of said reactive materials and said organic polymer such that said reaction product is less than about 30 percent of the total weight of said reaction product and said organic polymer particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
Claim 40
Independent Claim
184 words
The method of preparing a supported olefin polymerization and copolymerization catalyst active in the presence of an organometallic co-catalyst comprising mixing reactive materials comprising a lower alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n X 4-n where R is an alkyl group, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer to form a reaction product supported on said particles, said particulate organic polymer comprising a graft copolymer of about 70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weight percent of at least one monomer selected from the group consisting of polymerizable cyclic and polycyclic ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides, regulating the quantities of said reactive materials and said organic polymer such that said reaction product is less than about 30 percent of the total weight of said reaction product and said organic polymer particles, and evaporating said solvent at a temperature which is less than the softening temperature of said organic polymer.
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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) | 1984-05-18 | 1984-11-17 | 1985-05-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-05-18 | 1988-11-17 | 1989-05-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-05-18 | 1992-11-17 | 1993-05-19 | $7700.00 | Window Closed / Lapsed |