US4405769A
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US
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Catalyst, method of producing the catalyst, and polymerization process employing the catalyst
Assignee: Individual
•
Filing: 1982-02-22
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Granted: 1983-09-20
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Expires: 2002-02-22
Abstract
Abstract A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is rapidly mixed with a precipitating agent to form an active olefin polymerization catalyst.
Inventors
- 👤 Charles E. Capshew
- 👤 James N. Short
- 👤 M. Bruce Welch
- 👤 Richard E. Dietz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 14:28
CPC Classifications
C; C08; C08F; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/904
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
519 words
A process for producing a polyolefin comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated diolefins, and vinyl aromatic compounds under polymerization conditions with a cocatalyst comprising at least one organometallic compound selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table and a catalyst prepared by (A) preparing a first catalyst component by reacting in a suitable dry, essentially inert diluent reactants comprising (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group IIB metals of the Mendeleev Periodic Table; and (2) a transition metal compound in which the transition metal is selected from the group consisting of Group IVB and Group VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one radical selected from the group consisting of hydrocarbyloxides, amides, imides, and mercaptides; and (B) reacting a solution of said first catalyst component with a second catalyst component in the presence of an atmosphere of a polymerizable olefin monomer selected from the group consisting of aliphatic mono-1-olefins and conjugated dienes at a pressure in the range of about 1 to about 1,000 psia, wherein the molar ratio of the transition metal compound to the metal halide compound is in the range of about 10:1 to about 1:10, and wherein the concentration of the metal halide in said diluent is in the range of about 0.2 molar to about 1.2 molar, and wherein said second catalyst component comprises a precipitating agent selected from the group consisting of organometallic compounds of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and hydrocarbyl aluminum halides; metal halides and oxyhalides of metals of Groups IIIA, IVA, IVB, VA, and VB; hydrogen halides; and organic acid halides selected from the group consisting of compounds having the formula ##STR2## wherein R''' is an alkyl, aryl, or cycloalkyl group or combinations thereof and X is a halide, and wherein said precipitating agent is combined with said solution of said first catalyst component in either an undiluted form or as an admixture with a suitable essentially inert diluent, the concentration of said precipitating agent in said diluent being at least 0.2 molar, further wherein said solution of said first catalyst component and said second catalyst component are added together during an addition time of less than about two hours, and then (C) reacting the solid product resulting from step (B), which optionally has been reacted with a halide ion exchanging source selected from the group consisting of titanium tetrahalides, vanadium oxychloride, and zirconium tetrachloride, with a polymerizable olefin selected from aliphatic mono-1-olefins and conjugated dienes in the presence of an adequate amount of a cocatalyst selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table to produce a catalyst containing 1 to 50 weight percent prepolymer.
Claim 2
Dependent Claim
519 words
A process for producing a polyolefin comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated diolefins, and vinyl aromatic compounds under polymerization conditions with a cocatalyst comprising at least one organometallic compound selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table and a catalyst prepared by (A) preparing a first catalyst component by reacting in a suitable dry, essentially inert diluent reactants comprising (1) a metal halide compound selected from the group consisting of metal dihalide compounds and metal hydroxyhalide compounds and the metal of the metal halide compound is selected from the group consisting of Group IIA metals and Group IIB metals of the Mendeleev Periodic Table; and (2) a transition metal compound in which the transition metal is selected from the group consisting of Group IVB and Group VB transition metals of the Mendeleev Periodic Table and the transition metal is bonded to at least one radical selected from the group consisting of hydrocarbyloxides, amides, imides, and mercaptides; and (B) reacting a solution of said first catalyst component with a second catalyst component in the presence of an atmosphere of a polymerizable olefin monomer selected from the group consisting of aliphatic mono-1-olefins and conjugated dienes at a pressure in the range of about 1 to about 1,000 psia, wherein the molar ratio of the transition metal compound to the metal halide compound is in the range of about 10:1 to about 1:10, and wherein the concentration of the metal halide in said diluent is in the range of about 0.2 molar to about 1.2 molar, and wherein said second catalyst component comprises a precipitating agent selected from the group consisting of organometallic compounds of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and hydrocarbyl aluminum halides; metal halides and oxyhalides of metals of Groups IIIA, IVA, IVB, VA, and VB; hydrogen halides; and organic acid halides selected from the group consisting of compounds having the formula ##STR2## wherein R''' is an alkyl, aryl, or cycloalkyl group or combinations thereof and X is a halide, and wherein said precipitating agent is combined with said solution of said first catalyst component in either an undiluted form or as an admixture with a suitable essentially inert diluent, the concentration of said precipitating agent in said diluent being at least 0.2 molar, further wherein said solution of said first catalyst component and said second catalyst component are added together during an addition time of less than about two hours, and then (C) reacting the solid product resulting from step (B), which optionally has been reacted with a halide ion exchanging source selected from the group consisting of titanium tetrahalides, vanadium oxychloride, and zirconium tetrachloride, with a polymerizable olefin selected from aliphatic mono-1-olefins and conjugated dienes in the presence of an adequate amount of a cocatalyst selected from the group consisting of organometallic compounds of Groups I to III of the Periodic Table to produce a catalyst containing 1 to 50 weight percent prepolymer.
Claim 3
Dependent Claim
46 words
A process according to claim 1 wherein the cocatalysts for the polymerization and the prepolymerization can be the same or different and are selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, hydrocarbyl aluminum halides, and trihydrocarbyl aluminum compounds.
Claim 4
Dependent Claim
30 words
A process according to claim 2 wherein the solid product from step (C) is further treated with a halide ion exchanging source capable of enhancing the activity of the catalyst.
Claim 5
Dependent Claim
22 words
A method according to claim 3 wherein said halide ion exchanging source is selected from titanium tetrahalides, vanadium oxychloride, and zirconium tetrachloride.
Claim 6
Dependent Claim
31 words
A process according to claim 4 wherein said second catalyst component is selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and organoaluminum compounds.
Claim 7
Dependent Claim
42 words
A process according to claim 5 wherein said transition metal compound is selected from the group consisting of titanium tetraalkoxides of the formula Ti(OR) 4 wherein each R is individually selected from alkyl radicals containing 1 to 10 carbon atoms per radical.
Claim 8
Dependent Claim
13 words
A process according to claim 6 wherein said metal halide comprises magnesium dichloride.
Claim 9
Dependent Claim
15 words
A method according to claim 7 wherein the halide ion exchanging source is titanium tetrachloride.
Claim 10
Dependent Claim
13 words
A method according to claim 8 wherein said titanium tetraalkoxide is titanium tetraethoxide.
Claim 11
Dependent Claim
14 words
A process according to claim 9 wherein said precipitating agent comprises ethyl aluminum sesquichloride.
Claim 12
Dependent Claim
32 words
A method according to claim 10 wherein the addition time in step (C) is less than about 45 minutes and the catalyst produced contains about 3 to about 40 weight percent prepolymer.
Claim 13
Dependent Claim
17 words
A method according to claim 11 wherein the olefin employed to provide said olefin atmosphere is ethylene.
Claim 14
Dependent Claim
100 words
A method according to claim 12 wherein step (C) is conducted by contacting the product of step B with a polymerizable olefin consisting of aliphatic mono-1-olefins having 2 to 20 carbon atoms per molecule and conjugated dienes having from 4 to 8 carbon atoms per molecule in the presence of a cocatalyst comprising an organoaluminum compound selected from those having the formulas R' 2 AlX, RAlX 2 , and R' 3 Al 2 X 3 wherein R' is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to 20 carbon atoms and each X is a halogen atom.
Claim 15
Dependent Claim
16 words
A process according to claim 13 wherein said cocatalyst for step (C) consists essentially of triethylaluminum.
Claim 16
Dependent Claim
17 words
A process according to claim 14 wherein said polymerizable compound comprises at least 90 weight percent ethylene.
Claim 17
Dependent Claim
14 words
A process according to claim 14 wherein said polymerizable compound consists essentially of ethylene.
Claim 18
Dependent Claim
15 words
A process according to claim 9 wherein said precipitating agent comprises a dialkyl magnesium compound.
References Cited (Backward Citations)
US4187385A
Cited
US4158088A
Cited
GB2024832B
Cited
US4287328A
Cited
US4309521A
Cited
US4328121A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-09-19 | 1987-03-21 | 1987-09-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-09-19 | 1991-03-21 | 1991-09-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-09-19 | 1995-03-21 | 1995-09-20 | $7700.00 | Window Closed / Lapsed |