US4384087A
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Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst
Assignee: Phillips Petroleum Co
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Filing: 1981-08-20
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Granted: 1983-05-17
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Expires: 2001-08-20
Abstract
Abstract A transition metal compound and a metal halide compound selected from metal dihalide compounds and metal hydroxyhalide compounds are chemically combined to form a composition of matter. The composition of matter is suitable for use with an organometallic compound to produce an active olefin polymerization catalyst. Exceptionally high polymer yields are realized per gram of catalyst when the catalyst is treated with a halide ion exchanging source and used with an organometallic cocatalyst.
Inventors
- 👤 Charles E. Capshew
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 21:45
CPC Classifications
C; C08; C08F; C08F12/00; C08F12/02; C08F12/04; C08F12/06; C08F12/08; C08F10/00; C08F36/00; C08F36/02; C08F36/04; C08F4/00; C08F4/02; C08F4/022
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
224 words
A method for producing polymers comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated dienes, vinylaromatic compounds, and mixtures of any two or more thereof under polymerization conditions with a catalyst prepared by forming a first catalyst component by reacting (A) a metal halide selected from the group consisting of metal dihalides and metal hydroxyhalide compounds of Group IIA and IIB, and (B) a transition metal compound wherein the transition metal is titanium bonded to at least one radical selected from the group consisting of hydrocarbyl oxides, imides, amides, and mercaptides; and then reacting a solution of said first catalyst component with a second catalyst component selected from the group consisting of (a) 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 hydrocarbylaluminum halides; (b) metal halides and oxyhalides of Groups IIIA, IVA, IVB, and VB; (c) hydrogen halides; and (d) organic acid halides selected from the group consisting of compounds having the formula ##STR2## wherein R'" is an alkyl, aryl, or cycloalkyl group or combination thereof and X is a halide; and then treating the solid product resulting from the combination of said first and second catalyst components with a titanium tetrahalide capable of enhancing the activity of said catalyst.
Claim 2
Independent Claim
224 words
A method for producing polymers comprising contacting at least one polymerizable compound selected from the group consisting of aliphatic mono-1-olefins, conjugated dienes, vinylaromatic compounds, and mixtures of any two or more thereof under polymerization conditions with a catalyst prepared by forming a first catalyst component by reacting (A) a metal halide selected from the group consisting of metal dihalides and metal hydroxyhalide compounds of Group IIA and IIB, and (B) a transition metal compound wherein the transition metal is titanium bonded to at least one radical selected from the group consisting of hydrocarbyl oxides, imides, amides, and mercaptides; and then reacting a solution of said first catalyst component with a second catalyst component selected from the group consisting of (a) 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 hydrocarbylaluminum halides; (b) metal halides and oxyhalides of Groups IIIA, IVA, IVB, and VB; (c) hydrogen halides; and (d) organic acid halides selected from the group consisting of compounds having the formula ##STR2## wherein R'" is an alkyl, aryl, or cycloalkyl group or combination thereof and X is a halide; and then treating the solid product resulting from the combination of said first and second catalyst components with a titanium tetrahalide capable of enhancing the activity of said catalyst.
Claim 3
Dependent Claim
43 words
A process according to claim 1 wherein said catalyst is employed with a cocatalyst comprising an organometallic compound of Groups I, II, and III selected from the group consisting of lithium alkyls, Grignard reagents, dialkyl magnesium compounds, dialkyl zinc compounds, and hydrocarbylaluminum compounds.
Claim 4
Dependent Claim
53 words
A process according to claim 2 wherein said cocatalyst comprises at least one hydrocarbylaluminum compound represented by the general formulas R".sub.3 Al R"AlX.sub.2 R".sub.2 AlX R".sub.3 Al.sub.2 X.sub.3 wherein each R" is individually selected from linear and branched chain hydrocarbyl radicals containing 1 to 20 carbon atoms and X is a halogen atom.
Claim 5
Dependent Claim
13 words
A process according to claim 3 wherein said metal halide comprises magnesium dichloride.
Claim 6
Dependent Claim
39 words
A process according to claim 4 wherein said transition metal compound comprises a titanium compound of the formula Ti(OR).sub.4 wherein each R, which may be the same or different, is an alkyl radical containing 1 to 10 carbon atoms.
Claim 7
Dependent Claim
52 words
A process according to claim 5 wherein said second catalyst component is a hydrocarbylaluminum halide selected from those having formulas: RAlX.sub.2, R.sub.2 AlX, and R.sub.3 Al.sub.2 X.sub.3 wherein each R is individually selected from linear or branched chain hydrocarbyl radicals containing 1 to 20 carbon atoms and X is a halogen atom.
Claim 8
Dependent Claim
14 words
A method according to claim 6 wherein said second catalyst component comprises ethylaluminum sesquichloride.
Claim 9
Dependent Claim
19 words
A method according to claim 7 wherein said transition metal compound is selected from titanium tetraethoxide and titanium tetra-n-butoxide.
Claim 10
Dependent Claim
13 words
A method according to claim 8 wherein said titanium tetrahalide is titanium tetrachloride.
Claim 11
Dependent Claim
92 words
A method according to claim 9 wherein said transition metal compound is titanium tetraethoxide and wherein the reaction between (A) and (B) to form said first catalyst component is conducted in a hydrocarbon solvent, the first and second catalyst components are contacted together at a temperature within the range of about -100° C. to about 0° C., and the solid product resulting from the combination of the first and second catalyst components is contacted with the titanium tetrachloride at a temperature in the range of about 80° C. to about 180° C.
Claim 12
Dependent Claim
28 words
A method according to claim 10 wherein said first and second catalyst components are contacted together at a temperature in the range of -15° C. to -40° C.
Claim 13
Dependent Claim
39 words
A method according to claim 11 wherein the hydrocarbon solvent for said first catalyst component is aromatic and the treatment with titanium tetrachloride is conducted at a temperature in the range of about 100° C. to about 130° C.
Claim 14
Independent Claim
15 words
A method according to any one of claims 9-12 wherein said hydrocarbon solvent is xylene.
Claim 15
Dependent Claim
53 words
A method according to claim 13 wherein the molar ratio of the titanium of component (B) to the magnesium of component (A) is in the range of 10:1 to 1:10 and the molar ratio of the titanium of component (B) to the second catalyst component is in the range of 10:1 to 1:10.
Claim 16
Dependent Claim
20 words
A method according to claim 12 wherein the said molar ratios are 2:1 to 1:2 and 2:1 to 1:3 respectively.
Claim 17
Dependent Claim
40 words
A method according to claim 15 wherein the weight ratio of the titanium tetrachloride to the weight of the solid product resulting from the reaction of the first and second catalyst components is in the range of 7:1 to 1:4.
Claim 18
Dependent Claim
11 words
A method according to claim 10 wherein said cocatalyst is triethylaluminum.
Claim 19
Dependent Claim
25 words
A method according to claim 17 wherein the weight ratio of cocatalyst to the transition metal-containing catalyst is within the range of 4:1 to 40:1.
Claim 20
Dependent Claim
18 words
A method according to claim 18 wherein the polymerizable compound comprises at least about 90 weight percent ethylene.
Claim 21
Dependent Claim
28 words
A method according to claim 7 wherein said transition metal compound comprises orthopara cresyl titanate, wherein the molar ratio of butyl radicals to cresyl radicals is about 2:1.
Claim 22
Dependent Claim
16 words
A method according to claim 3 wherein said second catalyst component comprises a dialkyl magnesium compound.
Claim 23
Dependent Claim
13 words
A method according to claim 21 wherein said titanium tetrahalide is titanium tetrachloride.
References Cited (Backward Citations)
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| 3.5 Years (Year 4) | 1986-05-16 | 1986-11-15 | 1987-05-17 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-05-16 | 1990-11-15 | 1991-05-17 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-05-16 | 1994-11-15 | 1995-05-17 | $7700.00 | Window Closed / Lapsed |