US3865749A
Expired / Lapsed
US
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Butadiene polymerization catalyst
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1973-08-30
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Granted: 1975-02-11
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Expires: 1993-08-30
Abstract
Abstract Ziegler-type hydrocarbon-soluble catalyst systems for the polymerization of conjugated diolefins, or mixtures thereof, to obtain high molecular weight polymers possessing varying proportions of trans-1,4 units, in the range of 50-90%. The catalyst systems are based on a nonreduced salt of titanium, an organometallic compound, and an iodine-containing compound, or iodine corresponding to the generalized formula Ti(halide)4-MnImAlRaX3 a. M is aluminum or tetravalent tin, n is 0 or 1, m is the valence of M and when n is 0, m is 2, X is Cl, Br or I, a is 2 to 3, R is alkyl, halide is Cl, Br or I and when halide is I, MnIm is omitted.
Inventors
- 👤 Erik G M Tornqvist
- 👤 Charles Cozewith
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 09:00
CPC Classifications
C; C08; C08F; C08F36/00; C08F36/02; C08F36/04
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
157 words
A HYDROCARBON-SOLUBLE CATALYST SYSTEM FOR THE POLYMERIZATION OF CONJUGATED DIOLEFINS TO PRODUCE A POLYMER HAVING FROM 50 TO ABOUT 90% TRANS-1,4 ADDITION UNITS, CONSISTING ESSENTIALLY OF: A. TI(HALIDE)4-MNIM WHEREIN THE HALIDE MAY BE I, CL, OR BR; M IS ALUMINUM OR TETRAVALENT TIN; N IS 0 OR 1; M IS THE VALENCE OF M AND WHEN N IS 0, M IS 2; AND WHEN THE HALIDE IS I, MNIM IS OMITTED; B. AN ALUMINUM ALKYL HAVING THE FORMULA ALR2X3-A WHEREIN R IS AN ALKYL HAVING 1 TO 12 CARBON ATOMS, X IS CL, BR OR I, A IS A NUMBER 2 TO 3, AND THE MOLAR RATIO OF THE ALUMINUM ALKYL TO TI(HALIDE)4-MNIM BEING IN THE RANGE FROM 20:1 TO 1:1; C. A LEWIS BASE SELECTED FROM THE GROUP CONSISTING OF TETRAHYDROTHIOPHENE, TETRAHYDROTHIOPYRAN, TETRAHYDROFURAN, TETRAHYDROPYRAN, 2-METHYL TETRAHYDROTHIOPHENE AND 2,5DIMETHYL TETRAHYDROFURAN, THE MOLE RATIO OF LEWIS BASE TO TI(HALIDE)4 BEING IN THE RANGE OF FROM 1:1 TO 500:1.
Claim 2
Dependent Claim
157 words
A HYDROCARBON-SOLUBLE CATALYST SYSTEM FOR THE POLYMERIZATION OF CONJUGATED DIOLEFINS TO PRODUCE A POLYMER HAVING FROM 50 TO ABOUT 90% TRANS-1,4 ADDITION UNITS, CONSISTING ESSENTIALLY OF: A. TI(HALIDE)4-MNIM WHEREIN THE HALIDE MAY BE I, CL, OR BR; M IS ALUMINUM OR TETRAVALENT TIN; N IS 0 OR 1; M IS THE VALENCE OF M AND WHEN N IS 0, M IS 2; AND WHEN THE HALIDE IS I, MNIM IS OMITTED; B. AN ALUMINUM ALKYL HAVING THE FORMULA ALR2X3-A WHEREIN R IS AN ALKYL HAVING 1 TO 12 CARBON ATOMS, X IS CL, BR OR I, A IS A NUMBER 2 TO 3, AND THE MOLAR RATIO OF THE ALUMINUM ALKYL TO TI(HALIDE)4-MNIM BEING IN THE RANGE FROM 20:1 TO 1:1; C. A LEWIS BASE SELECTED FROM THE GROUP CONSISTING OF TETRAHYDROTHIOPHENE, TETRAHYDROTHIOPYRAN, TETRAHYDROFURAN, TETRAHYDROPYRAN, 2-METHYL TETRAHYDROTHIOPHENE AND 2,5DIMETHYL TETRAHYDROFURAN, THE MOLE RATIO OF LEWIS BASE TO TI(HALIDE)4 BEING IN THE RANGE OF FROM 1:1 TO 500:1.
Claim 3
Dependent Claim
11 words
The catalyst system of claim 1, wherein the Ti(halide)4-MnIm is TiI4.
Claim 4
Dependent Claim
11 words
The catalyst system of claim 1, wherein the Ti(halide)4-MnIm is TiCl4-I2.
Claim 5
Dependent Claim
11 words
The catalyst system of claim 1, wherein the Ti(halide)4-MnIm is TiCl4-AlI3.
Claim 6
Dependent Claim
11 words
The catalyst system of claim 1, wherein the Ti(halide)4-MnIm is TiCl4-SnI4.
Claim 7
Dependent Claim
11 words
The catalyst system of claim 1, wherein the Ti(halide)4-MnIm is TiBr4-SnI4.
Claim 8
Dependent Claim
13 words
The catalyst system of claim 1, wherein the aluminum alkyl is aluminum trialkyl.
Claim 9
Dependent Claim
12 words
The catalyst system of claim 1, wherein the Lewis base is tetrahydrothiophene.
Claim 10
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiCl4-AlI3; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiCl4-AlI3 being in the range of from 2:1 to 4:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-dimethyl tetrahydrofuran, the mole ratio of Lewis base to TiCl4 being in the range of 10:1 to 200:
Claim 11
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiCl4-AlI3; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiCl4-AlI3 being in the range of from 2:1 to 4:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-dimethyl tetrahydrofuran, the mole ratio of Lewis base to TiCl4 being in the range of 10:1 to 200:
Claim 12
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiI4; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiI4 being in the range of from 20:1 to 1:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-DIMETHYL tetrahydrofuran, the mole ratio of Lewis base to TiI4 being in the range of 10:1 to 200:
Claim 13
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiI4; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiI4 being in the range of from 20:1 to 1:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-DIMETHYL tetrahydrofuran, the mole ratio of Lewis base to TiI4 being in the range of 10:1 to 200:
Claim 14
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiCl4-I2; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiCl4-I2 being in the range of from 20:1 to 1:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-dimethyl tetrahydrofuran, the mole ratio of Lewis base to TiCl4 being in the range of 10:1 to 200:
Claim 15
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiCl4-I2; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiCl4-I2 being in the range of from 20:1 to 1:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-dimethyl tetrahydrofuran, the mole ratio of Lewis base to TiCl4 being in the range of 10:1 to 200:
Claim 16
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiCl4-SnI4; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiCl4-SnI4 being in the range of from 2:1 to 4:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-dimethyl tetrahydrofuran, the mole ratio of Lewis base to TiCl4 being in the range of 10:1 to 200:
Claim 17
Dependent Claim
72 words
A hydrocarbon-soluble catalyst system consisting essentially of: a. TiCl4-SnI4; b. an aluminum trialkyl where the alkyl has from 1-12 carbon atoms, the molar ratio of aluminum trialkyl to TiCl4-SnI4 being in the range of from 2:1 to 4:1; and c. a Lewis base selected from the group consisting of tetrahydrothiophene, tetrahydropyran, tetrahydrofuran, tetrahydrothiopyran, or 2,5-dimethyl tetrahydrofuran, the mole ratio of Lewis base to TiCl4 being in the range of 10:1 to 200:
References Cited (Backward Citations)
US3779944A
Cited
US3663450A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-02-10 | 1978-08-12 | 1979-02-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-02-10 | 1982-08-12 | 1983-02-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-02-10 | 1986-08-12 | 1987-02-11 | $7700.00 | Window Closed / Lapsed |