US3896102A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Preparation of polybutadiene
Assignee: Phillips Petroleum Co
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Filing: 1974-04-25
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Granted: 1975-07-22
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Expires: 1994-04-25
Abstract
Abstract 1,3-Butadiene is polymerized employing a four-component catalyst comprising: (a) an organoaluminum hydride; (b) an organolithium or organosodium compound; (c) a titanium halide component; and (d) an ether.
Inventors
- 👤 Floyd E Naylor
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 22:01
CPC Classifications
C; C08; C08F; C08F136/00; C08F136/02; C08F136/04; C08F136/06
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
188 words
A METHOD FOR POLYMERIZING 1,3-BUTADIENE COMPRISING CONTACTING 1,3-BUTADIENE UNDER POLYMERIZATION CONDITIONS WITH A FOUR-COMPONENT CATALYST COMPRISING, A. AN ORGANOALUMINUM HYDRIDE REPRESENTED BY THE GENERAL FORMULA RAALHB WHEREIN R IS ALKYL, CYCLOALKYL OR MIXTURES THEREOF CONTAINING FROM ABOUT 1 TO 16 CARBON ATOMS, A IS AN INTEGER FROM 1 TO 2, B IS AN INTEGER FROM 1 TO 2 SUCH THAT THE SUM OF A PLUS B EQUALS 3, B. AN ORGANOLITHIUM OR ORGANOSODIUM COMPOUND REPRESENTED BY THE GENERAL FORMULA R''MX WHEREIN X IS AN INTEGER FROM 1 TO 4, R'' IS A HYDROCARBON RADICAL SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND CYCLOALIPHATIC RADICALS CONTAINING FROM ABOUT 1 TO 20 CARBON ATOMS PER RADICAL AND M IS LITHIUM OR SODIUM, C. A TITANIUM HALIDE COMPONENT SELECTED FROM THE GROUP CONSISTING OF TITANIUM TERACHLORIDE PLUS MOLECULAR IODINE, TITANIUM TETRABROMIDE PLUS MOLECULAR IODINE, AND TITANIUM TETRAIODIDE, AND D. AN ETHER REPRESENTED BY THE GENERAL FORMULA R"OR''" WHEREIN R" AND R''" ARE ALKYL OR CYCLOALKYL GROUPS CONTAINING FROM ABOUT 1 TO 12 CARBON ATOMS PER R" OR R''" GROUP AND WHEREIN THE ETHER CONTAINS UP TO 20 CARBON ATOMS PER MOLECULE.
Claim 2
Independent Claim
188 words
A METHOD FOR POLYMERIZING 1,3-BUTADIENE COMPRISING CONTACTING 1,3-BUTADIENE UNDER POLYMERIZATION CONDITIONS WITH A FOUR-COMPONENT CATALYST COMPRISING, A. AN ORGANOALUMINUM HYDRIDE REPRESENTED BY THE GENERAL FORMULA RAALHB WHEREIN R IS ALKYL, CYCLOALKYL OR MIXTURES THEREOF CONTAINING FROM ABOUT 1 TO 16 CARBON ATOMS, A IS AN INTEGER FROM 1 TO 2, B IS AN INTEGER FROM 1 TO 2 SUCH THAT THE SUM OF A PLUS B EQUALS 3, B. AN ORGANOLITHIUM OR ORGANOSODIUM COMPOUND REPRESENTED BY THE GENERAL FORMULA R''MX WHEREIN X IS AN INTEGER FROM 1 TO 4, R'' IS A HYDROCARBON RADICAL SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND CYCLOALIPHATIC RADICALS CONTAINING FROM ABOUT 1 TO 20 CARBON ATOMS PER RADICAL AND M IS LITHIUM OR SODIUM, C. A TITANIUM HALIDE COMPONENT SELECTED FROM THE GROUP CONSISTING OF TITANIUM TERACHLORIDE PLUS MOLECULAR IODINE, TITANIUM TETRABROMIDE PLUS MOLECULAR IODINE, AND TITANIUM TETRAIODIDE, AND D. AN ETHER REPRESENTED BY THE GENERAL FORMULA R"OR''" WHEREIN R" AND R''" ARE ALKYL OR CYCLOALKYL GROUPS CONTAINING FROM ABOUT 1 TO 12 CARBON ATOMS PER R" OR R''" GROUP AND WHEREIN THE ETHER CONTAINS UP TO 20 CARBON ATOMS PER MOLECULE.
Claim 3
Dependent Claim
109 words
The method of claim 1 wherein the mole ratio of the organolithium or organosodium compound to the organoaluminum hydride is in the range of from about 1:1 to 1:3; wherein the mole ratio of the titanium tetrahalide in the titanium halide component to the organoaluminum hydride is in the range of from about 1:1 to 0.1:1; wherein the mole ratio of titanium tetrachloride or titanium tetrabromide to molecular iodine is in the range of from about 1:1 to 0.1:1; and wherein the amount of the ether present during the polymerization is in the range of from about 0.01 to 30 parts by weight per hundred parts by weight butadiene.
Claim 4
Dependent Claim
79 words
The method of claim 2 wherein the mole ratio of the organolithium or organosodium compound to the organoaluminum hydride is in the range of from about 1:1 to 1:1.5; wherein the mole ratio of the titanium tetrahalide in the titanium halide component to the organoaluminum hydride is in the range of from about 0.5:1 to 0.2:1; wherein the mole ratio of titanium tetrachloride or titanium tetrabromide to molecular iodine is in the range of from about 0.5:1 to 0.33:1.
Claim 5
Dependent Claim
40 words
The method of claim 3 wherein the amount of total catalyst present during the polymerization based on the organoaluminum compound is in the range of from about 0.3 to 30 gram millimoles of organoaluminum compound per hundred grams of butadiene.
Claim 6
Dependent Claim
40 words
The method of claim 4 wherein the amount of total catalyst present during the polymerization based on the organoaluminum compound is in the range of from about 0.5 to 10 gram millimoles of organoaluminum compound per hundred grams of butadiene.
Claim 7
Dependent Claim
84 words
The method of claim 1 wherein the polymerization is carried out in the presence of a diluent which is not detrimental to the polymerization process; wherein the concentration of butadiene in the diluent is in the range of from about 1 to 200 weight percent; wherein the polymerization is carried out at a temperature in the range of from about 0* to 120*C; and wherein the polymerization is carried out at a pressure sufficient to maintain the polymerization mixture substantially in the liquid phase.
Claim 8
Dependent Claim
78 words
The method of claim 5 wherein the polymerization is carried out in the presence of a diluent selected from the group consisting of paraffins, cycloparaffins, and mixtures thereof containing 4 to 8 carbon atoms, wherein the concentration of butadiene in the diluent is in the range of from about 5 to 50 weight percent, wherein the temperature is in the range of from about 30* to 80* C, and wherein the polymerization is carried out at autogenous pressure.
Claim 9
Dependent Claim
42 words
The method of claim 7 wherein the diluent is n-hexane or cyclohexane, the organoaluminum compound is diethyl aluminum hydride, the organolithium compound is normal or secondary butyllithium, the titanium halide component is titanium tetrachloride plus molecular iodine, and ether is dimethyl ether.
Claim 10
Dependent Claim
17 words
The method of claim 1 wherein butadiene is polymerized to produce polybutadiene containing a substantial trans content.
Claim 11
Dependent Claim
20 words
The method of claim 9 wherein the trans content is in the range of from about 60 to 95 percent.
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) | 1978-07-21 | 1979-01-20 | 1979-07-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-07-21 | 1983-01-20 | 1983-07-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-07-21 | 1987-01-20 | 1987-07-22 | $7700.00 | Window Closed / Lapsed |