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US3879366A
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Modification of polymer-lithium coupled with polyhalides
Assignee: Phillips Petroleum Co
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Filing: 1973-04-23
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Granted: 1975-04-22
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Expires: 1993-04-23
Abstract
Abstract In the preparation of conjugated diene polymers with multilithium initiators followed by termination with polyfunctional reagents, broader molecular weight distribution is obtained by modifying the polymerization reaction with a magnesium, calcium, strontium, or barium halide or hydrocarbylmetal halide.
Inventors
- 👤 Charles M Selman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 11:42
CPC Classifications
C; C08; C08F; C08F36/00; C08F36/02; C08F36/04; C08C; C08C19/00; C08C19/30; C08C19/42; C08C19/44
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
206 words
IN A PROCESS FOR PREPARING GEL-FREE COUPLED POLYMERS WHEREIN AT LEAST ONE POLYMERIZABLE MOMOMER IS POLYMERIZED WITH A MULTILITHIUM INITIATOR AND WHEREIN A POLYFUNCTIONAL COUPLING AGENT CONTAINING AT LEAST THREE REACTIVE SITES CAPABLE OF REACTING WITH A LITHIUM-CARBON BOND IN A POLYMER IS ADDED IN AN EFFECTIVE AMOUNT TO THE POLYMERIZATION REACTION AFTER INITIATION OF SAID POLYMERIZATION OF SAID MONOMER WITH SAID MULTILITHIUM INITIATOR AND PRIOR TO QUENCHING OF SAID POLYMERIZATION REACTION, THEREBY COUPLING SAID POLYMER, AND WHEREIN SAID POLYMERIZABLE MONOMER IS AT LEAST ONE CONJUGATED DIENE, AT LEAST ONE MONOVINYL-SUBSTITUTED AROMATIC COMPOUND, OR BOTH, THE IMPROVEMENT WHICH COMPRISES THE ADDITION TO THE POLYMERIZATION REACTION, AFTER CHARGING OF SAID POLYMERIZABLE MONOMER AND SAID MULTILITHIUM INITIATOR, OF A GROUP IIA METAL HALIDE OR HYDROCARBYLMETAL HALIDE MODIFIER WHEREIN THE GROUP IIA METAL THEREOF IS MAGNESIUM, CALCIUM, STRONTIUM, OR BARIUM, AND WHEREIN SAID MODIFIER IS EMPLOYED IN A RANGE OF ABOUT 1.25 TO 10 MILLIMOLES OF SAID MODIFIER PER EQUIVALENT OF LITHIUM IN SAID MULTILITHIUM INITIATOR, WHEREIN SAID MULTILITHIUM INITIATOR IS A LITHIUM METAL ADDUCT OF A CONJUGATED DIENE, A DILITHIUM ADDUCT OF A FUSED RING AROMATIC HYDROCARBON, OR IS REPRESENTED BY R''LI$ WHEREIN R'' IS A POLYVALENT HYDROCARBYL RADICAL WITH A VALENCE EQUAL TO THE VALUE OF X.
Claim 2
Dependent Claim
206 words
IN A PROCESS FOR PREPARING GEL-FREE COUPLED POLYMERS WHEREIN AT LEAST ONE POLYMERIZABLE MOMOMER IS POLYMERIZED WITH A MULTILITHIUM INITIATOR AND WHEREIN A POLYFUNCTIONAL COUPLING AGENT CONTAINING AT LEAST THREE REACTIVE SITES CAPABLE OF REACTING WITH A LITHIUM-CARBON BOND IN A POLYMER IS ADDED IN AN EFFECTIVE AMOUNT TO THE POLYMERIZATION REACTION AFTER INITIATION OF SAID POLYMERIZATION OF SAID MONOMER WITH SAID MULTILITHIUM INITIATOR AND PRIOR TO QUENCHING OF SAID POLYMERIZATION REACTION, THEREBY COUPLING SAID POLYMER, AND WHEREIN SAID POLYMERIZABLE MONOMER IS AT LEAST ONE CONJUGATED DIENE, AT LEAST ONE MONOVINYL-SUBSTITUTED AROMATIC COMPOUND, OR BOTH, THE IMPROVEMENT WHICH COMPRISES THE ADDITION TO THE POLYMERIZATION REACTION, AFTER CHARGING OF SAID POLYMERIZABLE MONOMER AND SAID MULTILITHIUM INITIATOR, OF A GROUP IIA METAL HALIDE OR HYDROCARBYLMETAL HALIDE MODIFIER WHEREIN THE GROUP IIA METAL THEREOF IS MAGNESIUM, CALCIUM, STRONTIUM, OR BARIUM, AND WHEREIN SAID MODIFIER IS EMPLOYED IN A RANGE OF ABOUT 1.25 TO 10 MILLIMOLES OF SAID MODIFIER PER EQUIVALENT OF LITHIUM IN SAID MULTILITHIUM INITIATOR, WHEREIN SAID MULTILITHIUM INITIATOR IS A LITHIUM METAL ADDUCT OF A CONJUGATED DIENE, A DILITHIUM ADDUCT OF A FUSED RING AROMATIC HYDROCARBON, OR IS REPRESENTED BY R''LI$ WHEREIN R'' IS A POLYVALENT HYDROCARBYL RADICAL WITH A VALENCE EQUAL TO THE VALUE OF X.
Claim 3
Dependent Claim
206 words
In a process for preparing gel-free coupled polymers wherein at least one polymerizable monomer is polymerized with a multilithium initiator and wherein a polyfunctional coupling agent containing at least three reactive siteS capable of reacting with a lithium-carbon bond in a polymer is added in an effective amount to the polymerization reaction after initiation of said polymerization of said monomer with said multilithium initiator and prior to quenching of said polymerization reaction, thereby coupling said polymer, and wherein said polymerizable monomer is at least one conjugated diene, at least one monovinyl-substituted aromatic compound, or both, the improvement which comprises the addition to the polymerization reaction, after charging of said polymerizable monomer and said multilithium initiator, of a Group IIA metal halide or hydrocarbylmetal halide modifier wherein the Group IIA metal thereof is magnesium, calcium, strontium, or barium, and wherein said modifier is employed in a range of about 1.25 to 10 millimoles of said modifier per equivalent of lithium in said multilithium initiator; wherein said multilithium initiator is a lithium metal adduct of a conjugated diene, a dilithium adduct of a fused ring aromatic hydrocarbon, or is represented by R''Lix wherein R'' is a polyvalent hydrocarbyl radical with a valence equal to the value of x.
Claim 4
Dependent Claim
206 words
In a process for preparing gel-free coupled polymers wherein at least one polymerizable monomer is polymerized with a multilithium initiator and wherein a polyfunctional coupling agent containing at least three reactive siteS capable of reacting with a lithium-carbon bond in a polymer is added in an effective amount to the polymerization reaction after initiation of said polymerization of said monomer with said multilithium initiator and prior to quenching of said polymerization reaction, thereby coupling said polymer, and wherein said polymerizable monomer is at least one conjugated diene, at least one monovinyl-substituted aromatic compound, or both, the improvement which comprises the addition to the polymerization reaction, after charging of said polymerizable monomer and said multilithium initiator, of a Group IIA metal halide or hydrocarbylmetal halide modifier wherein the Group IIA metal thereof is magnesium, calcium, strontium, or barium, and wherein said modifier is employed in a range of about 1.25 to 10 millimoles of said modifier per equivalent of lithium in said multilithium initiator; wherein said multilithium initiator is a lithium metal adduct of a conjugated diene, a dilithium adduct of a fused ring aromatic hydrocarbon, or is represented by R''Lix wherein R'' is a polyvalent hydrocarbyl radical with a valence equal to the value of x.
Claim 5
Dependent Claim
32 words
The process according to claim 1 wherein said modifier is added to said polymerization reaction at least one of incrementally and substantially continuously during at least a portion of said polymerization reaction.
Claim 6
Dependent Claim
96 words
The process according to claim 1 wherein said modifier can be represented by RaMXb wherein each R represents a hydrocarbyl radical containing up to 20 carbon atoms and each R is individually selected from alkyl, cycloalkyl, aryl, or combination, M is said metal of Group IIA, X is a halogen and is fluorine, chlorine, bromine, or iodine, a + b equals 2 and a is 0 or 1, and wherein said polyfunctional treating agent is added to said polymerization reaction after polymerization of said monomer with said multilithium initiator is substantially complete and prior to quenching.
Claim 7
Dependent Claim
49 words
The process according to claim 3 wherein said polyfunctional coupling agent containing at least three reactive sites is a polyepoxide, polyisocyanate, polyimine, polyaldehyde, polyketone, polyanhydride, polyester, polyhalide, or mixture, and is employed in a range of 0.1 to 1.5 equivalents of said polyfunctional treating agent per equivalent of lithium.
Claim 8
Dependent Claim
23 words
The process according to claim 1 employing at least about 2.5 milliequivalents of lithium per 100 gram of monomer employed in such polymerization.
Claim 9
Dependent Claim
45 words
A process according to claim 5 wherein said polymerization reaction is carried out in the presence of a diluent selected from hydrocarbons containing 4 to 12 carbon atoms per molecule, ethers, thioethers, tertiary amines of 2 to 30 carbon atoms per molecule, and mixtures thereof.
Claim 10
Dependent Claim
18 words
A process according to claim 3 wherein further is employed in said polymerization reaction an alkali metal alkoxide.
Claim 11
Dependent Claim
70 words
The process according to claim 4 wherein said multilithium initiator is said R''Lix wherein R'' contains up to 20 carbon atoms, has a valence equal to x, and is aliphatic, cycloaliphatic, aromatic, or combination, x is an integer of 2 to 6 inclusive, and wherein said multilithium initiator is employed in said polymerization process in an amount of 0.1 to 100 milliequivalents of lithium per 100 grams of polymerizable monomer.
Claim 12
Dependent Claim
33 words
The process according to claim 8 wherein said polymerizable conjugated diene contains 4 to 12 carbon atoms per molecule and said polymerizable vinyl-substituted aromatic compound contains 8 to 20 carbon atoms per molecule.
Claim 13
Dependent Claim
60 words
The process according to claim 9 wherein said polyepoxides are liquid epoxidized hydrocarbon polymers; said polyisocyanates can be represented by the formula R''''(NCO)m wherein R'''' is a polyvalent organic radical and is aliphatic, cycloaliphatic, or aromatic, containing from 2 to 30 carbon atoms, and m is an integer of at least 3; said polyimines can be represented by the formula
Claim 14
Dependent Claim
11 words
A process according to claim 10 wherein said RaMXb is RaMgXb.
Claim 15
Dependent Claim
14 words
The process according to claim 11 wherein said polyfunctional treating agent is silicon tetrahalide.
Claim 16
Dependent Claim
28 words
The process according to claim 12 wherein said multilithium initiator is a reaction product of divinylbenzene and sec-butyllithium, said modifier is magnesium chloride, and said monomer is 1,3-butadiene.
Claim 17
Dependent Claim
40 words
The process according to claim 9 wherein said polymerization reaction is conducted at a temperature of -50* C. to +150* C., under a pressure sufficient to maintain at least a portion of the polymerization reaction mixture in a liquid phase.
Claim 18
Dependent Claim
194 words
In a process for preparing gel-free coupled polymers wherein at least one polymerizable monomer is polymerized with a multilithium initiator and wherein a polyfunctional coupling agent containing at least three reactive sites capable of reacting with a lithium-carbon bond in a polymer is added to the polymerization reaction in an effective amount after initiation of said polymerization of said monomer with said multilithium initiator and prior to quenching of said polymerization reaction, thereby coupling said polymer, and wherein said polymerizable monomer is at least one conjugated diene, at least one monovinyl-substituted aromatic compound, or both, the improvement which comprises the addition to the polymerization reaction, after charging of said polymerizable monomer and said multilithium initiator, of a Group IIA metal halide or hydrocarbylmetal halide modifier in an amount effective to broaden the molecular weight distribution of said coupled polymer, wherein the Group IIA metal thereof is magnesium, calcium, strontium, or barium; wherein said multilithium initiator is a lithium metal adduct of a conjugated diene, a dilithium adduct of a fused ring aromatic hydrocarbon, or is represented by R''Lix wherein R'' is a polyvalent hydrocarbyl radical with a valence equal to the value of x.
Claim 19
Dependent Claim
194 words
In a process for preparing gel-free coupled polymers wherein at least one polymerizable monomer is polymerized with a multilithium initiator and wherein a polyfunctional coupling agent containing at least three reactive sites capable of reacting with a lithium-carbon bond in a polymer is added to the polymerization reaction in an effective amount after initiation of said polymerization of said monomer with said multilithium initiator and prior to quenching of said polymerization reaction, thereby coupling said polymer, and wherein said polymerizable monomer is at least one conjugated diene, at least one monovinyl-substituted aromatic compound, or both, the improvement which comprises the addition to the polymerization reaction, after charging of said polymerizable monomer and said multilithium initiator, of a Group IIA metal halide or hydrocarbylmetal halide modifier in an amount effective to broaden the molecular weight distribution of said coupled polymer, wherein the Group IIA metal thereof is magnesium, calcium, strontium, or barium; wherein said multilithium initiator is a lithium metal adduct of a conjugated diene, a dilithium adduct of a fused ring aromatic hydrocarbon, or is represented by R''Lix wherein R'' is a polyvalent hydrocarbyl radical with a valence equal to the value of x.
Claim 20
Dependent Claim
72 words
The process according to claim 15 employing as said polymerizable monomer at least one polymerizable conjugated diene and at least one copolymerizable monovinyl-substituted aromatic hydrocarbon, said polymerization is a random polymerization conducted in the presence of a randomizing amount of a polar organic compound randomizing agent, and wherein said modifier is employed in the range of about 0.75 to 10 millimoles of said modifier per equivalent of lithium in said multilithium initiator.
Claim 21
Dependent Claim
28 words
The process according to claim 16 employing said multilithium initiator in an amount sufficient to provide at least about 1.5 milliequivalents of lithium per 100 grams of monomer.
Claim 22
Dependent Claim
27 words
The process according to claim 17 wherein said polymerizable monomer is butadiene and styrene, said randomizer is potassium tert-butoxide, and said polyfunctional treating agent is silicon tetrachloride.
Claim 23
Dependent Claim
68 words
The process according to claim 15 employing as said polymerizable monomer at least one polymerizable conjugated diene, or at least one said conjugated diene and at least one copolymerizable monovinylsubstituted aromatic compound in the absence of a polar organic compound randomizing agent, and wherein said modifier is employed in the range of about 1.25 to 10 millimoles of said modifier per equivalent of lithium in said multilithium initiator.
Claim 24
Dependent Claim
28 words
The process according to claim 19 employing said multilithium initiator in an amount sufficient to provide at least about 2.5 milliequivalents of lithium per 100 grams of monomer.
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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) | 1978-04-21 | 1978-10-21 | 1979-04-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-04-21 | 1982-10-21 | 1983-04-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-04-21 | 1986-10-21 | 1987-04-22 | $7700.00 | Window Closed / Lapsed |