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US4067929A
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Promoters in the polymerization of monovinyl-aromatic compounds with primary lithium initiators
Assignee: Phillips Petroleum Co
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Filing: 1976-06-14
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Granted: 1978-01-10
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Expires: 1996-06-14
Abstract
Abstract 1,1-DIALKYLETHYLENES, SUCH AS ISOBUTENE, PROMOTE THE PRIMARY LITHIUM INITIATED POLYMERIZATION OF MONOVINYL-AROMATIC COMPOUNDS, SUCH AS STYRENE, EITHER IN HOMOPOLYMERIZATIONS, OR IN THE FORMATION OF A-B-A block copolymers or (A-B) a Z radial block copolymers, such as by sequential monomer addition with conjugated dienes.
Inventors
- 👤 Daniel H. Willis
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 18:15
CPC Classifications
C; C08; C08G; C08G81/00; C08G81/02; C08G81/021; C08G81/022; C08F; C08F12/00; C08F297/00; C08F297/02; C08F297/04; C08F297/044; Y; Y10; Y10S; Y10S525/00; Y10S525/901
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
183 words
A process for the preparation of a block copolymer which comprises the steps of polymerizing under solution polymerization conditions a first monomer charge selected from monovinyl-substituted aromatic hydrocarbons of 8 to 12 carbon atoms per molecule employing a primary hydrocarbyl lithium initiator and a 1,1-dialkylethylene promoter of the formula ##STR2## wherein each R is hydrogen, methyl, or ethyl, effective to promote the polymerization of said first monomer with said primary hydrocarbyl lithium initiator, employing a ratio of said promoter:primary hydrocarbyl lithium initiator in the range of about 50:1 to 7500:1, thereafter, after substantially complete polymerization of said first monovinyl-substituted aromatic hydrocarbon and prior to termination adding to the polymerization admixture a second monomer charge selected from conjugated dienes of 4 to 12 carbon atoms per molecule, and polymerizing said so added conjugated diene monomer, thereafter, prior to termination, adding to the polymerization admixture a polyfunctional treating agent in an amount in the range of about 0.1-1.5 equivalents per equivalent of lithium, thereby preparing a coupled branched polymer, wherein the weight ratio of polymerization first monomer:second monomer is in the range of about 10-50:90-50.
Claim 2
Dependent Claim
183 words
A process for the preparation of a block copolymer which comprises the steps of polymerizing under solution polymerization conditions a first monomer charge selected from monovinyl-substituted aromatic hydrocarbons of 8 to 12 carbon atoms per molecule employing a primary hydrocarbyl lithium initiator and a 1,1-dialkylethylene promoter of the formula ##STR2## wherein each R is hydrogen, methyl, or ethyl, effective to promote the polymerization of said first monomer with said primary hydrocarbyl lithium initiator, employing a ratio of said promoter:primary hydrocarbyl lithium initiator in the range of about 50:1 to 7500:1, thereafter, after substantially complete polymerization of said first monovinyl-substituted aromatic hydrocarbon and prior to termination adding to the polymerization admixture a second monomer charge selected from conjugated dienes of 4 to 12 carbon atoms per molecule, and polymerizing said so added conjugated diene monomer, thereafter, prior to termination, adding to the polymerization admixture a polyfunctional treating agent in an amount in the range of about 0.1-1.5 equivalents per equivalent of lithium, thereby preparing a coupled branched polymer, wherein the weight ratio of polymerization first monomer:second monomer is in the range of about 10-50:90-50.
Claim 3
Dependent Claim
82 words
The process according to claim 1 wherein the polymer resulting from said polymerization of said first monomer can be represented by A-Li; the polymer resulting from the polymerization of said second monomer can be represented by A-B-Li; the coupled polymer resulting from polyfunctional treating agent can be represented by (A-B) a Z wherein a represents the number of copolymer branches, Z the coupling agent residue, each A a block of polymerized first monomer, and each B a block of polymerized second monomer.
Claim 4
Dependent Claim
26 words
The process of claim 2 wherein the treating agent has a functionality of at least three such that the coupled polymer is a radial block copolymer.
Claim 5
Dependent Claim
36 words
The process of claim 3 wherein said monovinyl-substituted aromatic monomer is styrene; said conjugated diene is butadiene; said 1,1-dialkylethylene is isobutene; said primary hydrocarbyl lithium initiator in n-butyllithium; and said polyfunctional treating agent is silicon tetrachloride.
Claim 6
Dependent Claim
165 words
A process which comprises polymerizing at least one first monomer which is a polymerizable monovinyl-substituted aromatic compound monomer with a primary hydrocarbyl lithium polymerization initiator and a 1,1-dialkylethylene promoter under solution polymerization conditions of temperature and pressure, wherein said process employs an amount of said promoter effective to promote said polymerization of said monovinyl-substituted aromatic monomer with primary hydrocarbyl lithium initiator, and said 1,1dialkylethylene promoter contains up to 8 carbon atoms per molecule, after substantially complete polymerization of said first monomer and prior to termination, polymerizing at least one second monomer which is a polymerizable conjugated diene monomer, and polymerizing said conjugated diene monomer to substantially complete conversion, and thereafter and prior to termination adding to the resulting polymerization admixture a polyfunctional treating agent in an effective coupling amount, wherein said polyfunctional treating agent is a polyepoxide, polyisocyanate, polyamine, polyaldehyde, polyketone, polyanhydride, polyester, polyhalide, polyvinyl aromatic, carbon monoxide, carbon dioxide, or monoester, and wherein the functionality of said polyfunctional treating agent is at least two.
Claim 7
Dependent Claim
165 words
A process which comprises polymerizing at least one first monomer which is a polymerizable monovinyl-substituted aromatic compound monomer with a primary hydrocarbyl lithium polymerization initiator and a 1,1-dialkylethylene promoter under solution polymerization conditions of temperature and pressure, wherein said process employs an amount of said promoter effective to promote said polymerization of said monovinyl-substituted aromatic monomer with primary hydrocarbyl lithium initiator, and said 1,1dialkylethylene promoter contains up to 8 carbon atoms per molecule, after substantially complete polymerization of said first monomer and prior to termination, polymerizing at least one second monomer which is a polymerizable conjugated diene monomer, and polymerizing said conjugated diene monomer to substantially complete conversion, and thereafter and prior to termination adding to the resulting polymerization admixture a polyfunctional treating agent in an effective coupling amount, wherein said polyfunctional treating agent is a polyepoxide, polyisocyanate, polyamine, polyaldehyde, polyketone, polyanhydride, polyester, polyhalide, polyvinyl aromatic, carbon monoxide, carbon dioxide, or monoester, and wherein the functionality of said polyfunctional treating agent is at least two.
Claim 8
Dependent Claim
37 words
The process according to claim 5 wherein said monovinyl-substituted aromatic hydrocarbon monomer is styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, alpha-methylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 3-fluorostyrene, or 4-methoxystyrene, and wherein said conjuated diene monomer is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, or 2-phenyl-1,3-butadiene.
Claim 9
Dependent Claim
25 words
The process according to claim 5 wherein said 1,1-dialkylethylene promoter is represented by the formula: ##STR3##wherein each R is selected from hydrogen, methyl, or ethyl.
Claim 10
Dependent Claim
31 words
The process according to claim 7 wherein said effective amount of said 1,1-dialkylethylene is in the range of about 50:1 to 7500:1 weight ratio relative to said primary hydrocarbyl lithium compound.
Claim 11
Dependent Claim
18 words
The process according to claim 8 wherein said 1,1-dialkylethylene is isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-ethyl-1-butene, 2-ethyl-1-pentene, 2-propyl-1-pentene, or mixture.
Claim 12
Dependent Claim
57 words
The process according to claim 5 wherein said primary hydrocarbyl lithium compound is represented by R'(CH 2 Li) x wherein R' is a valence bond, hydrogen, saturated aliphatic radical, monoolefinic aliphatic radical, which radicals can be aromatic or saturated cycloaliphatic substituted, x is an integer of 1 to 4, and R' contains 1 to 18 carbon atoms.
Claim 13
Dependent Claim
28 words
The process according to claim 10 wherein said primary hydrocarbyl lithium compound is methyllithium, ethyllithium, n-propyllithium, n-butyllithium, n-dodecyllithium, 4-phenylbutyllithium, 4-cyclohexylbutyllithium, 1,2-dilithioethane, 1,4-dilithiobutane, 1,4-dilithio-2-butene, 1,10-dilithiodecane, 1,20-dilithioeicasane, 1,3-dilithio-2(lithiomethyl)-propane, or 1,4-dilithio-2,3-di(lithiomethyl)butane.
Claim 14
Dependent Claim
45 words
The process according to claim 5 wherein said functionality is at least 3, such that the resulting coupled polymer is a radial block copolymer wherein the weight ratio of polymerized monovinylaromatic compound monomer to polymerized conjugated diene monomer is in the ratio of about 5-50:95-50.
Claim 15
Dependent Claim
22 words
The process according to claim 5 wherein employed a ratio of said 1,1-dialkylethylene promoter:said primary hydrocarbon/lithium initiator of about 150:1 to 1000:1.
Claim 16
Dependent Claim
43 words
The process according to claim 13 wherein said polymerization conditions include a polymerization temperature in the range of about 0° to 150° C., and under a pressure sufficient to maintain polymerization components substantially in the liquid phase, and polymerization in a polymerization diluent.
Claim 17
Dependent Claim
16 words
The process according to claim 12 wherein said activator is isobutylene and said initiator is n-butyllithium.
Claim 18
Dependent Claim
46 words
The process according to claim 12 employing styrene as said first monovinyl-substituted aromatic monomer, butadiene as said conjugated diene, and styrene as said second monovinyl-substituted aromatic monomer, such that the resulting block copolymer is a block copolymer wherein a represents the functionality of said treating agent.
Claim 19
Dependent Claim
14 words
The process according to claim 16 wherein a is in the range of 3-7.
Claim 20
Dependent Claim
18 words
The process according to claim 17 wherein said polyfunctional treating agent is a polyhalide and is silicon tetrachloride.
Claim 21
Dependent Claim
141 words
A process which comprises polymerizing at least one polymerizable monovinyl-substituted aromatic compound with a primary hydrocarbyl lithium polymerization initiator and a 1,1-dialkylethylene promoter under solution polymerization conditions of temperature and pressure, wherein said process employs an amount of said promoter effective to promote said polymerization of said monovinyl-substituted aromatic compound with said primary hydrocarbyl lithium initiator, and said 1,1-dialkylethylene promoter contains up to 8 carbon atoms per molecule, adding to the polymerization admixture at least one polymerizable conjugated diene monomer, after substantially complete polymerization of said monovinyl-substituted aromatic compound and prior to termination, and polymerizing said conjugated diene monomer to substantially complete conversion, and adding to said polymerization admixture prior to termination a polyfunctional treating agent selected from polyhalides in an effective coupling amount, wherein the functionality of said polyfunctional treating agent is at least two, thereby preparing a coupled polymer.
Claim 22
Dependent Claim
141 words
A process which comprises polymerizing at least one polymerizable monovinyl-substituted aromatic compound with a primary hydrocarbyl lithium polymerization initiator and a 1,1-dialkylethylene promoter under solution polymerization conditions of temperature and pressure, wherein said process employs an amount of said promoter effective to promote said polymerization of said monovinyl-substituted aromatic compound with said primary hydrocarbyl lithium initiator, and said 1,1-dialkylethylene promoter contains up to 8 carbon atoms per molecule, adding to the polymerization admixture at least one polymerizable conjugated diene monomer, after substantially complete polymerization of said monovinyl-substituted aromatic compound and prior to termination, and polymerizing said conjugated diene monomer to substantially complete conversion, and adding to said polymerization admixture prior to termination a polyfunctional treating agent selected from polyhalides in an effective coupling amount, wherein the functionality of said polyfunctional treating agent is at least two, thereby preparing a coupled polymer.
Claim 23
Dependent Claim
37 words
The process according to claim 19 wherein the resulting coupled polymer has a weight ratio of about 5 to 50 for the copolymerized monovinyl-substituted aromatic compound, and about 95 to 50 for the copolymerized conjugated diene monomer.
Claim 24
Dependent Claim
29 words
The process according to claim 20 wherein said monovinyl-substituted aromatic compound is styrene, said conjugated diene is butadiene, and said polyhalide is a silicon polyhalide and is silicon tetrachloride.
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) | 1981-01-09 | 1981-07-11 | 1982-01-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-01-09 | 1985-07-11 | 1986-01-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-01-09 | 1989-07-11 | 1990-01-10 | $7700.00 | Window Closed / Lapsed |