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US4137391A Expired / Lapsed US ⏱️ 0.0 years remaining

Continuous solution polymerization of a conjugated diene with a monovinylaromatic compound using alkoxysilicon treating agents in the first reactor means of a reactor series

Assignee: Phillips Petroleum Co
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Filing: 1976-09-10
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Granted: 1979-01-30
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Expires: 1996-09-10
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Abstract

Abstract Processable substantially random conjugated diene/monovinylaromatic compound copolymers are produced by continuous polymerization employing an alkoxysilicon treating agent in the first of a series of reactor means.

Inventors

  • 👤 Richard L. Smith
  • 👤 Ralph C. Farrar

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-06 02:58
CPC Classifications
C; C08; C08F; C08F236/00; C08F236/02; C08F236/04; C08F236/10

Claims Analysis

Total Claims: 24
Claim 1
Independent Claim 193 words
A process for preparing a rubbery substantially random copolymer which comprises polymerizing monomers selected from at least one polymerizable conjugated diene with at least one copolymerizable monovinyl-substituted aromatic compound under solution polymerization conditions of temperature, pressure, diluent, an organolithium initiator, and at least one randomizing agent in an amount sufficient to substantially randomize the copolymerization of said conjugated diene and said monovinyl-substituted aromatic compound, wherein said polymerization process is conducted as a substantially continuous polymerization process employing at least two reactor means of which the first and optionally at least one second reactor means function as polymerization reactor means and the last as a terminating reactor means, wherein said conjugated diene, said monovinylaromatic compound, said organolithium initiator, said randomizing agent, said diluent, and at least one alkoxysilicon treating agent, are added to said first reactor means to form a polymerization mixture, wherein said polymerization of said monomers is substantially complete when said polymerization mixture enters said terminating reactor means, and said random copolymer is withdrawn as product from said last reactor means, wherein said alkoxysilicon treating agent is employed in an amount effective to substantially increase the processability of said random copolymer product.
Claim 2
Dependent Claim 193 words
A process for preparing a rubbery substantially random copolymer which comprises polymerizing monomers selected from at least one polymerizable conjugated diene with at least one copolymerizable monovinyl-substituted aromatic compound under solution polymerization conditions of temperature, pressure, diluent, an organolithium initiator, and at least one randomizing agent in an amount sufficient to substantially randomize the copolymerization of said conjugated diene and said monovinyl-substituted aromatic compound, wherein said polymerization process is conducted as a substantially continuous polymerization process employing at least two reactor means of which the first and optionally at least one second reactor means function as polymerization reactor means and the last as a terminating reactor means, wherein said conjugated diene, said monovinylaromatic compound, said organolithium initiator, said randomizing agent, said diluent, and at least one alkoxysilicon treating agent, are added to said first reactor means to form a polymerization mixture, wherein said polymerization of said monomers is substantially complete when said polymerization mixture enters said terminating reactor means, and said random copolymer is withdrawn as product from said last reactor means, wherein said alkoxysilicon treating agent is employed in an amount effective to substantially increase the processability of said random copolymer product.
Claim 3
Dependent Claim 31 words
The process according to claim 1 wherein said conjugated diene contains 4 to 12 carbon atoms per molecule, and said copolymerizable monovinylaromatic compound contains 8 to 20 carbon atoms per molecule.
Claim 4
Dependent Claim 37 words
The process according to claim 2 wherein said conjugated diene is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, or mixture; and wherein said monovinylaromatic compound is styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenylbutyl)styrene, or mixture.
Claim 5
Dependent Claim 36 words
The process according to claim 3 wherein said resulting copolymer represents the copolymerization of about 95 to 50 parts by weight of said conjugated diene and 5 to 50 parts by weight of said monovinylaromatic compound.
Claim 6
Dependent Claim 25 words
The process according to claim 4 employing said alkoxysilicon treating agent in a range of about 0.1 to 2 milliequivalents per 100 grams of monomer.
Claim 7
Dependent Claim 22 words
The process according to claim 5 wherein said conjugated diene is provided, at least in part, by a low concentration diene stream.
Claim 8
Dependent Claim 16 words
The process according to claim 1 wherein said organolithium initiator is a multifunctional species or compound.
Claim 9
Dependent Claim 38 words
The process according to claim 1 wherein said organolithium initiator is represented by R(Li) x wherein R is a hydrocarbon radical of 1 to 20 carbon atoms per molecule, and x is an integer of 1 to 4.
Claim 10
Dependent Claim 49 words
The process according to claim 8 wherein said organolithium compound is selected from the group consisting of methyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-decyllithium, phenyllithium, naphthyllithium, 4-butylphenyllithium, p-tolyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyllithium, dilithiomethane, 1,4-dilithiobutane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,4-dilithiocyclohexane, 1,4-dilithio-2-butene, 1,8-dilithio-3-decene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,2-dilithio-1,8-diphenyloctane, 1,3,5,-trilithiopentane, 1,5,15-trilithioeicosane, 1,3,5-trilithiocyclohexane, 1,3,5,8-tetralithiodecane, 1,5,10,20-tetralithioeicosane, 1,2,4,6-tetralithiocyclohexane, and 4,4'-dilithiobiphenyl.
Claim 11
Dependent Claim 28 words
The process according to claim 5 employing said organolithium initiator in an amount sufficient to provide about 0.2 to 5 milliequivalents of lithium per 100 grams of monomer.
Claim 12
Dependent Claim 40 words
The process according to claim 10 wherein said randomizing agent is a polar organic compound and is an ether, thioether, amine, alkali metal salt, or an alkali metal salt plus a hexaalkylphosphoramide, wherein said alkali metal is other than lithium.
Claim 13
Dependent Claim 40 words
The process according to claim 11 wherein said randomizing agent is a said alkali metal salt and is a potassium salt of an alcohol, and is employed in an amount sufficient to provide about 0.25:1 to 100:1 Li:K atom ratio.
Claim 14
Dependent Claim 56 words
The process according to claim 12 wherein said conjugated diene is butadiene, said monovinylaromatic compound is styrene, said hydrocarbon diluent comprises cyclohexane, said initiator is a 1,3-butadiene-solubilized multilithium initiator prepared from divinylbenzene and n-butyllithium, said randomizer is potassium t-amyloxide, said alkoxysilicon treating agent is tetraethoxysilane, and said polymerization reaction mixture further is terminated with silicon tetrachloride.
Claim 15
Dependent Claim 21 words
The process according to claim 13 wherein said butadiene is provided at least in part by a low concentration diene stream.
Claim 16
Dependent Claim 58 words
The process according to claim 1 further comprising the steps of terminating the polymerization with about 0.01 to 4.5 milliequivalents per 100 grams of monomer employed in said polymerization of a multivinylaromatic compound, multiepoxide, multiisocyanate, multiimine, multialdehyde, multiketone, multianhydride, multiester of a monocarboxylic acid with a polyalcohol, multihalide, or diester of a monohydric alcohol with a dicarboxylic acid.
Claim 17
Dependent Claim 37 words
The process according to claim 15 wherein said multihalide is a silicon, lead, germanium, or tin multihalide, employed in an amount sufficient to provide about 0.01 to 1.5 milliequivalents of branching agent per 100 grams of monomer.
Claim 18
Dependent Claim 18 words
The process according to claim 5 wherein said alkoxysilicon treating agent is an alkoxysilane, disiloxane, disilane, or mixture.
Claim 19
Dependent Claim 41 words
The process according to claim 17 wherein said alkoxysilicon treating agent is a said alkoxysilane represented by R' x --Si--(OR') 4-x wherein each R' is a hydrocarbyl radical of 1 to 12 carbon atoms, and x is 0, 1, or 2.
Claim 20
Dependent Claim 19 words
The process according to claim 18 wherein said alkoxysilane is dimethyldimethoxysilane, phenyltriethoxysilane, tetraethoxysilane, n-dodecyltrimethoxysilane, cyclohexyltriethoxysilane, di-n-propyldibenzyloxysilane, p-tolyltriethoxysilane, or mixture.
Claim 21
Dependent Claim 14 words
The process according to claim 17 wherein said alkoxysilicon treating agent is a disiloxane.
Claim 22
Dependent Claim 11 words
The process according to claim 20 wherein said disiloxane is hexaethoxydisiloxane.
Claim 23
Dependent Claim 32 words
The process according to claim 17 wherein said alkoxysilicon treating agent is a disilane represented by ##STR2## wherein each R' is a hydrocarbyl radical of 1 to 12 carbon atoms per R'.
Claim 24
Dependent Claim 11 words
The process according to claim 22 wherein said disilane is hexaethoxydisilane.

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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) 1982-01-29 1982-07-31 1983-01-30 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1986-01-29 1986-07-31 1987-01-30 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1990-01-29 1990-07-31 1991-01-30 $7700.00 Window Closed / Lapsed

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