US4943616A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Living cationic polymerization process
Assignee: Polysar Ltd
•
Filing: 1989-12-04
•
Granted: 1990-07-24
•
Expires: 2009-12-04
Abstract
Abstract A polymerization process is provided for producing a terminally functional polymer which comprises introducing a monomer charge, a Lewis acid and an organic peroxy compound into a suitable reaction vessel and polymerizing the monomer charge at a temperature of from about 0 DEG to about -80 DEG C. to form the terminally functional polymer, wherein the monomer charge comprises isobutylene and the organic peroxy compound is charged in an amount of from about 10-4 to about 10-1 moles per mole of the isobutylene. In a preferred embodiment, the monomer charge additionally comprises vinylidene aromatic or diolefin monomers. In another preferred embodiment the monomer charge comprises the sequential addition of isobutylene and vinylidene aromatic or diolefin monomers. In a further preferred embodiment said reaction vessel is additionally charged with an electron door having an electron door number of from about 22 to about 50 the amount of said electron door being from about 10-4 to about 10-1 moles of said isobutylene. The invention also provides a novel catalyst system comprising an organic peroxy compund and a Lewis acid for the polymerization of isobutylene or monomer mixtures containing isobutylene.
Inventors
- 👤 Munmaya K. Mishra
- 👤 Akhtar Osman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 17:39
CPC Classifications
C; C08; C08F; C08F210/00; C08F210/04; C08F210/08; C08F210/10; C08F10/00; C08F10/04; C08F10/08; C08F10/10; Y; Y10; Y10S; Y10S525/00; Y10S525/918
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
122 words
A living cationic polymerization process for producing a terminally functional polymer which comprises introducing a monomer charge, a Lewis acid and an organic peroxy compound selected from the group consisting of organic peroxide, organic hydroperoxide, peroxy carbonate, azo peroxy compound and peroxy esters into a suitable reaction vessel and polymerizing the monomer charge at a temperature of from about 0 degrees to about -80 degrees centigrade to form said terminally functional polymer, wherein said monomer charge comprises the sequential addition of isobutylene and a second monomer selected from the group consisting of conjugated diolefins and vinylidene aromatic monomers and said organic peroxy compound is charged in an amount of from 10 -4 to about 10 -1 moles per mole of said isobutylene.
Claim 2
Dependent Claim
122 words
A living cationic polymerization process for producing a terminally functional polymer which comprises introducing a monomer charge, a Lewis acid and an organic peroxy compound selected from the group consisting of organic peroxide, organic hydroperoxide, peroxy carbonate, azo peroxy compound and peroxy esters into a suitable reaction vessel and polymerizing the monomer charge at a temperature of from about 0 degrees to about -80 degrees centigrade to form said terminally functional polymer, wherein said monomer charge comprises the sequential addition of isobutylene and a second monomer selected from the group consisting of conjugated diolefins and vinylidene aromatic monomers and said organic peroxy compound is charged in an amount of from 10 -4 to about 10 -1 moles per mole of said isobutylene.
Claim 3
Dependent Claim
22 words
The process of claim 1, wherein said monomer charge is polymerized at a temperature of from about -40° to about -80° C.
Claim 4
Dependent Claim
22 words
The process of claim 1, wherein said organic peroxy compound is selected from the group consisting of peroxy esters and peroxy carbonates.
Claim 5
Dependent Claim
24 words
The process of claim 3, wherein said organic peroxy compound is a peroxy ester selected from the group consisting of α-cumylperoxypivalate, α-cumylperoxyneoheptanoate and 2,5-dimethyl-2,5-bis(benzoyl-peroxyhexane).
Claim 6
Dependent Claim
23 words
The process of claim 3, wherein said organic peroxy compound is a peroxy carbonate selected from the group consisting of o,o-t-butyl-o-isopropylmonoperoxycarbonate and o,o-t-butyl-o-(2-ethylhexyl)monoperoxycarbonate.
Claim 7
Dependent Claim
33 words
The process of claim 3, wherein the second monomer charge comprises a C 4 to C 8 conjugated diolefin in an amount of up to 60 mole percent of the total monomer charge.
Claim 8
Dependent Claim
11 words
The process of claim 6, wherein said conjugated diolefin is isoprene.
Claim 9
Dependent Claim
35 words
The process of claim 3, wherein the second monomer charge comprises a C 8 to C 20 vinylidene aromatic monomer in an amount of up to about 60 mole percent of the total monomer charge.
Claim 10
Dependent Claim
22 words
The process of claim 8, wherein said vinylidene aromatic monomer is selected from the group consisting of styrene, p-methylstyrene, 2,4,6-trimethylstyrene and indene.
Claim 11
Dependent Claim
46 words
The process of claim 3, wherein said Lewis acid is selected from the group consisting of BCl 3 , BF 3 , AlCl 3 , SnCl 4 , TiCl 4 , SbF 5 , SeCl 3 , ZnCl 2 , FeCl 3 and VCl 4 .
Claim 12
Dependent Claim
18 words
The process of claim 10, wherein said Lewis acid is selected from BCl 3 and TiCl 4 .
Claim 13
Dependent Claim
12 words
The process of claim 3, conducted in the presence of a diluent.
Claim 14
Dependent Claim
68 words
The process of claim 12 wherein said diluent is selected from the group consisting of C 1 to C 4 halogenated hydrocarbons, C 5 to C 8 aliphatic hydrocarbons, C 5 to C 10 cyclic hydrocarbons, mixtures of said halogenated hydrocarbons, mixtures of one of said halogenated hydrocarbons and one of said aliphatic hydrocarbons and mixtures of one of said halogenated hydrocarbons and one of said cyclic hydrocarbons.
Claim 15
Dependent Claim
21 words
The process of claim 13, wherein said diluent is selected from methyl chloride, methylene chloride, hexane and cyclohexane and mixtures thereof.
Claim 16
Dependent Claim
121 words
The process of claim 3, wherein said monomer charge comprises the sequential addition of isobutylene and a second monomer selected from the group consisting of isoprene, styrene, p-methylstyrene 2,4,6-trimethylstyrene and indene the amount of said second monomer charge being up to 60 mole percent of the total monomer charge, said Lewis acid is one of BCl 3 and TiCl 4 , said organic peroxy compound is a peroxy ester selected from the group consisting of α-cumylperoxy pivalate, α-cumylperoxy-neoheptanoate and 2,5-dimethyl-2,5-bis (benzoylperoxyhexane), the amount of said Lewis acid being from about 3 to about 40 moles per mole of said peroxy compound and a diluent is present selected from the group consisting of methyl chloride, methylene chloride, hexane, cyclohexane or mixtures thereof.
Claim 17
Dependent Claim
182 words
A living cationic polymerization process for producing a terminally functional polymer which comprises introducing a monomer charge, a Lewis acid, a peroxide or a hydroperoxide selected from the group consisting of 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, di(t-butyl) peroxide, t-butyl cumyl peroxide, di(cumyl) peroxide), t-amyl hydroperoxide, 2,5-di(hydroperoxy)-2,5-dimethyl-hexane, 3,3-dimethyl-2-methylhydroperoxybutene-1,2,7-di-(hydroperoxy)-2,7-dimethyloctane, diphenylhydroperoxymethane, benzyl hydroperoxide, p-methylhydroperoxytoluene, p-dicumyl dihydroperoxide, 1-isopropyl-3,5-dicumyl dihydroperoxide, cumylmethyl peroxide, triphenyl methyl hydroperoxide and bis-(m-2-hydroperoxy-2-propyl-alpha-cumyl) peroxide and an electron doner into a suitable reaction vessel and polymerizing the monomer charge at a temperature of from 0 degrees to about -80 degrees centigrade to form said terminally functional polymer, wherein said monomer charge comprises isobutylene, said peroxide or hydroperoxide is charged in an amount of from 10 -4 to about 10 -1 moles per mole of said isobutylene, and said electron donor is selected from the group consisting of electron donors having an electron donor number of from about 22 to about 50 and tetrahydrothiophene whose electron donor number is not presently known to us, the amount of said donor being from about 10 -4 to about 10 -1 moles per mole of isobutylene.
Claim 18
Dependent Claim
182 words
A living cationic polymerization process for producing a terminally functional polymer which comprises introducing a monomer charge, a Lewis acid, a peroxide or a hydroperoxide selected from the group consisting of 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, di(t-butyl) peroxide, t-butyl cumyl peroxide, di(cumyl) peroxide), t-amyl hydroperoxide, 2,5-di(hydroperoxy)-2,5-dimethyl-hexane, 3,3-dimethyl-2-methylhydroperoxybutene-1,2,7-di-(hydroperoxy)-2,7-dimethyloctane, diphenylhydroperoxymethane, benzyl hydroperoxide, p-methylhydroperoxytoluene, p-dicumyl dihydroperoxide, 1-isopropyl-3,5-dicumyl dihydroperoxide, cumylmethyl peroxide, triphenyl methyl hydroperoxide and bis-(m-2-hydroperoxy-2-propyl-alpha-cumyl) peroxide and an electron doner into a suitable reaction vessel and polymerizing the monomer charge at a temperature of from 0 degrees to about -80 degrees centigrade to form said terminally functional polymer, wherein said monomer charge comprises isobutylene, said peroxide or hydroperoxide is charged in an amount of from 10 -4 to about 10 -1 moles per mole of said isobutylene, and said electron donor is selected from the group consisting of electron donors having an electron donor number of from about 22 to about 50 and tetrahydrothiophene whose electron donor number is not presently known to us, the amount of said donor being from about 10 -4 to about 10 -1 moles per mole of isobutylene.
Claim 19
Dependent Claim
22 words
The process of claim 16, wherein said monomer charge is polymerized at a temperature of from about -40° to about -80° C.
Claim 20
Dependent Claim
27 words
The process of claim 16, wherein said organic peroxy compound is selected from the group consisting of t-butyl hydroperoxide, cumene hydroperoxide, p-dicumyl dihydroperoxide and triphenyl methyl hydroperoxide.
Claim 21
Dependent Claim
18 words
The process of claim 18, wherein said organic peroxy compound is selected from cumene hydroperoxide and p-dicumyl dihydroperoxide.
Claim 22
Dependent Claim
46 words
The process of claim 16, wherein said Lewis acid is selected from the group consisting of BCl 3 , BF 3 , AlCl 3 , SnCl 4 , TiCl 4 , SbF 5 , SeCl 3 , ZnCl 2 , FeCl 3 and VCl 4 .
Claim 23
Dependent Claim
22 words
The process of claim 20, wherein said Lewis acid is selected from the group consisting of BCl 3 and TiCl 4 .
Claim 24
Dependent Claim
12 words
The process of claim 16, conducted in the presence of a diluent.
Claim 25
Dependent Claim
68 words
The process of claim 22 wherein said diluent is selected from the group consisting of C 1 to C 4 halogenated hydrocarbons, C 5 to C 8 aliphatic hydrocarbons, C 5 to C 10 cyclic hydrocarbons, mixtures of said halogenated hydrocarbons, mixtures of one of said halogenated hydrocarbons and one of said aliphatic hydrocarbons and mixtures of one of said halogenated hydrocarbons and one of said cyclic hydrocarbons.
Claim 26
Dependent Claim
21 words
The process of claim 23, wherein said diluent is selected from methyl chloride, methylene chloride, hexane and cyclohexane and mixtures thereof.
Claim 27
Dependent Claim
105 words
The process of claim 16, wherein said Lewis acid is one of BCl 3 and TiCl 4 , said organic peroxy compound is one of cumene hydroperoxide and p-dicumyl dihydroperoxide, said electron donor is one of dimethyl sulfoxide, diethylene glycol dimethyl ether (diglyme) and tetrahydrothiophene, the amount of said Lewis acid being from about 3 to about 40 moles per mole of said peroxy compound, the amount of said electron donor being from about 2×10 -1 about 3 moles per mole of said peroxy compound and a diluent is present selected from the group consisting of methyl chloride, methylene chloride, hexane, cyclohexane or mixtures thereof.
Claim 28
Dependent Claim
31 words
The process of claim 16, wherein said monomer charge comprises the sequential addition of isobutylene and a second monomer selected from the group consisting of conjugated diolefins and vinylidene aromatic monomers.
Claim 29
Dependent Claim
22 words
The process of claim 26, wherein said monomer charge is polymerized at a temperature of from about -40° to about -80° C.
Claim 30
Dependent Claim
33 words
The process of claim 26, wherein the second monomer charge comprises a C 4 to C 8 conjugated diolefin in an amount of up to 60 mole percent of the total monomer charge.
Claim 31
Dependent Claim
11 words
The process of claim 28, wherein said conjugated diolefin is isoprene.
Claim 32
Dependent Claim
35 words
The process of claim 26, wherein the second monomer charge comprises a C 8 to C 20 vinylidene aromatic monomer in an amount of up to about 60 mole percent of the total monomer charge.
Claim 33
Dependent Claim
22 words
The process of claim 30, wherein said vinylidene aromatic monomer is selected from the group consisting of styrene, p-methylstyrene, 2,4,6-trimethylstyrene and indene.
Claim 34
Dependent Claim
43 words
The process of claim 26, wherein said Lewis acid is selected from the group consisting of BCl 3 , AlCl 3 , SnCl 4 , TiCl 4 , SbF 5 , SeCl 3 , ZnCl 2 , FeCl 3 and VCl 4 .
Claim 35
Dependent Claim
18 words
The process of claim 32, wherein said Lewis acid is selected from BCl 3 and TiCl 4 .
Claim 36
Dependent Claim
12 words
The process of claim 26 conducted in the presence of a diluent.
Claim 37
Dependent Claim
68 words
The process of claim 34 wherein said diluent is selected from the group consisting of C 1 to C 4 halogenated hydrocarbons, C 5 to C 8 aliphatic hydrocarbons, C 5 to C 10 cyclic hydrocarbons, mixtures of said halogenated hydrocarbons, mixtures of one of said halogenated hydrocarbons and one of said aliphatic hydrocarbons and mixtures of one of said halogenated hydrocarbons and one of said cyclic hydrocarbons.
Claim 38
Dependent Claim
21 words
The process of claim 35, wherein said diluent is selected from methyl chloride, methylene chloride, hexane and cyclohexane and mixtures thereof.
Claim 39
Dependent Claim
142 words
The process of claim 26, wherein said monomer charge comprises the sequential addition of isobutylene and a second monomer selected from the group consisting of isoprene, styrene, p-methylstyrene, 2,4,6-trimethylstyrene and indene, the amount of said second monomer charge being up to 60 mole percent of the total monomer charge, said Lewis acid is one of BCl 3 and TiCl 4 , said organic peroxy compound is one of cumene hydroperoxide and p-dicumyl dihydroperoxide, said electron donor is one of dimethylsulfoxide, diethylene glycol dimethyl ether (diglyme) and tetrahydrothiophene, the amount of said Lewis acid being from about 3 to about 40 moles per mole of said peroxy compound, the amount of said electron donor being from about 2×10 -1 to about 3 moles per mole of said peroxy compound and a diluent is present selected from the group consisting of methyl chloride, methylene.
References Cited (Backward Citations)
US3629215A
Cited
US3959225A
Cited
US4276394A
Cited
US4316973A
Cited
US4342849A
Cited
US4524188A
Cited
EP0206756A2
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1993-07-23 | 1994-01-22 | 1994-07-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-07-23 | 1998-01-22 | 1998-07-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-07-23 | 2002-01-22 | 2002-07-24 | $7700.00 | Window Closed / Lapsed |