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US4248986A
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Selective cyclization of block copolymers
Assignee: GOODYER TIRE & RUBBER COMPANY
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Filing: 1979-08-27
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Granted: 1981-02-03
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Expires: 1999-08-27
Abstract
Abstract There is disclosed a process for selectively cyclizing block polymers which comprises reacting 1 to 30 percent by weight solution of a block copolymer comprised of at least two different blocks, at least one of which blocks is a cyclizable block derived from a conjugated diene monomer of the general structure ##STR1## wherein: R 1 is selected from a hydrocarbyl group containing one to twelve carbon atoms, R 2 is selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; and at least one of which blocks is a non-cyclizable block derived from at least one member selected from the following classes of compounds: (a) polymers of conjugated diene monomers of general structure ##STR2## wherein: R 3 , R 4 and R 5 are the same or different and are selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; R 6 is selected from hydrogen, a hydrocarbyl group containing one to twelve carbon atoms or a cyano group, (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes, (c) polymethacrylonitrile, polycaprolactam, polycaprolactone or polydimethylsiloxane, with a cationic catalyst at concentrations from about 0.1 to about 20 parts by weight per hundred parts by weight of said block copolymer at a temperature of about 0°-200° C. for a reaction time ranging from 0.2 to 25 hours and stopping the reaction, said cyclized blocks constituting about 5-95 weight percent of cyclized block copolymer and said non-cyclized blocks constituting about 95-5 weight percent of cyclized block copolymer.
Inventors
- 👤 Joginder Lal
- 👤 Richard R. Smith
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 09:48
CPC Classifications
C; C08; C08F; C08F8/00; C08F8/48
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
265 words
A process for selectively cyclizing block copolymers having a number average molecular weight of from about 10,000 to about 300,000 which comprises reacting 1 to 30 percent by weight solution of a block copolymer comprised of at least two different blocks, at least one of which blocks is a cyclizable block derived from a conjugated diene monomer of the general structure ##STR10## wherein: R 1 is selected from a hydrocarbyl group containing one to twelve carbon atoms, R 2 is selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; and at least one of which blocks is a non-cyclizable block derived from at least one member selected from the following classes of compounds: (a) polymers of conjugated diene monomers of general structure ##STR11## wherein: R 3 , R 4 and R 5 are the same or different and are selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; R 6 is selected from hydrogen, a hydrocarbyl group containing one to twelve carbon atoms or a cyano group, (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes, (c) polymethacrylonitrile, polycaprolactam, polycaprolactone or polydimethylsiloxane, with a cationic catalyst at concentrations from about 0.1 to about 20 parts by weight per hundred parts by weight of said block copolymer at a temperature of about 0°-200° C. for a reaction time ranging from 0.2 to 25 hours and stopping the reaction, said cyclized blocks constituting about 5-95 weight percent of cyclized block copolymer and said non-cyclized blocks constituting about 95-5 weight percent of cyclized block copolymer.
Claim 2
Dependent Claim
265 words
A process for selectively cyclizing block copolymers having a number average molecular weight of from about 10,000 to about 300,000 which comprises reacting 1 to 30 percent by weight solution of a block copolymer comprised of at least two different blocks, at least one of which blocks is a cyclizable block derived from a conjugated diene monomer of the general structure ##STR10## wherein: R 1 is selected from a hydrocarbyl group containing one to twelve carbon atoms, R 2 is selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; and at least one of which blocks is a non-cyclizable block derived from at least one member selected from the following classes of compounds: (a) polymers of conjugated diene monomers of general structure ##STR11## wherein: R 3 , R 4 and R 5 are the same or different and are selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; R 6 is selected from hydrogen, a hydrocarbyl group containing one to twelve carbon atoms or a cyano group, (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes, (c) polymethacrylonitrile, polycaprolactam, polycaprolactone or polydimethylsiloxane, with a cationic catalyst at concentrations from about 0.1 to about 20 parts by weight per hundred parts by weight of said block copolymer at a temperature of about 0°-200° C. for a reaction time ranging from 0.2 to 25 hours and stopping the reaction, said cyclized blocks constituting about 5-95 weight percent of cyclized block copolymer and said non-cyclized blocks constituting about 95-5 weight percent of cyclized block copolymer.
Claim 3
Dependent Claim
85 words
A process as recited in claim 1 wherein the monomers of the cyclizable block are selected from the group consisting of isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 3-n-propyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 3-methyl-1,3-heptadiene and 3-butyl-1,3-octadiene and the non-cyclizable block is derived from (a) a conjugated diene monomer selected from the group consisting of 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene and 1-cyano-1,3-butadiene and/or (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes and/or (c) polymethacrylonitrile, polycaprolactam, polycaprolactone or polydimethylsiloxane.
Claim 4
Dependent Claim
87 words
The process as recited in claim 1 in which the non-cyclizable block is derived from: (a) polymers of conjugated diene monomers of general structure ##STR12## wherein: R 3 , R 4 and R 5 are the same or different and are selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; R 6 is selected from hydrogen, a hydrocarbyl group containing one to twelve carbon atoms or a cyano group, (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes.
Claim 5
Dependent Claim
29 words
The process as recited in claim 1 wherein the cyclization reaction is carried out in a solvent selected from the group consisting of aliphatic, cycloaliphatic, aromatic and chlorinated solvents.
Claim 6
Dependent Claim
41 words
The process as recited in claim 1 wherein the cyclization catalyst is selected from the group consisting of SnCl 4 , TiCl 4 , TiBr 4 , BF 3 , BCl 3 and any of the preceding compounds with a cocatalyst.
Claim 7
Dependent Claim
15 words
The process as recited in claim 3 further comprising hydrogenation of the cyclized block copolymer.
Claim 8
Dependent Claim
15 words
The process as recited in claim 3 further comprising hydrochlorination of the cyclized block copolymer.
Claim 9
Dependent Claim
37 words
The process as recited in claim 5 wherein the block copolymer is synthesized by a polymerization process consisting of either sequential addition or sequential addition followed by coupling, in which the polymerization catalyst is an organolithium compound.
Claim 10
Dependent Claim
33 words
The process as recited in claim 2 wherein the block polymer has at least one non-cyclizable polymer block which is selected from the group consisting of poly(α-methylstyrene), polystyrene, polymethacrylonitrile, polydimethylsiloxane, polycaprolactone and polycaprolactam.
Claim 11
Dependent Claim
16 words
The process as recited in claim 2 wherein the block copolymer is an IBS (polyisoprene-polybutadienepolystyrene) triblock.
Claim 12
Dependent Claim
39 words
The process as recited in claim 2 wherein the cyclizable block is derived from monomers of the group of isoprene, 2ethyl-1,3-butadiene and 2-phenyl-1,3-butadiene and the non-cyclizable block is derived from monomers of the group of 1,3-butadiene, piperylene and 2,4-hexadiene.
Claim 13
Dependent Claim
25 words
The process as recited in claim 11 wherein the block copolymer is selected from the group consisting of IB (polyisoprene-polybutadiene) diblocks and IBI (polyisoprene-polybutadiene-polyisoprene) triblocks.
Claim 14
Dependent Claim
97 words
The process as recited in claim 12 wherein a 5 to 15 weight percent solution of the block copolymer is reacted with a catalyst selected from the group consisting of SnCl 4 with CCl 3 COOH cocatalyst in a molar ratio of cocatalyst to SnCl 4 of about 0.4 to 0.8/l, TiCl 4 with CCl 3 COOH cocatalyst in a molar ratio of cocatalyst to TiCl 4 of about 0.4 to 0.8/l, and BF 3 .Et 2 O, at a temperature of about 25° to 100° C., and a reaction time ranging from 1 to 16 hours.
Claim 15
Dependent Claim
39 words
The process as recited in claim 1 wherein the block copolymer is a [(IB) n --X] radial block copolymer wherein I represents polyisoprene block and B represents polybutadiene block and X is a nucleus derived from divinylbenzene coupling agent.
Claim 16
Dependent Claim
27 words
The process as recited in claim 2 wherein the microstructure of the block copolymer which is cyclized has been modified by the use of diglyme during synthesis.
Claim 17
Dependent Claim
24 words
The process as recited in claim 14 wherein the microstructure of the polybutadiene block has been modified by the use of diglyme during synthesis.
Claim 18
Dependent Claim
29 words
The process as recited in claim 2 from which the microstructure of the cyclizable block is modified by the use of diglyme during the synthesis of the block copolymer.
Claim 19
Dependent Claim
29 words
The process as recited in claim 2 in which the microstructure of the non-cyclizable block is modified by the use of diglyme during the synthesis of the block copolymer.
Claim 20
Dependent Claim
74 words
A process as recited in claim 1 in which the cyclizable block is derived from a conjugated diene monomer of the general structure ##STR13## wherein R 1 is selected from a hydrocarbyl group containing 1 to 12 carbon atoms and R 2 is selected from hydrogen or a hydrocarbyl group containing 1 to 12 carbon atoms and the non-cyclizable block is selected from the group consisting of poly(α-methylstyrene), polystyrene, polymethacrylonitrile, polydimethylsiloxane, polycaprolactone and polycaprolactam.
Claim 21
Dependent Claim
20 words
A process as recited in claim 19 in which the cyclizable block is polyisoprene and the non-cyclizable block is polystyrene.
Claim 22
Dependent Claim
257 words
A cyclized block copolymer according to claim 1 which is obtained by subjecting a 1 to 30 percent by weight solution of a block copolymer comprised of at least two different blocks, at least one of which blocks is a cyclizable block derived from a conjugated diene monomer of the general structure ##STR14## wherein: R 1 is selected from a hydrocarbyl group containing one to twelve carbon atoms; R 2 is selected from hydrogen or hydrocarbyl group containing one to twelve carbon atoms; and at least one of which blocks is a non-cyclizable block derived from at least one member selected from the following classes of compounds: (a) polymers of conjugated diene monomers of general structure ##STR15## wherein, R 3 , R 4 and R 5 are the same or different and are selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; R 6 is selected from hydrogen, a hydrocarbyl group containing one to twelve carbon atoms or a cyano group, (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes, with a cationic catalyst at concentrations from about 0.1 to about 20 parts by weight per hundred parts by weight of said block copolymer at a temperature of about 0°-200° C. for a reaction time ranging from 0.2 to 25 hours and stopping the reaction, said cyclized blocks constituting about 5-95 weight percent of cyclized block copolymer and said non-cyclized blocks constituting about 95-5 weight percent of cyclized block copolymer, wherein said block copolymer has been subsequently hydrogenated.
Claim 23
Dependent Claim
257 words
A cyclized block copolymer according to claim 1 which is obtained by subjecting a 1 to 30 percent by weight solution of a block copolymer comprised of at least two different blocks, at least one of which blocks is a cyclizable block derived from a conjugated diene monomer of the general structure ##STR16## wherein, R 1 is selected from a hydrocarbyl group containing one to twelve carbon atoms; R 2 is selected from hydrogen or hydrocarbyl group containing one to twelve carbon atoms; and at least one of which blocks is a non-cyclizable block derived from at least one member selected from the following classes of compounds: (a) polymers of conjugated diene monomers of general structure ##STR17## wherein, R 3 , R 4 and R 5 are the same or different and are selected from hydrogen or a hydrocarbyl group containing one to twelve carbon atoms; R 6 is selected from hydrogen, a hydrocarbyl group containing one to twelve carbon atoms or a cyano group, (b) polymers of α-methylstyrene, styrene, alkyl or aryl substituted styrenes or halogen substituted styrenes, with a cationic catalyst at concentrations from about 0.1 to about 20 parts by weight per hundred parts by weight of said block copolymer at a temperature of about 0°-200° C. for a reaction time ranging from 0.2 to 25 hours and stopping the reaction, said cyclized blocks constituting about 5-95 weight percent of cyclized block copolymer and said non-cyclized blocks constituting about 95-5 weight percent of cyclized block copolymer, wherein said block copolymer has been subsequently hydrochlorinated.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-02-03 | 1984-08-04 | 1985-02-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-02-03 | 1988-08-04 | 1989-02-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-02-03 | 1992-08-04 | 1993-02-03 | $7700.00 | Window Closed / Lapsed |