US5395885A
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US
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Multi-arm cationic star-polymers
Assignee: University of Akron
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Filing: 1993-12-17
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Granted: 1995-03-07
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Expires: 2013-12-17
Abstract
Abstract The first synthesis of a multi-arm radial-star polyisobutylene is described. The synthesis occurred by the addition of excess divinylbenzene (DVB) linking reagent to a living polyisobutylene (PIB.sup.⊕), charge, i.e., by the "arm first" method under specific conditions. The radial structure of the star-PIB was proven by determining the molecular weight of a sample by light scattering, then selectively destroying the aromatic polydivinylbenzene core, and finally determining the molecular weight of the surviving aliphatic PIB arms. The synthesis strategy, kinetic observations during synthesis, and procedures leading to a representative star-PIB are described. This product whose M w =1,134,400 g/mole with M w /M n =2.83, contained ˜90.3 mole % (˜78 wt. %) PIB arms and ˜9.7 mole % (˜22 wt. %) aromatic core; thus the number of PIB arms emanating from the core was N n , arm =56 or N w , arm (weight average number of arms)=110.
Inventors
- 👤 Joseph P. Kennedy
- 👤 Timea M. Marsalko
- 👤 Istvan J. Majoros
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 09:57
CPC Classifications
C; C08; C08F; C08F297/00
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
155 words
A star polymer comprising: (a) at least two molecules of a multifunctional linking agent selected from the group consisting of divinyl aromatics, trivinyl aromatics, diepoxides, diketones and dialdehydes which forms a core; and (b) three or more cationically polymerized polymer arms attached to the core, the polymer arms selected from the group consisting of homopolymers, copolymers, block copolymers having at least one polyolefin segment and at least one polyaryl segment, graft copolymers and mixtures thereof, and further wherein when the polymer arms are selected from the group consisting of homopolymers, copolymers and graft copolymers, the polymer arms are selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene), and further wherein when the polymer arms are block copolymers, the at least one polyolefin segment is selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene) and the at least one polyaryl segment is selected from the group consisting of polystyrene and alkylated polystyrene.
Claim 2
Dependent Claim
155 words
A star polymer comprising: (a) at least two molecules of a multifunctional linking agent selected from the group consisting of divinyl aromatics, trivinyl aromatics, diepoxides, diketones and dialdehydes which forms a core; and (b) three or more cationically polymerized polymer arms attached to the core, the polymer arms selected from the group consisting of homopolymers, copolymers, block copolymers having at least one polyolefin segment and at least one polyaryl segment, graft copolymers and mixtures thereof, and further wherein when the polymer arms are selected from the group consisting of homopolymers, copolymers and graft copolymers, the polymer arms are selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene), and further wherein when the polymer arms are block copolymers, the at least one polyolefin segment is selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene) and the at least one polyaryl segment is selected from the group consisting of polystyrene and alkylated polystyrene.
Claim 3
Dependent Claim
97 words
The star polymer of claim 1 wherein the divinyl aromatic is selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl and mixtures thereof, and wherein the trivinyl aromatic is selected from the group consisting of 1,2,4-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-triisopropenylbenzene, 1,3,5-triisopropenylbenzene, 3,5,4'-trivinylbiphenyl, and 1,5,6-trivinyl-3,7-diethylnaphthalene, and wherein the diepoxide is selected from the group consisting of cyclohexane diepoxide, 1,4-pentane diepoxide, and 1,5-hexane diepoxide and wherein the diketone is selected from the group consisting of 2,4-hexane-di-one, 2,5-hexane-di-one, and 2,6-heptane-di-one, and the dialdehyde is selected from the group consisting of 1,4-butanedial, 1,5-pentanedial and 1,6-hexanedialdivinylbenzene.
Claim 4
Dependent Claim
15 words
The star polymer of claim 2 wherein the number of arms is at least seven.
Claim 5
Dependent Claim
47 words
A cationically synthesized star polymer comprising: (a) at least two molecules of a difunctional linking agent selected from the group consisting of m-divinyl benzene, p-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof which form a core; and (b) at least three or more polyisobutylene arms attached to the core.
Claim 6
Dependent Claim
47 words
A cationically synthesized star polymer comprising: (a) at least two molecules of a difunctional linking agent selected from the group consisting of m-divinyl benzene, p-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof which form a core; and (b) at least three or more polyisobutylene arms attached to the core.
Claim 7
Dependent Claim
15 words
The star polymer of claim 4 wherein the number of arms is at least seven.
Claim 8
Dependent Claim
61 words
A cationically synthesized star polymer comprising: (a) at least two molecules of a difunctional linking agent selected from the group consisting of m-divinyl benzene, p-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof which form a core; and (b) at least three or more block copolymer arms attached to the core and wherein the block copolymer comprises a polyolefin segment and a polyaryl segment.
Claim 9
Dependent Claim
61 words
A cationically synthesized star polymer comprising: (a) at least two molecules of a difunctional linking agent selected from the group consisting of m-divinyl benzene, p-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof which form a core; and (b) at least three or more block copolymer arms attached to the core and wherein the block copolymer comprises a polyolefin segment and a polyaryl segment.
Claim 10
Dependent Claim
15 words
The star polymer of claim 6 wherein the number of arms is at least seven.
Claim 11
Dependent Claim
22 words
The star polymer of claim 6 wherein the polyolefin is polyisobutylene and the polyaryl is selected from polystyrene and derivatives of polystyrene.
Claim 12
Dependent Claim
164 words
A star polymer which comprises: (a) a core consisting essentially of at least two molecules of a multifunctional linking agent selected from the group consisting of divinyl aromatics, trivinyl aromatics, diepoxides, diketones and dialdehydes, and at least one molecule of ethylstyrene; and (b) three or more cationically polymerized polymer arms attached to the core, the polymer arms selected from the group consisting of homopolymers, copolymers, block copolymers having at least one polyolefin segment and at least one polyaryl segment, graft copolymers and mixtures thereof, and further wherein when the polymer arms are selected from the group consisting of homopolymers, copolymers and graft copolymers, the polymer arms are selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene), and further wherein when the polymer arms are block copolymers, the at least one polyolefin segment is selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene) and the at least one polyaryl segment is selected from the group consisting of polystyrene and alkylated polystyrene.
Claim 13
Dependent Claim
164 words
A star polymer which comprises: (a) a core consisting essentially of at least two molecules of a multifunctional linking agent selected from the group consisting of divinyl aromatics, trivinyl aromatics, diepoxides, diketones and dialdehydes, and at least one molecule of ethylstyrene; and (b) three or more cationically polymerized polymer arms attached to the core, the polymer arms selected from the group consisting of homopolymers, copolymers, block copolymers having at least one polyolefin segment and at least one polyaryl segment, graft copolymers and mixtures thereof, and further wherein when the polymer arms are selected from the group consisting of homopolymers, copolymers and graft copolymers, the polymer arms are selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene), and further wherein when the polymer arms are block copolymers, the at least one polyolefin segment is selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene) and the at least one polyaryl segment is selected from the group consisting of polystyrene and alkylated polystyrene.
Claim 14
Dependent Claim
97 words
The star polymer of claim 9 wherein the divinyl aromatic is selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4-propylbiphenyl and mixtures thereof, and wherein the trivinyl aromatic is selected from the group consisting of 1,2,4-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-triisopropenylbenzene, 1,3,5-triisopropenylbenzene, 3,5,4'-trivinylbiphenyl, and 1,5,6-trivinyl-3,7-diethylnaphthalene, and wherein the diepoxide is selected from the group consisting of cyclohexane diepoxide, 1,4-pentane diepoxide, and 1,5-hexane diepoxide and wherein the diketone is selected from the group consisting of 2,4-hexane-di-one, 2,5-hexane-di-one, and 2,6-heptane-di-one, and the dialdehyde is selected from the group consisting of 1,4-butanedial, 1,5-pentanedial and 1,6-hexanedialdivinylbenzene.
Claim 15
Dependent Claim
15 words
The star polymer of claim 10 wherein the number of arms is at least seven.
Claim 16
Dependent Claim
67 words
A cationically synthesized star polymer comprising: (a) a microgel core consisting essentially of at least two molecules of a difunctional linking agent selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof, the core additionally including ethylstyrene; and (b) at least three or more arms selected from the group consisting of homopolymers, copolymers, block copolymers, graft copolymers and mixtures thereof attached to the core.
Claim 17
Dependent Claim
67 words
A cationically synthesized star polymer comprising: (a) a microgel core consisting essentially of at least two molecules of a difunctional linking agent selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof, the core additionally including ethylstyrene; and (b) at least three or more arms selected from the group consisting of homopolymers, copolymers, block copolymers, graft copolymers and mixtures thereof attached to the core.
Claim 18
Dependent Claim
15 words
The star polymer of claim 12 wherein the number of arms is at least seven.
Claim 19
Dependent Claim
69 words
A cationically synthesized star polymer consisting essentially of: (a) a microgel core consisting essentially of at least two molecules of a difunctional linking agent selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof, the core additionally including ethylstyrene; and (b) at least three or more arms selected from the group consisting of homopolymers, copolymers, block copolymers, graft copolymers and mixtures thereof attached to the core.
Claim 20
Dependent Claim
69 words
A cationically synthesized star polymer consisting essentially of: (a) a microgel core consisting essentially of at least two molecules of a difunctional linking agent selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene and mixtures thereof, the core additionally including ethylstyrene; and (b) at least three or more arms selected from the group consisting of homopolymers, copolymers, block copolymers, graft copolymers and mixtures thereof attached to the core.
Claim 21
Dependent Claim
15 words
The star polymer of claim 14 wherein the number of arms is at least seven.
Claim 22
Dependent Claim
164 words
A star polymer which comprises: (a) a microgel core which comprises at least four molecules of a multifunctional linking agent selected from the group consisting of divinyl aromatics, trivinyl aromatics, diepoxides, diketones and dialdehydes and at least one molecule of ethylstyrene; and (b) three or more cationically polymerized polymer arms attached to the core, the polymer arms selected from the group consisting of homopolymers, copolymers, block copolymers having at least one polyolefin segment and at least one polyaryl segment, graft copolymers and mixtures thereof, and further wherein when the polymer arms are selected from the group consisting of homopolymers, copolymers and graft copolymers, the polymer arms are selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene), and further wherein when the polymer arms are block copolymers, the at least one polyolefin segment is selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene) and the at least one polyaryl segment is selected from the group consisting of polystyrene and alkylated polystyrene.
Claim 23
Dependent Claim
164 words
A star polymer which comprises: (a) a microgel core which comprises at least four molecules of a multifunctional linking agent selected from the group consisting of divinyl aromatics, trivinyl aromatics, diepoxides, diketones and dialdehydes and at least one molecule of ethylstyrene; and (b) three or more cationically polymerized polymer arms attached to the core, the polymer arms selected from the group consisting of homopolymers, copolymers, block copolymers having at least one polyolefin segment and at least one polyaryl segment, graft copolymers and mixtures thereof, and further wherein when the polymer arms are selected from the group consisting of homopolymers, copolymers and graft copolymers, the polymer arms are selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene), and further wherein when the polymer arms are block copolymers, the at least one polyolefin segment is selected from the group consisting of polyisobutylene, poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and poly(β-pinene) and the at least one polyaryl segment is selected from the group consisting of polystyrene and alkylated polystyrene.
Claim 24
Dependent Claim
97 words
The star polymer of claim 16 wherein the divinyl aromatic is selected from the group consisting of 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl and mixtures thereof, and wherein the trivinyl aromatic is selected from the group consisting of 1,2,4-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-triisopropenylbenzene, 1,3,5-triisopropenylbenzene, 3,5,4'-trivinylbiphenyl, and 1,5,6-trivinyl-3,7-diethylnaphthalene, and wherein the diepoxide is selected from the group consisting of cyclohexane diepoxide, 1,4-pentane diepoxide, and 1,5-hexane diepoxide and wherein the diketone is selected from the group consisting of 2,4-hexane-di-one, 2,5-hexane-di-one, and 2,6-heptane-di-one, and the dialdehyde is selected from the group consisting of 1,4-butanedial, 1,5-pentanedial and 1,6-hexanedialdivinylbenzene.
Claim 25
Dependent Claim
12 words
The star polymer of claim 16 wherein the homopolymer is a polyolefin.
Claim 26
Dependent Claim
11 words
The star polymer of claim 18 wherein the polyolefin is polyisobutylene.
Claim 27
Dependent Claim
15 words
The star polymer of claim 17 wherein the number of arms is at least seven.
Claim 28
Dependent Claim
25 words
The star polymer of claim 3 wherein a ratio of a cationic polymerization initiator to the multifunctional linking agent is at least 5 to 1.
Claim 29
Dependent Claim
13 words
The star polymer of claim 21 wherein the ratio is at least 10:1.
Claim 30
Dependent Claim
25 words
The star polymer of claim 5 wherein a ratio of a cationic polymerization initiator to the multifunctional linking agent is at least 5 to 1.
Claim 31
Dependent Claim
13 words
The star polymer of claim 23 wherein the ratio is at least 10:1.
Claim 32
Dependent Claim
25 words
The star polymer of claim 8 wherein a ratio of a cationic polymerization initiator to the multifunctional linking agent is at least 5 to 1.
Claim 33
Dependent Claim
13 words
The star polymer of claim 25 wherein the ratio is at least 10:1.
Claim 34
Dependent Claim
25 words
The star polymer of claim 11 wherein a ratio of a cationic polymerization initiator to the multifunctional linking agent is at least 5 to 1.
Claim 35
Dependent Claim
13 words
The star polymer of claim 27 wherein the ratio is at least 10:1.
Claim 36
Dependent Claim
25 words
The star polymer of claim 15 wherein a ratio of a cationic polymerization initiator to the multifunctional linking agent is at least 5 to 1.
Claim 37
Dependent Claim
13 words
The star polymer of claim 29 wherein the ratio is at least 10:1.
Claim 38
Dependent Claim
25 words
The star polymer of claim 20 wherein a ratio of a cationic polymerization initiator to the multifunctional linking agent is at least 5 to 1.
Claim 39
Dependent Claim
13 words
The star polymer of claim 31 wherein the ratio is at least 10:1.
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