Patent US5087681A successfully refreshed from Google Patents.
US5087681A
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Composition from reacting vinylidene terminated polybutadiene/acrylonitrile and bisimide
Assignee: UK Secretary of State for Defence
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Filing: 1989-08-08
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Granted: 1992-02-11
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Expires: 2009-08-08
Abstract
Abstract A novel method for preparing a thermosetting imide resin composition which consists of chemically reacting a liquid mixture of a carboxy-(CTBN) or vinylidene-(VTBN) polybutadiene/acrylonitrile and a co-reactant comprising a. at least one N,N'-bisimide of an unsaturated carboxylic acid of general formula I ##STR1## wherein B represents a divalent radical containing a carbon-carbon double bond and A represents a divalent radical having at least two carbon atoms, or b. the imide resin reaction product of an least one N,N'-bisimide of general formula I and at least one primary organic diamine or organic hydrazide, or c. the imide resin reaction product of at least one N,N'-bisimide of general formula I, at least one monoimide, and at least one organic hydrazide, to yield a thermosetting imide resin composition containing copolymerized CTBN or VTBN and co-reactant. A resin composition prepared by this method may be cured at a temperature between 100° C. and 350° C. to yield a full cross-linked polyimide matrix containing a dispersion of phase-separated solid particles of copolymerized CTBN or VTBN and co-reactant.
Inventors
- 👤 Anthony J. Kinloch
- 👤 Stephen J. Shaw
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 22:36
CPC Classifications
C; C08; C08C; C08C19/00; C08C19/30; C08C19/34; C08C19/36; C08F; C08F290/00; C08F290/02; C08F290/04; C08F290/048; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/12; C08G73/121
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
199 words
A method for preparing a thermosetting imide resin composition which comprises chemically reacting a liquid mixture of a vinylidene terminated polybutadiene/acrylonitrile (VTBN) polymer having a polybutadiene/acrylonitrile backbone and terminal groups at both ends of the formula --C(R)═CH 2 wherein R is independently selected from the group consisting of H and an alkyl group containing 1 to 4 carbon atoms, with a co-reactant selected from the group consisting of: (a) at least one N,N'-bisimide of an unsaturated carboxylic acid of the formula I ##STR18## wherein B represents a divalent radical containing a carbon-carbon double bond and A represents a divalent radical having at least two carbon atoms, (b) the imide resin reaction product of at least one N,N'-bisimide of formula I and at least one primary organic diamine or organic hydrazide, and (c) the imide resin reaction product of at least one N,N'-bisimide of formula I, at least one monoimide, and at least one organic hydrazide, to yield a thermosetting imide resin composition containing copolymerised VTBN and co-reactant, said composition being curable at a temperature between 100° C. and 350° C. to a fully cross-linked polyimide matrix containing a dispersion of phase separated solid particles of copolyermised VTBN and co-reactant.
Claim 2
Independent Claim
199 words
A method for preparing a thermosetting imide resin composition which comprises chemically reacting a liquid mixture of a vinylidene terminated polybutadiene/acrylonitrile (VTBN) polymer having a polybutadiene/acrylonitrile backbone and terminal groups at both ends of the formula --C(R)═CH 2 wherein R is independently selected from the group consisting of H and an alkyl group containing 1 to 4 carbon atoms, with a co-reactant selected from the group consisting of: (a) at least one N,N'-bisimide of an unsaturated carboxylic acid of the formula I ##STR18## wherein B represents a divalent radical containing a carbon-carbon double bond and A represents a divalent radical having at least two carbon atoms, (b) the imide resin reaction product of at least one N,N'-bisimide of formula I and at least one primary organic diamine or organic hydrazide, and (c) the imide resin reaction product of at least one N,N'-bisimide of formula I, at least one monoimide, and at least one organic hydrazide, to yield a thermosetting imide resin composition containing copolymerised VTBN and co-reactant, said composition being curable at a temperature between 100° C. and 350° C. to a fully cross-linked polyimide matrix containing a dispersion of phase separated solid particles of copolyermised VTBN and co-reactant.
Claim 3
Dependent Claim
35 words
A method according to claim 1 wherein the average particle size of the phase separated particles, as determined by Scanning Electron Microscopy, lies in the range 0.1 to 10 microns, preferably 0.5 to 8 microns.
Claim 4
Dependent Claim
94 words
The method according to claim 1 wherein the co-reactant comprises the reaction product of at least one N,N'-bisimide of formula I wherein A and B are as defined in claim 1, and at least one primary organic diamine of formula II H.sub.2 N--D--NH.sub.2 (II) wherein D represents a divalent radical having not more than 30 carbon atoms, and wherein the ratio of the total number of moles of bisimide of formula I to the total number of moles of diamine of formula II in the reaction mixture lies in the range 1.2:1 to 50:1.
Claim 5
Dependent Claim
85 words
A method according to claim 1 wherein the co-reactant comprises the reaction product of at least one N,N'-bisimide of formula I, wherein A and B are as defined in claim 1, and at least one organic hydrazide of formula III ##STR19## wherein E represents a divalent organic group, and wherein the ratio of the total number of moles of bisimide of formula I to the total number of moles of hydrazide of formula III in the reaction mixture lies in the range 1.1:1 to 10:1.
Claim 6
Dependent Claim
78 words
A method according to claim 1 wherein the co-reactant comprises the reaction product of at least one N,N'-bisimide of formula I, wherein A and B are as defined in claim 1, and at least one organic hydrazide of formula IV ##STR20## wherein G represents a divalent organic group, and wherein the total number of moles of bisimide of formula I to the total number of moles of hydrazide of formula IV lies in the range 1.1:1 to 10:1.
Claim 7
Dependent Claim
18 words
A method according to claim 1 wherein B represents a group selected from the group consisting of ##STR21##
Claim 8
Dependent Claim
70 words
A method according to claim 1 wherein the at least one bisimide of general formula I comprises at least one of the following bisimides 1,2-bismaleimido ethane, 1,4-bismaleimido butane, 1,6-bismaleimido hexane, 1,12-bismaleimido dodecane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,3-bismaleimido benzene, 1,4-bismaleimido benzene, 4,4'-bismaleimido diphenyl methane, 4,4'-bismaleimido diphenyl ether, 4,4'-bismaleimido diphenyl sulfide, 4,4'-bismaleimido diphenyl sulfone, 4,4'-bismaleimido dicyclohexyl methane, 2,4- bismaleimido toluene, 2,6-bismaleimido toluene, N,N'-m-xylylene bismaleimide, N,N'-p-xylylene bismaleimide, N,N'-m-phenylene biscitraconic acid imide, N,N'-4,4'-diphenylmethane citraconimide, and N,N'-4,4'-diphenylmethane bisitaconimide.
Claim 9
Dependent Claim
27 words
A method according to claim 1 wherein the molar ratio of butadiene groups to acrylonitrile groups in the VTBN polymer lies in the range 99:1 to 65:35.
Claim 10
Dependent Claim
25 words
A method according to claim 1 wherein the VTBN polymer is a VTBN of general formula VIA ##STR22## wherein B is a polybutadiene/acrylonitrile polymeric backbone.
Claim 11
Dependent Claim
78 words
A method according to claim 1 wherein the VTBN polymer is a VTBN of Formula VII ##STR23## wherein B is a polybutadiene/acrylonitrile polymeric backbone; Z is selected from the group consisting of --O--, --S--, --NH--, --O--CO--, and --O--CH 2 --CH 2 --; A is selected from the group consisting of --CO.--O--CH 2 --, --CH 2 --O--CH 2 --, and --CH 2 --O--; and each R is independently hydrogen or an alkyl group containing 1 to 4 carbon atoms.
Claim 12
Dependent Claim
33 words
A method according to claim 1 wherein the matrix has a lap shear strength at 20° C. at least 50% greater than that of a fully cross-linked polyimide cured from the co-reactant alone.
Claim 13
Dependent Claim
48 words
A method according to claim 1 which further comprises the subsequent step of heating the thermosetting imide resin composition to a temperature between 100° C. and 350° C. to yield a fully cross-linked polymer matrix containing a dispersion of phase-separated solid particles of copolymerised VTBN polymer and co-reactant.
Claim 14
Dependent Claim
13 words
A thermosetting imide resin composition prepared by the method according to claim 1.
Claim 15
Dependent Claim
24 words
A fully cross-linked polyimide matrix containing a dispersion of phase-separated solid particles of TBN polymer and co-reactant prepared by the method of claim 12.
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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) | 1995-02-10 | 1995-08-12 | 1996-02-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1999-02-10 | 1999-08-12 | 2000-02-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2003-02-10 | 2003-08-12 | 2004-02-11 | $7700.00 | Window Closed / Lapsed |