Patent US4510272A successfully refreshed from Google Patents.
US4510272A
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Bis-maleimide-epoxy compositions and prepregs
Assignee: Textron Systems Corp
•
Filing: 1983-03-16
•
Granted: 1985-04-09
•
Expires: 2003-03-16
Abstract
Abstract A novel composition is described comprising an admixture of an unsaturated polyimide prepolymer essentially free of terminal amine groups and an epoxy resin having a homopolymerization temperature that is greater than the temperature at which the polyimide polymerizes. These compositions maintain the superior glass transition temperatures and moisture resistance of the polyimide while picking up the desirable handling properties of the epoxy. These compositions have excellent high temperature and moisture resistant properties and excellent storage stability. For instance, carbon composites made with these materials have exhibited 60% shear property retention at 450° F. after being boiled in water for one week. Also described are prepregs comprising the novel composition, methods for curing the novel composition to obtain the superior properties, and articles of manufacture comprising the novel composition.
Inventors
- 👤 Raymond C. Loszewski
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 14:46
CPC Classifications
C; C08; C08L; C08L79/00; C08L79/04; C08L79/08; C08L79/085; C08G; C08G59/00; C08G59/18; C08G59/40; C08G59/4007; C08G59/4014; C08G59/4042; C08J; C08J5/00; C08J5/24; C08J5/241; C08J5/243; C08L63/00; C08J2379/00; C08J2379/04; C08J2379/08; Y; Y10; Y10S; Y10S525/00; Y10S525/903
Claims Analysis
Total Claims: 87
Claim 1
Independent Claim
32 words
A resinous composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 2
Dependent Claim
32 words
A resinous composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 3
Dependent Claim
98 words
The composition of claim 1 wherein said polyimide is a bis-maleimide having the formula: ##STR7## wherein: each R is independently selected from hydrogen, an aliphatic radical having 1 or 2 carbon atoms, a benzenoid radical, or a halogen; and Z is a polyaliphatic ether having a molecular weight in the range of about 300 to 10,000, or a bifunctional benzenoid radical selected from the group consisting of ##STR8## wherein X is selected from the group consisting of --O--, --S--, --SO 2 --, --CH 2 --, --C 2 H 4 --, --CO--, --C 3 H 6 --, and ##STR9##
Claim 4
Dependent Claim
46 words
The composition of claim 1 wherein said polyimide is a N,N'-bis-imide selected from the N,N'-bis-maleimides of ethylene diamine, hexamethylene diamine, phenylene diamine, trimethyl-hexamethylene diamine, methylene dianiline, toluene diamine, 4,4'-diphenylmethane diamine, 3,3'-diphenylsulfone diamine, 4,4'-dipenylether diamine, 4,4'-diphenylfulsone diamine, 4,4'-dicyclohexanemethane diamine, metaxylylene diamine, or 4,4'-diphenylcyclohexane diamine and mixtures thereof.
Claim 5
Dependent Claim
12 words
The compositions of claim 1 wherein said polyimide is selected from: ##STR10##
Claim 6
Dependent Claim
25 words
The composition of claim 1 wherein said polyimide is present in an amount of from 10 to 99 percent by weight of the resin admixture.
Claim 7
Dependent Claim
25 words
The composition of claim 1 wherein said polyimide is present in an amount of from 40 to 90 percent by weight of the resin admixture.
Claim 8
Dependent Claim
12 words
The composition of claim 1 wherein said epoxy is selected from: ##STR11##
Claim 9
Dependent Claim
40 words
The composition of claim 1 wherein said polyimide is present in an amount of from about 50 to 80 percent by weight of the resin admixture and said epoxy has a viscosity less than about 1000 cp at room temperatures.
Claim 10
Dependent Claim
84 words
A cured composition comprised of an admixture of an unsaturated polyimide essentially free of terminal amine groups and epoxy resin wherein said admixture of said polyimide and said epoxy resin has been heated to temperature for a period of time sufficient to polymerize said polyimide but not sufficient to substantially homopolymerize said epoxy resin and, after such polymerization of said polyimide, said admixture has been further heated to a higher temperature for a period of time sufficient to cause said epoxy resin to polymerize.
Claim 11
Dependent Claim
84 words
A cured composition comprised of an admixture of an unsaturated polyimide essentially free of terminal amine groups and epoxy resin wherein said admixture of said polyimide and said epoxy resin has been heated to temperature for a period of time sufficient to polymerize said polyimide but not sufficient to substantially homopolymerize said epoxy resin and, after such polymerization of said polyimide, said admixture has been further heated to a higher temperature for a period of time sufficient to cause said epoxy resin to polymerize.
Claim 12
Dependent Claim
41 words
The composition of claim 9 wherein said polyimide is a bis-imide having the formula: ##STR12## wherein: Y is a divalent radical having at least 2 carbon atoms; and Z is a divalent radical having from 1 to about 20 carbon atoms.
Claim 13
Dependent Claim
19 words
The composition of claim 10 wherein Y is derived from malaeic acid, citraconic acid, tetrahydrophthalic acid, or anhydrides thereof.
Claim 14
Dependent Claim
17 words
The composition of claim 10 wherein Z is selected from an aliphatic, cycloaliphtic, aromatic or heterocyclic radical.
Claim 15
Dependent Claim
98 words
The composition of claim 9 wherein said polyimide is a bis-maleimide having the formula: ##STR13## wherein: each R is independently selected from hydrogen, an aliphatic radical having 1 or 2 carbon atoms, a benzenoid radical, or a halogen; and Z is a polyaliphatic ether having a molecular weight in the range of about 300 to 10,000, or a bifunctional benzenoid radical selected from the group consisting of ##STR14## wherein X is selected from the group consisting of --O--, --S--, --SO 2 --, --CH 2 --, --C 2 H 4 --, --CO--, --C 3 H 6 --, and ##STR15##
Claim 16
Dependent Claim
46 words
The composition of claim 9 wherein said polyimide is a N,N'-bis-imide selected from the N,N'-bis-maleimides of ethylene diamine, hexamethylene diamine, phenylene diamine, trimethyl-hexamethylene diamine, methylene dianiline, toluene diamine, 4,4'-diphenylmethane diamine, 3,3'-diphenylsulfone diamine, 4,4'-dipenylether diamine, 4,4'-diphenylfulsone diamine, 4,4'-dicyclohexanemethane diamine, metaxylylene diamine, or 4,4'-diphenylcyclohexane diamine and mixtures thereof.
Claim 17
Dependent Claim
12 words
The composition of claim 9 wherein said polyimide is selected from: ##STR16##
Claim 18
Dependent Claim
25 words
The composition of claim 9 wherein said polyimide is present in an amount of from 10 to 99 percent by weight of the resin admixture.
Claim 19
Dependent Claim
25 words
The composition of claim 9 wherein said polyimide is present in an amount of from 30 to 90 percent by weight of the resin admixture.
Claim 20
Dependent Claim
19 words
The composition of claim 9 wherein said epoxy has a viscosity less than about 10,000 cp at 120° F.
Claim 21
Dependent Claim
13 words
The composition of claim 9 wherein said epoxy is a glycidyl amine epoxy.
Claim 22
Dependent Claim
20 words
The composition of claim 19 wherein said epoxy has a viscosity of less than about 1000 cp at room temperature.
Claim 23
Dependent Claim
12 words
The composition of claim 9 wherein said epoxy is selected from: ##STR17##
Claim 24
Dependent Claim
40 words
The composition of claim 9 wherein said polyimide is present in an amount of from about 50 to 80 percent by weight of the resin admixture and said epoxy has a viscosity less than about 1000 cp at room temperatures.
Claim 25
Dependent Claim
25 words
The composition of claim 9 wherein said polyimide is substantially polymerized before the epxoy resin is 25% homopolymerized, after which the epoxy resin is homopolymerized.
Claim 26
Dependent Claim
41 words
A prepreg comprising a fibrous material coated or impregnated with a composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 27
Dependent Claim
41 words
A prepreg comprising a fibrous material coated or impregnated with a composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 28
Dependent Claim
42 words
The prepreg of claim 24 wherein said polyimide is a bis-imide having the formula: ##STR18## wherein: Y is an unsaturated divalent radical having at least 2 carbon atoms; and Z is a divalent radical having from 1 to about 20 carbon atoms.
Claim 29
Dependent Claim
19 words
The prepreg of claim 25 wherein Y is derived from malaeic acid, citraconic acid, tetrahydrophthalic acid, or anhydrides thereof.
Claim 30
Dependent Claim
17 words
The prepreg of claim 25 wherein Z is selected from an aliphatic, cycloaliphtic, aromatic or heterocyclic radical.
Claim 31
Dependent Claim
98 words
The prepreg of claim 24 wherein said polyimide is a bis-maleimide having the formula: ##STR19## wherein: each R is independently selected from hydrogen, an aliphatic radical having 1 or 2 carbon atoms, a benzenoid radical, or a halogen; and Z is a polyaliphatic ether having a molecular weight in the range of about 300 to 10,000, or a bifunctional benzenoid radical selected from the group consisting of ##STR20## wherein X is selected from the group consisting of --O--, --S--, --SO 2 --, --CH 2 --, --C 2 H 4 --, --CO--, --C 3 H 6 --, and ##STR21##
Claim 32
Dependent Claim
46 words
The prepreg of claim 24 wherein said polyimide is a N,N'-bis-imide selected from the N,N'-bis-maleimides of ethylene diamine, hexamethylene diamine, phenylene diamine, trimethyl-hexamethylene diamine, methylene dianiline, toluene diamine, 4,4'-diphenylmethane diamine, 3,3'-diphenylsulfone diamine, 4,4'-diphenylether diamine, 4,4'-diphenylfulsone diamine, 4,4'-dicyclohexanemethane diamine, metaxylylene diamine, or 4,4'-diphenylcyclohexane diamine and mixtures thereof.
Claim 33
Dependent Claim
12 words
The prepreg of claim 24 wherein said polyimide is selected from: ##STR22##
Claim 34
Dependent Claim
25 words
The prepreg of claim 24 wherein said polyimide is present in an amount of from 10 to 99 percent by weight of the resin admixture.
Claim 35
Dependent Claim
25 words
The prepreg of claim 24 wherein said polyimide is present in an amount of from 30 to 90 percent by weight of the resin admixture.
Claim 36
Dependent Claim
19 words
The prepreg of claim 24 wherein said epoxy has a viscosity less than about 10,000 cp at 120° F.
Claim 37
Dependent Claim
13 words
The prepreg of claim 24 wherein said epoxy is a glycidyl amine epoxy.
Claim 38
Dependent Claim
20 words
The prepreg of claim 31 wherein said epoxy has a viscosity of less than about 1000° F. at room temperature.
Claim 39
Dependent Claim
12 words
The prepreg of claim 24 wherein said epoxy is selected from: ##STR23##
Claim 40
Dependent Claim
39 words
The prepreg claim 24 wherein said polyimide is present in an amount of from about 50 to 80 percent by weight of the resin admixture and said epoxy has a viscosity less than about 1000 cp at room temperatures.
Claim 41
Dependent Claim
24 words
The prepreg claim 24 wherein said polyimide is substantially polymerized before the epoxy resin is 25% homopolymerized, after which the epoxy resin is homopolymerized.
Claim 42
Dependent Claim
22 words
The prepreg of claim 24 wherein said composition is applied in amount of about 20 to 50% by weight of resin solids.
Claim 43
Dependent Claim
38 words
The prepreg of claim 24 wherein said fibrous material is a woven web, a non-woven web, a roving, or a filament comprising glass fibers, carbon fibers, boron carbide fibers, silicon carbide fibers, organic synthetic fibers, or mixtures thereof.
Claim 44
Dependent Claim
74 words
An article of manufacture comprising a cured composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes, wherein said article is cured by heating said article at a first temperature to polymerize said polyimide while said epoxy functions as a diluent, and subsequently heating said at a second temperature to substantially homopolymerize said epoxy.
Claim 45
Dependent Claim
74 words
An article of manufacture comprising a cured composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes, wherein said article is cured by heating said article at a first temperature to polymerize said polyimide while said epoxy functions as a diluent, and subsequently heating said at a second temperature to substantially homopolymerize said epoxy.
Claim 46
Dependent Claim
44 words
The article of manufacture of claim 41 wherein said polyimide is a bis-imide having the formula: ##STR24## wherein: Y is an unsaturated divalent radical having at least 2 carbon atoms; and Z is a divalent radical having from 1 to about 20 carbon atoms.
Claim 47
Dependent Claim
21 words
The article of manufacture of claim 42 wherein Y is derived from malaeic acid, citraconic acid, tetrahydrophthalic acid, or anhydrides thereof.
Claim 48
Dependent Claim
19 words
The article of manufacture of claim 42 wherein Z is selected from an aliphatic, cycloaliphtic, aromatic or heterocyclic radical.
Claim 49
Dependent Claim
100 words
The article of manufacture of claim 41 wherein said polyimide is a bis-maleimide having the formula: ##STR25## wherein: each R is independently selected from hydrogen, an aliphatic radical having 1 or 2 carbon atoms, a benzenoid radical, or a halogen; and Z is a polyaliphatic ether having a molecular weight in the range of about 300 to 10,000, or a bifunctional benzenoid radical selected from the group consisting of ##STR26## wherein X is selected from the group consisting of --O--, --S--, --SO 2 --, --CH 2 --, --C 2 H 4 --, --CO--, --C 3 H 6 --, and ##STR27##
Claim 50
Dependent Claim
48 words
The article of manufacture of claim 41 wherein said polyimide is a N,N'-bis-imide selected from the N,N'-bis-maleimides of ethylene diamine, hexamethylene diamine, phenylene diamine, trimethyl-hexamethylene diamine, methylene dianiline, toluene diamine, 4,4'-diphenylmethane diamine, 3,3'-diphenylsulfone diamine, 4,4'-diphenylether diamine, 4,4'-diphenylsulfone diamine, 4,4'-dicyclohexanemethane diamine, metaxylylene diamine, or 4,4'-diphenylcyclohexane diamine and mixtures thereof.
Claim 51
Dependent Claim
14 words
The article of manufacture of claim 41 wherein said polyimide is selected from: ##STR28##
Claim 52
Dependent Claim
27 words
The article of manufacture of claim 41 wherein said polyimide is present in an amount of from 10 to 99 percent by weight of the resin admixture.
Claim 53
Dependent Claim
27 words
The article of manufacture of claim 41 wherein said polyimide is present in an amount of from 30 to 90 percent by weight of the resin admixture.
Claim 54
Dependent Claim
21 words
The article of manufacture of claim 41 wherein said epoxy has a viscosity less than about 10,000 cp at 120° F.
Claim 55
Dependent Claim
15 words
The article of manufacture of claim 50 herein said epoxy is a glycidyl amine epoxy.
Claim 56
Dependent Claim
22 words
The article of manufacture of claim 41 wherein said epoxy has a viscosity of less than about 1000 cp at room temperature.
Claim 57
Dependent Claim
14 words
The article of manufacture of claim 41 wherein said epoxy is selected from: ##STR29##
Claim 58
Dependent Claim
42 words
The article of manufacture of claim 41 wherein said polyimide is present in an amount of from about 50 to 80 percent by weight of the resin admixture and said epoxy has a viscosity less than about 1000 cp at room temperatures.
Claim 59
Dependent Claim
27 words
The article of manufacture of claim 41 wherein said polyimide is substantially polymerized before the epxoy resin is 25% homopolymerized, after which the epoxy resin is homopolymerized.
Claim 60
Dependent Claim
19 words
The article of manufacture of claim 41 further comprising an additive selected from fillers, pigments, extenders, plasticizers and flexibilizers.
Claim 61
Dependent Claim
35 words
The article of manufacture of claim 56 wherein said additive is selected from glass fibers, carbon fibers, organic high-modulus fibers, quartz powder, Kaolin, silicon dioxide, cab-o-sil, powdered metal, powdered metal oxides or powdered metal salts.
Claim 62
Dependent Claim
68 words
A process for polymerizing an unsaturated polyimide with an epoxy resin, said process comprising: admixing said polyimide and said epoxy to form an admixture; first heating said admixture to initiate the polymerization of said polyimide in said epoxy which acts substantially as a diluent; subsequently further heating said admixture to substantially homopolymerize said epoxy, thereby creating in situ reaction groups that crosslink the epoxy into the polyimide backbone.
Claim 63
Dependent Claim
68 words
A process for polymerizing an unsaturated polyimide with an epoxy resin, said process comprising: admixing said polyimide and said epoxy to form an admixture; first heating said admixture to initiate the polymerization of said polyimide in said epoxy which acts substantially as a diluent; subsequently further heating said admixture to substantially homopolymerize said epoxy, thereby creating in situ reaction groups that crosslink the epoxy into the polyimide backbone.
Claim 64
Dependent Claim
17 words
The process of claim 58 wherein said reaction groups are selected from vinyl groups and hydroxyl groups.
Claim 65
Dependent Claim
27 words
The process of claim 58 wherein said admixing step comprises heating said epoxy to a temperature less than 115° C. and dissolving said polyimide into the epoxy.
Claim 66
Dependent Claim
32 words
The process of claim 58 wherein said first heating step comprises heating said admixture to a temperature of at least about 150° C. for a period of from one to four hours.
Claim 67
Dependent Claim
12 words
The process of claim 61 wherein said temperature is about 175° C.
Claim 68
Dependent Claim
12 words
The process of claim 62 wherein said period is about 11/2 hours.
Claim 69
Dependent Claim
22 words
The process of claim 58 wherein said further heating step comprises heating said admixture to a temperature greater than about 200° C.
Claim 70
Dependent Claim
20 words
The process of claim 64 wherein said temperature is in the range of about 200° C. to about 275° C.
Claim 71
Dependent Claim
15 words
The process of claim 58 wherein said polyimide is essentially free of terminal amine groups.
Claim 72
Dependent Claim
28 words
A composition comprising from 30 to 70 parts by weight of a polyimide and from 25 to 40 parts by weight of an epoxy having the formula: ##STR30##
Claim 73
Dependent Claim
28 words
A composition comprising from 30 to 70 parts by weight of a polyimide and from 25 to 40 parts by weight of an epoxy having the formula: ##STR30##
Claim 74
Dependent Claim
32 words
A composition comprising from 30 to 70 parts by weight of a polyimide having the formula: ##STR31## and from 25 to 45 parts by weight of an epoxy having the formula: ##STR32##
Claim 75
Dependent Claim
32 words
A composition comprising from 30 to 70 parts by weight of a polyimide having the formula: ##STR31## and from 25 to 45 parts by weight of an epoxy having the formula: ##STR32##
Claim 76
Dependent Claim
25 words
The composition of claim 68 further comprising from 1 to about 5 parts by weight of an impact modified epoxy having the generalized formula: ##STR33##
Claim 77
Dependent Claim
66 words
A resinous composition comprising an admixture of an unsaturated bis-imide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes, wherein said bis-imide has the formula: ##STR34## wherein: Y is an unsaturated divalent radical having at least 2 carbon atoms; and Z is a divalent radical having from 1 to about 20 carbon atoms.
Claim 78
Dependent Claim
66 words
A resinous composition comprising an admixture of an unsaturated bis-imide essentially free of terminal amine groups and an epoxy having a homopolymerization temperature greater than the temperature at which the polyimide polymerizes, wherein said bis-imide has the formula: ##STR34## wherein: Y is an unsaturated divalent radical having at least 2 carbon atoms; and Z is a divalent radical having from 1 to about 20 carbon atoms.
Claim 79
Dependent Claim
19 words
The composition of claim 70 wherein said epoxy has a viscosity less than about 10,000 cp at 120° F.
Claim 80
Dependent Claim
19 words
The composition of claim 70 wherein Y is derived from maleic acid, citraconic acid, tetrahydrophthalic acid, or anhydrides thereof.
Claim 81
Dependent Claim
17 words
The composition of claim 70 wherein Z is selected from an aliphatic, cycloaliphtic aromatic or heterocyclic radical.
Claim 82
Dependent Claim
99 words
A resinous composition comprising an admixture of an unsaturated bis-imide essentially free of terminal amine groups and an epoxy having a viscosity less than about 10,000 cp at 120° F. and a homopolymerization temperature greater than the temperature at which the polyimide polymerizes, wherein said bis-imide has the formula: ##STR35## wherein: Y is an unsaturated divalent radical derived from malaeic acid, citraconic acid, tetrahydrophthalic acid, or anhydrides thereof and has at least 2 carbon atoms; and Z is a divalent radical selected from an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, and has from 1 to about 20 carbon atoms.
Claim 83
Dependent Claim
99 words
A resinous composition comprising an admixture of an unsaturated bis-imide essentially free of terminal amine groups and an epoxy having a viscosity less than about 10,000 cp at 120° F. and a homopolymerization temperature greater than the temperature at which the polyimide polymerizes, wherein said bis-imide has the formula: ##STR35## wherein: Y is an unsaturated divalent radical derived from malaeic acid, citraconic acid, tetrahydrophthalic acid, or anhydrides thereof and has at least 2 carbon atoms; and Z is a divalent radical selected from an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, and has from 1 to about 20 carbon atoms.
Claim 84
Dependent Claim
46 words
An resinous composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and a a glycidyl amine epoxy having a viscosity less than about 10,000 cp at 120° F. and a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 85
Dependent Claim
46 words
An resinous composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and a a glycidyl amine epoxy having a viscosity less than about 10,000 cp at 120° F. and a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 86
Dependent Claim
43 words
A resinous composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a viscosity less than about 10,000 cp at 120° F. and a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
Claim 87
Dependent Claim
43 words
A resinous composition comprising an admixture of an unsaturated polyimide essentially free of terminal amine groups and an epoxy having a viscosity less than about 10,000 cp at 120° F. and a homopolymerization temperature greater than the temperature at which the polyimide polymerizes.
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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) | 1988-04-08 | 1988-10-08 | 1989-04-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-04-08 | 1992-10-08 | 1993-04-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-04-08 | 1996-10-08 | 1997-04-09 | $7700.00 | Window Closed / Lapsed |