US4395514A
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Process for preparing a carbon fiber reinforced composite article which utilizes a polyimide matrix
Assignee: SUBJECT TO AGREEMENT RECITED SEE DOCUMENT FOR DETAILS
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Filing: 1982-01-29
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Granted: 1983-07-26
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Expires: 2002-01-29
Abstract
Abstract The present invention provides an improvement in a process for preparing carbon fiber reinforced polyimide compositions from a mixture of monomers by the application of heat in two stages. The improvement comprises incorporating a cyclic peroxyketal catalyst, such as 3,6,6,9,9,-pentamethyl-3-(ethylacetate)-1,2,4,5-tetraoxycyclononane, into the monomer mixture prior to reaction.
Inventors
- 👤 Robert Edelman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 15:34
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1003; C08G73/1007; C08G73/1021; Y; Y10; Y10T; Y10T428/00; Y10T428/30; Y10T428/31504; Y10T428/31721
Claims Analysis
Total Claims: 9
Claim 1
Independent Claim
492 words
A process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase which comprises: (1) providing a polyimide forming catalyst-monomer mixture comprising: (a) at least one ester of the formula: ##STR16## wherein R 3 is a tetravalent aryl radical, and R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen, with two R 4 groups being alkyl and two R 4 groups being hydrogen; (b) at least one amine of the formula: H.sub.2 N--R.sub.5 --NH.sub.2 wherein R 5 is a divalent aryl radical; and (c) at least one ester of the formula: ##STR17## wherein R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen with one R 4 group being alkyl and one R 4 group being hydrogen, and R 6 is a divalent radical of the formula: ##STR18## wherein Y, which is the same or different, is selected from the group consisting of hydrogen, and methyl and X is an alkylidene radical of from 1 to 6 carbon atoms; wherein monomers (a), (b) and (c) are present in said mixture at a molar ratio of n:(n+x):y respectively, wherein n is an integer of from about 1 to about 20, x is an integer of from about 0.5 to about 1, and y is an integer of from about 1.5 to about 2, and from about 0.5 to about 15%, by weight, based on the weight of the monomer mixture, of at least one peroxide catalyst represented by the structural formula: ##STR19## wherein R, which is the same or different, is a lower alkyl group having from 1 to about 3 carbon atoms, and R 1 is an alkyl acetate group of the formula: ##STR20## wherein R 2 is an alkyl group having from 1 to about 4 carbon atoms; (2) impregnating at least one carbon fiber lamina with said polyimide forming catalyst-monomer mixture of step (1); (3) reacting said polyimide forming catalyst-monomer mixture in the presence of the at least one carbon fiber lamina at a temperature of from about 250° to about 350° F. for a period of from about 0.5 to about 3 hours and at a pressure of from about 2 to about 30 in.Hg to form a prepolymer; and (4) curing the prepolymer to form a carbon fiber reinforced composite article while employing a short cure procedure which comprises the steps of heating the prepolymer to a temperature of from about 375° to about 425° F. at a continuous or intermittent pressure of from about 175 to about 225 psi; raising the temperature of the prepolymer to a temperature of from about 450° to about 625° F. while under a continuous or intermittent pressure of from about 175 to about 225 psi; and maintaining the temperature of the prepolymer thereat for a period of about 10 to about 120 minutes.
Claim 2
Dependent Claim
492 words
A process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase which comprises: (1) providing a polyimide forming catalyst-monomer mixture comprising: (a) at least one ester of the formula: ##STR16## wherein R 3 is a tetravalent aryl radical, and R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen, with two R 4 groups being alkyl and two R 4 groups being hydrogen; (b) at least one amine of the formula: H.sub.2 N--R.sub.5 --NH.sub.2 wherein R 5 is a divalent aryl radical; and (c) at least one ester of the formula: ##STR17## wherein R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen with one R 4 group being alkyl and one R 4 group being hydrogen, and R 6 is a divalent radical of the formula: ##STR18## wherein Y, which is the same or different, is selected from the group consisting of hydrogen, and methyl and X is an alkylidene radical of from 1 to 6 carbon atoms; wherein monomers (a), (b) and (c) are present in said mixture at a molar ratio of n:(n+x):y respectively, wherein n is an integer of from about 1 to about 20, x is an integer of from about 0.5 to about 1, and y is an integer of from about 1.5 to about 2, and from about 0.5 to about 15%, by weight, based on the weight of the monomer mixture, of at least one peroxide catalyst represented by the structural formula: ##STR19## wherein R, which is the same or different, is a lower alkyl group having from 1 to about 3 carbon atoms, and R 1 is an alkyl acetate group of the formula: ##STR20## wherein R 2 is an alkyl group having from 1 to about 4 carbon atoms; (2) impregnating at least one carbon fiber lamina with said polyimide forming catalyst-monomer mixture of step (1); (3) reacting said polyimide forming catalyst-monomer mixture in the presence of the at least one carbon fiber lamina at a temperature of from about 250° to about 350° F. for a period of from about 0.5 to about 3 hours and at a pressure of from about 2 to about 30 in.Hg to form a prepolymer; and (4) curing the prepolymer to form a carbon fiber reinforced composite article while employing a short cure procedure which comprises the steps of heating the prepolymer to a temperature of from about 375° to about 425° F. at a continuous or intermittent pressure of from about 175 to about 225 psi; raising the temperature of the prepolymer to a temperature of from about 450° to about 625° F. while under a continuous or intermittent pressure of from about 175 to about 225 psi; and maintaining the temperature of the prepolymer thereat for a period of about 10 to about 120 minutes.
Claim 3
Dependent Claim
91 words
The process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase according to claim 1 wherein monomer (a) comprises the diethyl ester of benzophenone tetracarboxylic acid, monomer (c) comprises the monoethyl ester of 5-norborene-2,3-dicarboxylic anhydride, and monomer(b) comprises at least one polyamine having the formula: ##STR21## wherein n is an integer the average value of which can vary from about 0 to about 2, and wherein the ratio of monomers a, b, and c in said mixture is from about 1:1.6:1.5 to about 1:1.6:2, respectively.
Claim 4
Dependent Claim
61 words
The process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase according to claim 2 wherein the polyamine monomer (b) comprises 75 mole percent methylene dianiline, and about 25 mole percent of a mixture of the polyamine wherein n of the structural formula is from about 1 to about 2, and the catalyst is 3,6,6,9,9,-pentamethyl-3(ethylacetate)-1,2,4,5-tetraoxycyclononane.
Claim 5
Dependent Claim
484 words
A process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase which comprises: (1) providing a polyimide forming catalyst-monomer mixture comprising: (a) at least one ester of the formula: ##STR22## wherein R 3 is a tetravalent aryl radical, and R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen, with two R 4 groups being alkyl and two R 4 groups being hydrogen; (b) at least one amine of the formula: H.sub.2 N--R.sub.5 --NH.sub.2 wherein R 5 is a divalent aryl radical; and (c) at least one ester of the formula: ##STR23## wherein R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen with one R 4 group being alkyl and one R 4 group being hydrogen, and R 6 is a divalent radical of the formula: ##STR24## wherein Y, which is the same or different, is selected from the group consisting of hydrogen, and methyl and X is an alkylidene radical of from 1 to 6 carbon atoms; wherein monomers (a), (b) and (c) are present in said mixture at a molar ratio of n:(n+x):y respectively, wherein n is an integer of from about 1 to about 20, x is an integer of from about 0.5 to about 1, and y is an integer of from about 1.5 to about 2, and from about 0.5 to about 15%, by weight, based on the weight of the monomer mixture, of at least one peroxide catalyst represented by the structural formula: ##STR25## wherein R, which is the same or different, is a lower alkyl group having from 1 to about 3 carbon atoms, and R 1 is an alkyl acetate group of the formula: ##STR26## wherein R 2 is an alkyl group having from 1 to about 4 carbon atoms; (2) impregnating at least one carbon fiber lamina with said polyimide forming catalyst-monomer mixture of step (1); (3) reacting said polyimide forming catalyst-monomer mixture in the presence of the at least one carbon fiber lamina at a temperature of about 250° to about 350° F. for a period of from about 0.5 to about 3 hours and at a pressure of from about 2 to 30 in.Hg to form a prepolymer; and (4) curing the prepolymer to form a carbon fiber reinforced composite article while employing a low temperature cure procedure which comprises the steps of heating the prepolymer to a temperature of from about 300° to about 330° F. while under a continuous or intermittent pressure of from about 2 to about 30 in.Hg; raising the temperature of the prepolymer therefrom until a temperature of from about 375° to about 390° F. is attained; maintaining the temperature of the prepolymer thereat for a period of from about 4 to about 10 hours to form a polyimide.
Claim 6
Dependent Claim
484 words
A process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase which comprises: (1) providing a polyimide forming catalyst-monomer mixture comprising: (a) at least one ester of the formula: ##STR22## wherein R 3 is a tetravalent aryl radical, and R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen, with two R 4 groups being alkyl and two R 4 groups being hydrogen; (b) at least one amine of the formula: H.sub.2 N--R.sub.5 --NH.sub.2 wherein R 5 is a divalent aryl radical; and (c) at least one ester of the formula: ##STR23## wherein R 4 is selected from the group consisting of a lower alkyl radical having 1 to 4 carbon atoms, and hydrogen with one R 4 group being alkyl and one R 4 group being hydrogen, and R 6 is a divalent radical of the formula: ##STR24## wherein Y, which is the same or different, is selected from the group consisting of hydrogen, and methyl and X is an alkylidene radical of from 1 to 6 carbon atoms; wherein monomers (a), (b) and (c) are present in said mixture at a molar ratio of n:(n+x):y respectively, wherein n is an integer of from about 1 to about 20, x is an integer of from about 0.5 to about 1, and y is an integer of from about 1.5 to about 2, and from about 0.5 to about 15%, by weight, based on the weight of the monomer mixture, of at least one peroxide catalyst represented by the structural formula: ##STR25## wherein R, which is the same or different, is a lower alkyl group having from 1 to about 3 carbon atoms, and R 1 is an alkyl acetate group of the formula: ##STR26## wherein R 2 is an alkyl group having from 1 to about 4 carbon atoms; (2) impregnating at least one carbon fiber lamina with said polyimide forming catalyst-monomer mixture of step (1); (3) reacting said polyimide forming catalyst-monomer mixture in the presence of the at least one carbon fiber lamina at a temperature of about 250° to about 350° F. for a period of from about 0.5 to about 3 hours and at a pressure of from about 2 to 30 in.Hg to form a prepolymer; and (4) curing the prepolymer to form a carbon fiber reinforced composite article while employing a low temperature cure procedure which comprises the steps of heating the prepolymer to a temperature of from about 300° to about 330° F. while under a continuous or intermittent pressure of from about 2 to about 30 in.Hg; raising the temperature of the prepolymer therefrom until a temperature of from about 375° to about 390° F. is attained; maintaining the temperature of the prepolymer thereat for a period of from about 4 to about 10 hours to form a polyimide.
Claim 7
Dependent Claim
92 words
The process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase according to claim 4 wherein monomer (a) comprises the diethyl ester of benzophenone tetracarboxylic acid, monomer (c) comprises the monoethyl ester of 5-norborene-2,3-dicarboxylic anhydride, and monomer (b) comprises at least one polyamine having the formula: ##STR27## wherein n is an integer the average value of which can vary from about 0 to about 2, and wherein the ratio of monomers a, b, and c in said mixture is from about 1:1.6:1.5 to about 1:1.6:2, respectively.
Claim 8
Dependent Claim
62 words
The process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase according to claim 4 wherein the polyamine monomer (b) comprises about 75 mole percent methylene dianiline, and about 25 mole percent of a mixture of the polyamine wherein n of the structural formula is from about 1 to about 2, and the catalyst is 3,6,6,9,9,-pentamethyl-3(ethylacetate)-1,2,4,5-tetraoxycyclononane.
Claim 9
Dependent Claim
103 words
The process for preparing a carbon fiber reinforced composite article wherein a polyimide constitutes the continuous phase of claim 4 wherein the low temperature cure procedure is followed by a post-cure which comprises heating the polyimide to a temperature of from about 375° to about 385° F. for a period of about 20 to about 30 minutes, raising the temperature of the polyimide in a stepwise manner in increments of about 20° to about 25° F., until a temperature of about 450° to about 525° F. is reached, and maintaining the temperature thereat for a period of about 30 to about 60 minutes.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1986-07-25 | 1987-01-24 | 1987-07-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-07-25 | 1991-01-24 | 1991-07-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-07-25 | 1995-01-24 | 1995-07-26 | $7700.00 | Window Closed / Lapsed |