US5338827A
Expired / Lapsed
US
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Polyimide resins useful at high temperatures
Assignee: Northrop Grumman Systems Corp
•
Filing: 1991-12-27
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Granted: 1994-08-16
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Expires: 2011-12-27
Abstract
Abstract Polyimide resins useful at high temperatures are prepared from: (a) a dialkyl, trialkyl or tetraalkylester of biphenyltetracarboxylic acid; (b) phenylenediamine, preferably the phenylenediamine comprises a mixture of meta-and para-phenylenediamine; and (c) a divalent end cap compound that is capable of undergoing addition polymerization.
Inventors
- 👤 Tito T. Serafini
- 👤 Paul G. Cheng
- 👤 Kenneth K. Ueda
- 👤 Ward F. Wright
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 20:45
CPC Classifications
C; C07; C07D; C07D209/00; C07D209/02; C07D209/44; C07D209/48; C07D405/00; C07D405/14; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1003; C08G73/1007; C08G73/101; C08G73/1014; C08G73/1017; C08G73/12; C08G73/121
Claims Analysis
Total Claims: 40
Claim 1
Independent Claim
109 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR17## where (i) each E 1 is independently an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, (ii) the nitrogen of the structure: ##STR18## consists essentially of nitrogen in the meta- and para- positions, the ratio between the meta- and para- nitrogen being from about 3:2 to about 4:1, and (iii) n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 2
Dependent Claim
109 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR17## where (i) each E 1 is independently an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, (ii) the nitrogen of the structure: ##STR18## consists essentially of nitrogen in the meta- and para- positions, the ratio between the meta- and para- nitrogen being from about 3:2 to about 4:1, and (iii) n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 3
Dependent Claim
73 words
A composition of matter comprising low molecular weight prepolymer suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR19## where E 1 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 4
Dependent Claim
73 words
A composition of matter comprising low molecular weight prepolymer suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR19## where E 1 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 5
Dependent Claim
73 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR20## where E 1 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 6
Dependent Claim
73 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR20## where E 1 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 7
Dependent Claim
109 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR21## where (i) each E 2 is independently an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, (ii) the nitrogen of the structure: ##STR22## consists essentially of nitrogen in the meta- and para- positions, the ratio between the meta- and para- nitrogen being from about 3:2 to about 4:1, and (iii) n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 8
Dependent Claim
109 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR21## where (i) each E 2 is independently an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, (ii) the nitrogen of the structure: ##STR22## consists essentially of nitrogen in the meta- and para- positions, the ratio between the meta- and para- nitrogen being from about 3:2 to about 4:1, and (iii) n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 9
Dependent Claim
73 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR23## where E 2 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 10
Dependent Claim
73 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR23## where E 2 is an end cap radical having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 11
Dependent Claim
72 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR24## where E 2 is an end cap having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 12
Dependent Claim
72 words
A composition of matter comprising low molecular weight prepolymers suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula: ##STR24## where E 2 is an end cap having at least one unsaturated moiety and being capable of undergoing addition polymerization, and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 13
Dependent Claim
234 words
A composition of matter consisting essentially of a mixture of the monomers: (a) a dialkyl, trialkyl, or tetraalkylester of biphenyltetracarboxylic acid; (b) phenylenediamine; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the phenylenediamine or the ester to form an end cap radical that precludes further reaction of the phenylenediamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), phenylenediamine (b), and end cap compound (c) are present in a molar ratio such that heating the mixture forms low molecular weight prepolymers having one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula of either: ##STR25## where E 3 is an end cap radical provided by the end cap compound when the prepolymers are of formula (d), E 4 is an end cap radical provided by the end cap compound when the prepolymers are of formula (e), E 5 is an end cap radical provided by the end cap compound when the prepolymers are of formula (f), and E 6 is an end cap radical provided by the end cap compound when the prepolymers are of formula (g), and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 14
Dependent Claim
234 words
A composition of matter consisting essentially of a mixture of the monomers: (a) a dialkyl, trialkyl, or tetraalkylester of biphenyltetracarboxylic acid; (b) phenylenediamine; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the phenylenediamine or the ester to form an end cap radical that precludes further reaction of the phenylenediamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), phenylenediamine (b), and end cap compound (c) are present in a molar ratio such that heating the mixture forms low molecular weight prepolymers having one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula of either: ##STR25## where E 3 is an end cap radical provided by the end cap compound when the prepolymers are of formula (d), E 4 is an end cap radical provided by the end cap compound when the prepolymers are of formula (e), E 5 is an end cap radical provided by the end cap compound when the prepolymers are of formula (f), and E 6 is an end cap radical provided by the end cap compound when the prepolymers are of formula (g), and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 15
Dependent Claim
211 words
A composition of matter consisting essentially of a mixture of the monomers: (a) a dialkyl, trialkyl, or tetralkylester of biphenyltetracarboxylic acid; (b) phenylenediamine, consisting essentially of meta-phenylenediamine mixed with para-phenylenediamine in the molar ratio of from about 3:2 to about 4:1; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the phenylenediamine or the ester to form an end cap radical that precludes further reaction of the phenylenediamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), phenylenediamine (b), and end cap compound (c) are present in a molar ratio such that heating the mixture forms low molecular weight prepolymers having two end cap radicals and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula of either: ##STR26## where E 1 is an end cap radical provided by the end cap compound when the prepolymers are of formula (d), E 2 is an end cap radical provided by the end cap compound when the prepolymers are of formula (e), and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 16
Dependent Claim
211 words
A composition of matter consisting essentially of a mixture of the monomers: (a) a dialkyl, trialkyl, or tetralkylester of biphenyltetracarboxylic acid; (b) phenylenediamine, consisting essentially of meta-phenylenediamine mixed with para-phenylenediamine in the molar ratio of from about 3:2 to about 4:1; and (c) a divalent end cap compound characterized by (i) having at least one unsaturated moiety, (ii) being capable of reacting with the phenylenediamine or the ester to form an end cap radical that precludes further reaction of the phenylenediamine with the ester, and (iii) being capable of undergoing addition polymerization, wherein the ester (a), phenylenediamine (b), and end cap compound (c) are present in a molar ratio such that heating the mixture forms low molecular weight prepolymers having two end cap radicals and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides, the prepolymers having the formula of either: ##STR26## where E 1 is an end cap radical provided by the end cap compound when the prepolymers are of formula (d), E 2 is an end cap radical provided by the end cap compound when the prepolymers are of formula (e), and n is at least 2 and is sufficiently small that the average molecular weight of the prepolymers is less than about 50,000.
Claim 17
Dependent Claim
109 words
A composition of matter consisting essentially of a mixture of compounds: (a) an ester of the formula: ##STR27## wherein each R 1 is independently selected from a group consisting of alkyl and hydrogen; at least two R 1 are alkyl; (b) phenylenediamine; and (c) a divalent end cap compound selected from the group consisting of (i) a mono or dialkyl ester of a dicarboxylic acid, and (ii) an aromatic amine; and wherein the molar ratio of a:b:c is such that heating the mixture forms a low molecular weight prepolymer having one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides.
Claim 18
Dependent Claim
109 words
A composition of matter consisting essentially of a mixture of compounds: (a) an ester of the formula: ##STR27## wherein each R 1 is independently selected from a group consisting of alkyl and hydrogen; at least two R 1 are alkyl; (b) phenylenediamine; and (c) a divalent end cap compound selected from the group consisting of (i) a mono or dialkyl ester of a dicarboxylic acid, and (ii) an aromatic amine; and wherein the molar ratio of a:b:c is such that heating the mixture forms a low molecular weight prepolymer having one end cap radical and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides.
Claim 19
Dependent Claim
127 words
A composition of matter consisting essentially of a mixture of compounds: (a) an ester of the formula: ##STR28## wherein each R 1 is independently selected from a group consisting of alkyl and hydrogen; at least two R 1 are alkyl; (b) phenylenediamine, consisting essentially of meta-phenylenediamine mixed with para-phenylenediamine in the molar ratio of from about 3:2 to about 4:1; and (c) a divalent end cap compound selected from the group consisting of (i) a mono or dialkyl ester of a dicarboxylic acid, and (ii) an aromatic amine; and wherein the molar ratio of a:b:c is such that heating the mixture forms a low molecular weight prepolymer having two end cap radicals and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides.
Claim 20
Dependent Claim
127 words
A composition of matter consisting essentially of a mixture of compounds: (a) an ester of the formula: ##STR28## wherein each R 1 is independently selected from a group consisting of alkyl and hydrogen; at least two R 1 are alkyl; (b) phenylenediamine, consisting essentially of meta-phenylenediamine mixed with para-phenylenediamine in the molar ratio of from about 3:2 to about 4:1; and (c) a divalent end cap compound selected from the group consisting of (i) a mono or dialkyl ester of a dicarboxylic acid, and (ii) an aromatic amine; and wherein the molar ratio of a:b:c is such that heating the mixture forms a low molecular weight prepolymer having two end cap radicals and suitable for chain extension and crosslinking to form high molecular weight, thermally stable polyimides.
Claim 21
Dependent Claim
41 words
The composition of matter of claim 9, wherein the end cap (c) is a mono or dialkyl ester of a dicarboxylic acid, and wherein the molar ratio of a:b:c: is n:n:1, and wherein n is of from 2 to about 20.
Claim 22
Dependent Claim
40 words
The composition of matter of claim 9, wherein the end cap (c) is a mono or dialkyl ester of a dicarboxylic acid, wherein the molar ratio of a:b:c: is n:n+1:1, and wherein n is of from 2 to about 20.
Claim 23
Dependent Claim
34 words
The composition of matter of claim 9, wherein the end cap (c) is an aromatic amine, wherein the molar ratio of a:b:c: is n+1:n:1, and wherein n is of from 2 to about 20.
Claim 24
Dependent Claim
34 words
The composition of matter of claim 9, wherein the end cap (c) is an aromatic amine, wherein the molar ratio of a:b:c: is n:n:1, and wherein n is of from 2 to about 20.
Claim 25
Dependent Claim
43 words
The composition of matter of any one of claims 7, 9, 11, 12, 13 or 14 wherein the phenylenediamine consists essentially of meta-phenylenediamine alone, or sufficient meta-phenylenediamine mixed with para-phenylenediamine, so that the composition has a shelf life of at least 24 hours.
Claim 26
Dependent Claim
21 words
The composition of matter of claim 15 wherein the molar ratio of meta-phenylenediamine: para-phenylenediamine is from about 1:0 to about 1:1.
Claim 27
Dependent Claim
21 words
The composition of matter of claim 15 wherein the molar ratio of meta-phenylenediamine: para-phenylenediamine is from about 3:2 to about 4:1.
Claim 28
Dependent Claim
19 words
The composition of matter of claim 9 or 10 wherein the molar ratio of meta-phenylenediamine: para-phenylenediamine is about 1:1.
Claim 29
Dependent Claim
34 words
A polyimide resin having a molecular weight greater than 50,000 prepared by the steps of heating the composition of matter of any one of claims 7-14 to form prepolymers and crosslinking the formed prepolymers.
Claim 30
Dependent Claim
31 words
A polyimide resin having a molecular weight greater than 50,000 prepared by the steps of heating the composition of matter of claim 15 to form prepolymers and crosslinking the formed prepolymers.
Claim 31
Dependent Claim
43 words
An article of manufacture comprising fibers impregnating a polyimide resin matrix having a molecular weight greater than 50,000 and prepared by the steps of heating the composition of matter of any one of claims 7-14 to form prepolymers and crosslinking the formed prepolymers.
Claim 32
Dependent Claim
40 words
An article of manufacture comprising fibers impregnating a polyimide resin matrix having a molecular weight greater than 50,000 and prepared by the steps of heating the composition of matter of claim 15 to form prepolymers and crosslinking the formed prepolymers.
Claim 33
Dependent Claim
14 words
The polyimide resin of claim 19 having a T g greater than 800° F.
Claim 34
Dependent Claim
25 words
The polyimide resin of claim 23 having a weight loss of less than 5 percent when heated in air at 700° F. for 100 hours.
Claim 35
Dependent Claim
14 words
The polyimide resin of claim 20 having a T g greater than 800° F.
Claim 36
Dependent Claim
25 words
The polyimide resin of claim 25 having a weight loss of less than 5 percent when heated in air at 700° F. for 100 hours.
Claim 37
Dependent Claim
39 words
The composition of claim 2, 3, 5, or 6 wherein the nitrogen of the structure: ##STR29## consists essentially of nitrogen in the meta- and para-positions, the ratio between the meta- and para-nitrogen being from about 3:2 to about 4:1.
Claim 38
Dependent Claim
28 words
The composition of claim 27 wherein sufficient nitrogen in the structure (1) is in the meta-position that the composition has a shelf life of at least 24 hours.
Claim 39
Dependent Claim
30 words
The composition of claim 1 or 4 wherein sufficient nitrogen in the structure: ##STR30## is in the meta-position that the composition has a shelf life of at least 24 hours.
Claim 40
Dependent Claim
22 words
The composition of claim 8 or 10 comprising sufficient meta-phenylenediamine that the composition has a shelf life of at least 24 hours.
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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) | 1997-08-15 | 1998-02-14 | 1998-08-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2001-08-15 | 2002-02-14 | 2002-08-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2005-08-15 | 2006-02-14 | 2006-08-16 | $7700.00 | Window Closed / Lapsed |