US4489185A
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Carbinol-containing polyimides capable of self-crosslinking at low temperature
Assignee: Ingredion Inc
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Filing: 1983-09-26
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Granted: 1984-12-18
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Expires: 2003-09-26
Abstract
Abstract Novel carbinol-containing polyimides capable of self-crosslinking at low temperatures are prepared by reacting a molar excess of selected 3,3',4,4'-benzhydrol tetracarboxylic acid compounds (the tetraacid, diester-diacid, or (dianhydride) with polyfunctional polyamines (e.g. 4,4'-methylenedianiline, 1,6-hexanediamine, etc.) in an inert organic solvent at about 100 DEG -150 DEG C. The molar ratio of tetracarboxylic acid compound to diamine must be between 2:1 and 9:8. The polyimides may be crosslinked at less than 200 DEG C. via a reaction between the carbinol group(s) and the end group(s) of the polyimide.
Inventors
- 👤 Jules E. Schoenberg
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:23
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
181 words
A carbinol-containing polyimide curable at temperatures less than 200° C., which is prepared by reacting a molar excess of a 3,3',4,4'-benzhydrol tetracarboxylic acid compound selected from the group consisting of the tetraacid, diester-diacid, and dianhydride with a polyfunctional aliphatic, cycloaliphatic, heterocyclic, or aromatic primary amine using a molar ratio of between 2:1 and 9:8, the reaction being carried out in an inert organic solvent at a temperature sufficient to effect polymerization and imidization, the polyimide comprising a chain of recurring units having the formula: ##STR3## wherein R is a divalent aliphatic, cycloaliphatic, aromatic, or heterocyclic radical; Ar is the same or different aromatic radical with the two pairs of attached carbonyl groups situated on adjacent carbon atoms in the Ar radical, wherein at least a substantial number of the Ar groups have the formula ##STR4## X and Y are --OH, or X is --OH when Y is --OR' or Y is --OH when X is --OR', or X and Y together are an O group; R' is the same or a different lower alkyl group; and n is 0 to 7.
Claim 2
Dependent Claim
181 words
A carbinol-containing polyimide curable at temperatures less than 200° C., which is prepared by reacting a molar excess of a 3,3',4,4'-benzhydrol tetracarboxylic acid compound selected from the group consisting of the tetraacid, diester-diacid, and dianhydride with a polyfunctional aliphatic, cycloaliphatic, heterocyclic, or aromatic primary amine using a molar ratio of between 2:1 and 9:8, the reaction being carried out in an inert organic solvent at a temperature sufficient to effect polymerization and imidization, the polyimide comprising a chain of recurring units having the formula: ##STR3## wherein R is a divalent aliphatic, cycloaliphatic, aromatic, or heterocyclic radical; Ar is the same or different aromatic radical with the two pairs of attached carbonyl groups situated on adjacent carbon atoms in the Ar radical, wherein at least a substantial number of the Ar groups have the formula ##STR4## X and Y are --OH, or X is --OH when Y is --OR' or Y is --OH when X is --OR', or X and Y together are an O group; R' is the same or a different lower alkyl group; and n is 0 to 7.
Claim 3
Dependent Claim
28 words
The polyimide of claim 1, wherein the polyimide has an intrinsic viscosity of up to about 0.40 when determined on 1 g./dl. solutions at 25° C. in 1-methyl-2-pyrrolidinone.
Claim 4
Dependent Claim
28 words
The polyimide of claim 2, wherein the molar ratio is between 2:1 and 6:5 and n is 0-4 and wherein the curing temperature is 150° C. or less.
Claim 5
Dependent Claim
12 words
The polyimide of claim 3, wherein the intrinsic viscosity is about 0.10-0.40.
Claim 6
Dependent Claim
26 words
The polyimide of claim 1, wherein the amine is selected from the group consisting of 4,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-sulfonyldianiline, 4,4'-bis(3-aminobenzoyl)diphenyl ether, m-phenylenediamine, bis(3-aminopropyl)tetramethyl disiloxane, 1,6-hexanediamine, and 1,3-bis(3-aminophenoxy)benzene.
Claim 7
Dependent Claim
27 words
The polyimide of claim 5, wherein the polyimide has an intrinsic viscosity up to about 0.40 when determined on 1 g./dl. solutions at 25° C. in 1-methyl-2-pyrrolidinone.
Claim 8
Dependent Claim
18 words
The polyimide of claim 6, wherein the molar ratio is between 2:1 and 6:5 and n is 0-4.
Claim 9
Dependent Claim
12 words
The polyimide of claim 5, wherein the amine is 4,4'-oxydianiline or 4,4'-methylenedianiline.
Claim 10
Dependent Claim
25 words
The polyimide of claim 5, wherein a mixture of the bis(methyl half-ester) of 3,3',4,4'-benzhydroltetracarboxylic acid and the bis(methyl half-ester) of 3,3'4,4'-benzophenone tetracarboxylic acid is used.
Claim 11
Dependent Claim
18 words
The polyimide of claim 8, wherein the molar ratio is between 2:1 and 4:3 and n is 0-2.
Claim 12
Dependent Claim
26 words
The polyimide of claim 10, wherein the polyimide has an intrinsic viscosity of about 0.15-0.25 when determined on 1 g./dl. solutions at 25° C. in 1-methyl-2-pyrrolidinone.
Claim 13
Dependent Claim
22 words
The polyimide of claim 11, wherein the amine is 4,4'-oxydianiline and wherein the molar ratio is about 4:3 and n is 2.
Claim 14
Dependent Claim
15 words
The polyimide of claim 1, wherein the reaction is carried out at about 100°-150° C.
Claim 15
Dependent Claim
12 words
The polyimide of claim 13, wherein the solvent is a polar solvent.
Claim 16
Dependent Claim
32 words
The polyimide of claim 14, wherein the solvent is selected from the group consisting of phenols, glycol ethers, amides, dimethylsulfoxide, dimethyl sulfone, tetramethyl urea, dioxane, pyridine, quinoline, 1-methyl-2-pyrrolidinone, N-acetylpyrrolidinone, hexamethylphosphotriamide, and tetramethylenesulfone.
Claim 17
Dependent Claim
10 words
The polyimide of claim 15, wherein the solvent is 1-methyl-2-pyrrolidinone.
Claim 18
Dependent Claim
91 words
An organic solution containing a carbinol-containing polyimide, useful for preparing an adhesive film curable at less than 200° C., which is prepared by reacting a molar excess of a 3,3',4,4'-benzhydroltetracarboxylic acid compound selected from the groups consisting of the tetraacid, diester-diacid, or dianhydride with an aromatic or aliphatic diamine selected from the group consisting of 4,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-sulfonyldianiline, 4,4'-bis(3-aminobenzoyl)diphenyl ether, m-phenylenediamine, bis(3-aminopropyl)tetramethyl disiloxane, 1,6-hexanediamine, and 1,3-bis(3-aminophenoxy)benzene using a molar ratio of between 2:1 and 9:8, the reaction being carried out in a inert polar organic solvent at between about 100°-150° C.
Claim 19
Dependent Claim
91 words
An organic solution containing a carbinol-containing polyimide, useful for preparing an adhesive film curable at less than 200° C., which is prepared by reacting a molar excess of a 3,3',4,4'-benzhydroltetracarboxylic acid compound selected from the groups consisting of the tetraacid, diester-diacid, or dianhydride with an aromatic or aliphatic diamine selected from the group consisting of 4,4'-methylenedianiline, 4,4'-oxydianiline, 4,4'-sulfonyldianiline, 4,4'-bis(3-aminobenzoyl)diphenyl ether, m-phenylenediamine, bis(3-aminopropyl)tetramethyl disiloxane, 1,6-hexanediamine, and 1,3-bis(3-aminophenoxy)benzene using a molar ratio of between 2:1 and 9:8, the reaction being carried out in a inert polar organic solvent at between about 100°-150° C.
Claim 20
Dependent Claim
19 words
The polyimide of claim 17, wherein the solvent is 1-methyl-2-pyrrolidinone and wherein the cure temperature is about 150° C.
Claim 21
Dependent Claim
74 words
A process for preparing a polyimide curable at temperatures less than 200° C., which comprises the steps of: a. reacting a 3,3',4,4'-benzhydroltetracarboxylic acid compound selected from the group consisting of the tetraacid, diester-diacid, or dianhydride with an aromatic or aliphatic diamine at about 100°-150° C. in an inert polar organic solvent using a molar ratio of tetracarboxylic acid compound to diamine of between 2:1 and 9:8; and b. removing the water and/or alcohol by-products.
Claim 22
Dependent Claim
74 words
A process for preparing a polyimide curable at temperatures less than 200° C., which comprises the steps of: a. reacting a 3,3',4,4'-benzhydroltetracarboxylic acid compound selected from the group consisting of the tetraacid, diester-diacid, or dianhydride with an aromatic or aliphatic diamine at about 100°-150° C. in an inert polar organic solvent using a molar ratio of tetracarboxylic acid compound to diamine of between 2:1 and 9:8; and b. removing the water and/or alcohol by-products.
Claim 23
Dependent Claim
14 words
The process of claim 19, further comprising the step of (c) removing the solvent.
References Cited (Backward Citations)
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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) | 1987-12-18 | 1988-06-18 | 1988-12-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-12-18 | 1992-06-18 | 1992-12-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-12-18 | 1996-06-18 | 1996-12-18 | $7700.00 | Window Closed / Lapsed |