US4736015A
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Aromatic polyimide compositions of high solubility and their uses
Assignee: IFP Energies nouvelles
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Filing: 1982-10-19
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Granted: 1988-04-05
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Expires: 2002-10-19
Abstract
Abstract Aromatic polyimide compositions, useful in particular for manufacturing adhesive materials, varnishes and films withstanding high temperatures, having a high solubility in organic solvents, particularly polar solvents and which are manufactured by reacting, in such a solvent, a tetraester or diacid-diester of benzhydrol 3,3', 4, 4' tetracarboxylic acid with an aromatic diamine for a sufficient time to obtain a polycondensation reaction product having an inherent viscosity at 30 DEG C., at a concentration of 5 g/liter in N-methyl pyrrolidone, ranging from 0.1 to 2 dl/g.
Inventors
- 👤 Guy Rabilloud
- 👤 Michel Senneron
- 👤 Choua Cohen
- 👤 Paul Mariaggi
- 👤 Bernard Sillion
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 20:30
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10
Claims Analysis
Total Claims: 55
Claim 1
Independent Claim
102 words
A polyimide composition of high solubility, in polar organic solvents which is manufactured by reacting at least one aromatic diamine with at least one tetraester or diacid-diester derived from benzhydrol 3,3',4,4'-tetracarboxylic acid, under conditions which effect polycondensation and imide cyclization thereof, the reaction being continued until an inherent viscosity of at least 0.1 dl/g and at most 2 dl/g is obtained, said viscosity being measured in N-methyl pyrrolidone at 30° C. at a concentration of 5 g of composition per liter of N-methyl pyrrolidone, and to a rate of progress of 90-99.9%, thereby removing a major part of the volatile polycondensation/imidization products.
Claim 2
Dependent Claim
102 words
A polyimide composition of high solubility, in polar organic solvents which is manufactured by reacting at least one aromatic diamine with at least one tetraester or diacid-diester derived from benzhydrol 3,3',4,4'-tetracarboxylic acid, under conditions which effect polycondensation and imide cyclization thereof, the reaction being continued until an inherent viscosity of at least 0.1 dl/g and at most 2 dl/g is obtained, said viscosity being measured in N-methyl pyrrolidone at 30° C. at a concentration of 5 g of composition per liter of N-methyl pyrrolidone, and to a rate of progress of 90-99.9%, thereby removing a major part of the volatile polycondensation/imidization products.
Claim 3
Dependent Claim
23 words
A composition according to claim 1, wherein said reaction is effected in a polar solvent at a temperature from 100° to 250° C.
Claim 4
Dependent Claim
32 words
A composition according to claim 2, wherein said polar solvent is selected from phenols, glycol ethers, glycol esters, amides, dimethylsulfoxide, dimethylsulfone, tetramethylurea, dioxane, pyridine, quinoline, N-methyl pyrrolidone, N-acetyl pyrrolidone, hexamethylphosphotriamide and tetramethylenesulfone.
Claim 5
Dependent Claim
26 words
A composition according to claim 1, wherein said reaction is continued until said inherent viscosity is at least 0.15 dl/g and at most 1 dl/g .
Claim 6
Dependent Claim
81 words
A composition according to claim 1, wherein said at least one diamine has the formula: H.sub.2 N--AR--NH.sub.2 wherein Ar is a divalent, carbocyclic or heterocyclic aromatic radical, the NH 2 groups being fixed to separate carbon atoms of said radical, not located in ortho position with respect to each other; and wherein said at least one tetraester or diacid-diester has the formula: ##STR2## wherein R' is a monovalent hydrocarbon radical and R is a hydrogen atom or a monovalent hydrocarbon radical.
Claim 7
Dependent Claim
27 words
A composition according to claim 5, the wherein said aromatic diamine is bis(4-amino phenyl)ether, and said tetraester or diacid-diester is the ethyl diester of benzhydrol 3,3',4,4'-tetracarboxylic acid.
Claim 8
Dependent Claim
26 words
A composition according to claim 5, wherein said aromatic diamine is bis(4-amino phenyl)methane, and said tetraester or diacid-diester is the methyl diester of benzhydrol 3,3',4,4'-tetracarboxylic acid.
Claim 9
Dependent Claim
21 words
A composition according to claim 5, wherein said aromatic diamine is bis(4-amino phenyl)ether, and said tetraester or diacid-diester is 3,3',4,4'-tetramethoxycarbonyl benzhydrol.
Claim 10
Dependent Claim
20 words
A solution comprising 10 to 80% by weight of a polyimide composition according to claim 1, in an organic solvent.
Claim 11
Dependent Claim
22 words
A solution according to claim 9, wherein at least a major part by weight of said organic solvent is a polar solvent.
Claim 12
Dependent Claim
25 words
A composition according to claim 10, wherein said crosslinking agent is selected from epoxides, isocyanates, alkyl titanates, anhydrides and halogenides of carboxylic acids and siloxanes.
Claim 13
Dependent Claim
15 words
A composition according to claim 11, wherein said crosslinking agent is diglycidyl ether or bis-phenol-A.
Claim 14
Dependent Claim
13 words
A composition according to claim 11, wherein said crosslinking agent is bis(4-isocyanato phenyl)methane.
Claim 15
Dependent Claim
13 words
A composition according to claim 11, wherein said crosslinking agent is tetrabutyl titanate.
Claim 16
Dependent Claim
14 words
A method according to claim 13, wherein the substrate is a metal or glass.
Claim 17
Dependent Claim
13 words
A method according to claim 13, wherein the substrate is a glass fabric.
Claim 18
Dependent Claim
11 words
An article of manufacture produced by the process of claim 15.
Claim 19
Dependent Claim
50 words
In a method of forming an adhesive layer on a substrate, wherein a layer of a solution of an adhesive composition is deposited on said substrate, and the layer is dried and heated to produce an adhesive coating, the improvement wherein said solution is a solution according to claim 9.
Claim 20
Dependent Claim
32 words
A solution according to claim 10, wherein said polar solvent is selected from phenols, glycol ethers, glycol esters, amides, dimethylsulfoxide, dimethylsulfone, tetramethylurea, dioxane, pyridine, quinoline, N-methyl pyrrolidone, N-acetyl pyrrolidone, hexamethylphosphotriamide and tetramethylenesulfone.
Claim 21
Dependent Claim
43 words
A crosslinked polyimide composition produced by crosslinking a polyimide composition according to claim 1 with a monomer or a prepolymer crosslinking agent containing at least two reactive functional groups for reacting with benzhydrol alcohol groups on the polyimide to crosslink the polymer chains.
Claim 22
Dependent Claim
26 words
A composition according to claim 5, wherein Ar is a single aromatic 5-7-membered carbocyclic ring or heterocyclic ring containing any of oxygen, sulfur or nitrogen heteroatoms.
Claim 23
Dependent Claim
60 words
A composition according to claim 5, wherein Ar is formed of 2-6 aromatic 5-7-membered carbocyclic and/or oxygen-, sulfur- and/or nitrogen-containing heterocyclic rings, said rings being fused, linked by a single bond and/or linked by at least one of --O--, --S--, --SO--, --SO 2 --, --CH 2 --, --CF 2 --, --C(CH 3 ) 2 --, --CO--, --CHOH--, --COO-- and --CONH--.
Claim 24
Dependent Claim
27 words
A composition according to claim 5, wherein each R and R' is independently a monovalent C 1-13 alkyl radical or a C 6-13 cycloalkyl or aryl radical.
Claim 25
Dependent Claim
29 words
A composition according to claim 5, wherein R is H, and each R' is independently a monovalent C 1-13 alkyl radical or a C 6-13 cycloalkyl or aryl radical.
Claim 26
Dependent Claim
20 words
A composition according to claim 1, wherein said diamine and said tetraester or diacid-diester are reacted in substantially equimolar proportions.
Claim 27
Dependent Claim
23 words
A composition according to claim 1, wherein 95-100% of the amine groups of said diamine are cyclized to imide groups in said polyimide.
Claim 28
Dependent Claim
26 words
A composition according to claim 1, wherein said reaction is continued to a conversion of about 98-99% and a degree of imidization of at least 98%.
Claim 29
Dependent Claim
20 words
A composition according to claim 1, wherein the molar proportion of diamine to tetraester or diacid-diester is 0.67:1 to 1.5:1.
Claim 30
Dependent Claim
20 words
A composition according to claim 25, wherein the molar proportion of diamine to tetraester or diacid-diester is 0.83:1 to 1.2:1.
Claim 31
Dependent Claim
73 words
A carbinol containing polyimide curable at temperatures of about 200°-400° C., which is prepared by reacting a 3,3+,4,4'-benzhydrol tetracarboxylic diester-diacid, with a polyfunctional heterocyclic or aromatic primary amine using a molar ratio of 0.67:1 to 1.5:1, the reaction being carried out in an inert organic solvent at a temperature sufficient to effect polymerization and imidization and at a rate of progress of 90-99.9%, thereby removing a major part of the volatile polycondensation/imidization products.
Claim 32
Dependent Claim
73 words
A carbinol containing polyimide curable at temperatures of about 200°-400° C., which is prepared by reacting a 3,3+,4,4'-benzhydrol tetracarboxylic diester-diacid, with a polyfunctional heterocyclic or aromatic primary amine using a molar ratio of 0.67:1 to 1.5:1, the reaction being carried out in an inert organic solvent at a temperature sufficient to effect polymerization and imidization and at a rate of progress of 90-99.9%, thereby removing a major part of the volatile polycondensation/imidization products.
Claim 33
Dependent Claim
12 words
The polyimide of claim 30, wherein the solvent is a polar solvent.
Claim 34
Dependent Claim
28 words
The polyimide of claim 30, wherein the polyimide has an intrinsic viscosity of 0.1 to 2 when determined on 0.5 g/dl solutions at 30° C. in N-methyl pyrrolidone.
Claim 35
Dependent Claim
25 words
The polyimide of claim 30, 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, and 1,3-bis(3-aminophenoxy)benzene.
Claim 36
Dependent Claim
26 words
The polyimide of claim 32, wherein a mixture of the bis(methyl half-ester) of 3,3',4,4'-benzhydroltetra-carboxylic acid and the bis (methyl half-ester) of 3,3+,4,4'-benzophenone tetracarboxylic acid is used.
Claim 37
Dependent Claim
92 words
An organic solution containing a carbonyl containing polyimide, useful for preparing an adhesive film curable at 200°-400° C., which is prepared by reacting a molar excess of a 3,3',4,4'-benzhydroltetracarboxylic diester-diacid, with an aromatic 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, and 1,3-bis(3-aminophenoxy)benzene using a molar ratio of up to 1.5:1, the reaction being carried out in an inert polar organic solvent at between about 100°-250° C. and at a rate of progress of 90-99.9%, thereby removing a major part of the volatile polycondensation/imidization products.
Claim 38
Dependent Claim
92 words
An organic solution containing a carbonyl containing polyimide, useful for preparing an adhesive film curable at 200°-400° C., which is prepared by reacting a molar excess of a 3,3',4,4'-benzhydroltetracarboxylic diester-diacid, with an aromatic 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, and 1,3-bis(3-aminophenoxy)benzene using a molar ratio of up to 1.5:1, the reaction being carried out in an inert polar organic solvent at between about 100°-250° C. and at a rate of progress of 90-99.9%, thereby removing a major part of the volatile polycondensation/imidization products.
Claim 39
Dependent Claim
67 words
A process for preparing a polyimide curable at temperatures of 200°-400° C., which comprises the steps of: (a) reacting a 3,3',4,4'-benzhydroyltetracarboxylic diester-diacid compound with an aromatic diamine at about 100°-150° C. in an inert polar organic solvent using a molar ratio of tetracarboxylic acid compound to diamine of 0.67:1 to 1.5:1; and at a rate of progress of 90-99.9%, and (b) removing the water and/or alcohol byproducts.
Claim 40
Dependent Claim
67 words
A process for preparing a polyimide curable at temperatures of 200°-400° C., which comprises the steps of: (a) reacting a 3,3',4,4'-benzhydroyltetracarboxylic diester-diacid compound with an aromatic diamine at about 100°-150° C. in an inert polar organic solvent using a molar ratio of tetracarboxylic acid compound to diamine of 0.67:1 to 1.5:1; and at a rate of progress of 90-99.9%, and (b) removing the water and/or alcohol byproducts.
Claim 41
Dependent Claim
33 words
A composition according to claim 5, wherein said tetraester is selected from the group consisting essentially of the tetramethyl, tetraethyl, tetrabutyl, dimethyl diphenyl, dimethyl dibutyl and diethyl diphenyl esters of benzhydrol 3,3',4,4'-tetracarboxylic acid.
Claim 42
Dependent Claim
13 words
A composition according to claim 37, wherein said tetraester is 3,3',4,4'-tetramethoxy carbonyl benzhydrol.
Claim 43
Dependent Claim
56 words
A composition according to claim 5, wherein the diamine is 1,3-diaminobenzene, 1,4-diaminobenzene, 3,3'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, benzidine, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzanilide, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 4,3'-diaminobenzanilide, 3,3'-diaminophenyl benzoate, 4,4'-diaminophenyl benzoate, bis(4-amino phenyl)dimethyl silane, 2,4-diamino pyridine, 2,6-diamino pyridine, 3,5-diamino pyridine, 3,3'-dimethoxy benzidine, 3,3'-diamino benzophenone, 4,4'-diamino benzophenone, 3,3+-diamino benzhydrol, 4,4'-diamino benzhydrol.
Claim 44
Dependent Claim
22 words
A composition according to claim 5, wherein the tetraester or diacid-diester is a mixture of 3,3'-dicarboxy-4,4'-dimethoxycarbonyl benzhydrol, 4,4'-dicarboxy-3,3'-dimethoxycarbonyl benzhydrol and 3,4'-dicarboxy-4,3+-dimethoxycarbonyl benzhydrol.
Claim 45
Dependent Claim
26 words
A composition according to claim 5, wherein said aromatic diamine is bis(4-amino phenyl)ether and said tetraester or diacid-diester is the methyl diester of benzhydrol 3,3+4,4'-tetracarboxylic acid.
Claim 46
Dependent Claim
25 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3'4,4'-tetracarboxylic acid and said aromatic diamine is m-phenylene diamine.
Claim 47
Dependent Claim
24 words
A composition to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3'4,4'-tetracarboxylic acid and said aromatic diamine is 4,4'-methylene dianiline.
Claim 48
Dependent Claim
24 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 4,4'-oxydianiline.
Claim 49
Dependent Claim
24 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 3,3'-diaminobenzaniline.
Claim 50
Dependent Claim
24 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 4,4'-diaminobenzophenone.
Claim 51
Dependent Claim
25 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 3,3'-diamino benzhydrol.
Claim 52
Dependent Claim
25 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 4,4'-diamino benzhydrol.
Claim 53
Dependent Claim
24 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 4,4'-diaminodiphenyl.
Claim 54
Dependent Claim
24 words
A composition according to claim 5, wherein said tetraester or diacid-diester is the methyl diester of 3,3',4,4'-tetracarboxylic acid and said aromatic diamine is 4,4'-diaminodiphenylsulfone.
Claim 55
Dependent Claim
20 words
A composition according to claim 5, wherein said diamine and said tetraester or diacid-diester are reacted in substantially equimolar proportions.
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) | 1991-04-05 | 1991-10-05 | 1992-04-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-04-05 | 1995-10-05 | 1996-04-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-04-05 | 1999-10-05 | 2000-04-05 | $7700.00 | Window Closed / Lapsed |