# US 5,328,979 A · Thermoplastic copolyimides and composites therefrom

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- Number: US 5,328,979 A
- Document ID: US5328979A
- Status: Granted
- Kind: A
- Application number: 07/976,484
- Filed: 1992-11-16
- Granted: 1994-07-12
- Earliest claimed: 1992-11-16
- Assignees: The University of Akron
- Inventors: Frank Harris; Patricia A. Gabori
- Web page: https://patentgrep.com/patent/US5328979A

## CPC

- C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds}
- C08L 79/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- Y10T 428/29: Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T 428/2933: Coated or with bond, impregnation or core
- Y10T 428/2969: Polyamide, polyimide or polyester
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Copolyimide compositions and methods for their preparation which are melt-processible at relative low pressures, i.e. less than 1000 psi, and are suited for laminating and molding, are described. The invention additionally encompasses copolyimide precursors, reinforced polyimide composites and laminates made from said polyimides where the composite is reinforced by fibrous materials. This is achieved by reacting at least one aromatic dianhydride where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another, with at least one diamine which is capable of a transmidization reaction upon incorporation into the polyimide backbone, and with at least one other diamine which is not capable of undergoing such reaction, the diamine which is capable of undergoing the transimidization reaction being present in an amount of from about 1-50 mole percent in relation to the diamine that is not susceptable to transimidization.

## Claims

### Claim 1

A process for improving the melt processibility of a thermoplastic copolyimide comprising the steps of:
(a) reacting one or more of dianhydrides of formula (I) ##STR7## where Z is a tetravalent organic radical selected from the group consisting of a carbocyclic-aromatic containing radical and a hetero-cyclic aromatic containing radical where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another;
(b) adding at least one first diamine of formula (II) wherein the first diamine has a basicity constant of less than 10.sup.-10,
H.sub.2 N--Q--NH.sub.2 (II)
and at least one second diamine of formula (III) wherein the second diamine has a basicity constant of at least 10.sup.-10,
H.sub.2 N--Q'--NH.sub.2 (III)
where Q is divalent organic radical selected independently from the group consisting of a carbocyclic aliphatic radical, a carbocyclic aromatic containing radical, and a heterocyclic containing radical, the term carbocyclic aromatic containing radical and heterocyclic aromatic containing radical used to define Q includes any radical which has the anhydride groups attached to one or more aromatic ring(s) and has the amine groups attached to one or more aromatic ring(s), and where Q' is an electron-deficient divalent heterocyclic group having a 5- or a 6-membered ring containing from 1-3 heteroatoms, at least one of the heteroatoms being nitrogen and further wherein a first diamine is capable of a transimidization reaction upon incorporation into the polyimide backbone, and wherein a second diamine is not capable of undergoing a transimidization reaction upon incorporation into the polyimide backbone, the first diamine being added in an amount of about 1-50 mole percent in relation to the second diamine; and
(c) forming from about 1-50 mole percent of a thermoplastic polyimide of repeating unit formula (IV), ##STR8## a balance of the thermoplastic polyimide of repeating unit formula (V), ##STR9## the thermoplastic polyimide being melt processible at a pressure less than or equal to 250 psi, and capable of undergoing transimidization in the melt allowing for enhanced melt flow and the rearrangement of repeat unit sequences along the polymer backbone.

### Claim 2 (depends on 1)

The process of claim 1 wherein a rate of transimidization is accelerated by a catalyst effective for the transimidization reaction.

### Claim 3

A process for improving the melt processibility of a thermoplastic copolyimide comprising the steps of:
(a) reacting one or more of dianhydrides of formula (I) ##STR10## where Z is a tetravalent organic radical selected from the group consisting of a carbocyclic aromatic containing radical and a heterocyclic aromatic containing radical where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another with an alcohol to form a dialkyl diester;
(b) dissolving the dialkyl diester in a solvent containing at least one first diamine of formula (II) wherein the first diamine has a basicity constant of less than 10.sup.-10,
H.sub.2 N--Q--NH.sub.2 (II)
and at least one second diamine of formula (III) wherein the second diamine has a basicity constant of at least 10.sup.-10,
H.sub.2 N--Q'--NH.sub.2 (III)
where Q is divalent organic radical selected independently from the group consisting of a carbocyclic aliphatic radical, a carbocyclic aromatic containing radical, and a heterocyclic containing radical, the term carbocyclic aromatic containing radical and heterocyclic aromatic containing radical used to define Q includes any radical which has the anhydride groups attached to one or more aromatic ring(s) and has the amine groups attached to one or more aromatic ring(s), and where Q' is an electron-deficient divalent heterocyclic group having a 5- or a 6-membered ring containing from 1-3 heteroatoms, at least one of the heteroatoms being nitrogen and further wherein a first diamine is capable of a transimidization reaction upon incorporation into the polyimide backbone, and wherein a second diamine is not capable of undergoing a transimidization reaction upon incorporation into the polyimide backbone, the first diamine being added in an amount of about 1-50 mole percent in relation to the second diamine; and
(c) heating until the dialkyl diester and the first and second diamines react thereby forming from about 1-50 mole percent of a thermoplastic polyimide of repeating unit formula (IV), ##STR11## a balance of the thermoplastic polyimide of repeating unit formula (V), ##STR12## the thermoplastic polyimide being melt processible at a pressure less than or equal to 250 psi, and capable of undergoing transimidization in the melt allowing for enhanced melt flow and the rearrangement of repeat unit sequences along the polymer backbone.

### Claim 4 (depends on 3)

The process of claim 3 wherein the solvent is selected from the group consisting of N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidinone, tetrahydrofuran, alcohols and mixtures thereof.

### Claim 5

A process for improving the melt processibility of a thermoplastic copolyimide having comprising the steps of:
(a) reacting one or more of dianhydrides of formula (I) ##STR13## where Z is a tetravalent organic radical selected from the group consisting of a carbocyclic-aromatic containing radical and a hetero-cyclic aromatic containing radical where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another with an alcohol to form a dialkyl diester;
(b) reacting the dialkyl diester with at least one first diamine of formula (II) wherein the first diamine has a basicity constant of less than 10.sup.-10,
H.sub.2 N--Q--NH.sub.2 (II)
in a solvent to form a precursor oligomer solution;
(c) reacting at least one second diamine of formula (III) wherein the second diamine has a basicity constant of at least 10.sup.-10,
H.sub.2 N--Q'--NH.sub.2 (III)
with the oligomer solution, where Q is divalent organic radical selected independently from the group consisting of a carbocyclic aliphatic radical, a carbocyclic aromatic containing radical, and a heterocyclic containing radical, the term carbocyclic aromatic containing radical and heterocyclic aromatic containing radical used to define Q includes any radical which has the anhydride groups attached to one or more aromatic ring(s), and has the amine groups attached to one or more aromatic ring(s), and where Q'is a highly electron-deficient divalent heterocyclic group having a 5- or a 6-membered ring containing from 1-3 heteroatoms, at least one of the heteroatoms being nitrogen and further wherein a first diamine is capable of a transimidization reaction upon incorporation into the polyimide backbone, and wherein a second diamine is not capable of undergoing a transimidization reaction upon incorporation into the polyimide backbone, the first diamine being added in an amount of about 1-50 mole percent in relation to the second diamine to form a viscous oligomer solution;
(d) coating the viscous solution on a substrate;
(e) drying the coated substrate to remove the solvent thereby forming from about 1-50 mole percent of a thermoplastic polyimide of repeating unit formula (IV), ##STR14## a balance of the thermoplastic polyimide of repeating unit formula (V); and ##STR15## (f) consolidating the coated substrate in an autoclave by subjecting the substrate to a heating and pressure cycle wherein the pressure is less than or equal to 250 psi.

### Claim 6 (depends on 5)

The process of claim 5 wherein the solvent is selected from the group consisting of N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidinone, tetrahydrofuran, alcohols and mixtures thereof.

### Claim 7 (depends on 5)

The process of claim 5 wherein the substrate is selected from the group consisting of carbon fibers, polyamide fibers, polyester fibers, polyimide fibers, cellulose fibers, cellulose-derived fibers, inorganic fibers and metallic fibers.

### Claim 8 (depends on 7)

The process of claim 7 wherein the substrate is a carbon fiber.

### Claim 9 (depends on 5)

The process of claim 5 wherein a rate of transimidization is accelerated by a catalyst effective for the transimidization reaction.

### Claim 10

A thermoplastic copolyimide melt-processible at a pressure less than or equal to 250 psi, comprising:
(a) from 1-50 mole percent of a thermoplastic polyimide of repeating unit formula (IV); and ##STR16## (b) a balance of the thermoplastic polyimide of repeating unit formula (V) ##STR17## wherein the thermoplastic copolyimide is the product of a reaction of one or more dianhydrides of formula (I) ##STR18## where Z is a tetravalent organic radical selected from the group consisting of a carbocyclic-aromatic containing radical and a hetero-cyclic aromatic containing radical where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another, with at least one first diamine of formula (II) wherein the first diamine has a basicity constant of less than 10.sup.-10,
H.sub.2 N--Q--NH.sub.2 (II)
and at least one second diamine of formula (III) wherein the second diamine has a basicity constant of at least 10.sup.-10,
H.sub.2 N--Q'--NH.sub.2 (III)
where Q is divalent organic radical selected independently from the group consisting of a carbocyclic aliphatic radical, a carbocyclic aromatic containing radical, and a heterocyclic containing radical, the term carbocyclic aromatic containing radical and heterocyclic aromatic containing radical used to define Q includes any radical which has the anhydride groups attached to one or more aromatic ring(s) and has the amine groups attached to one or more aromatic ring(s), and where Q' is an electron-deficient divalent heterocyclic group having a 5- or a 6-membered ring containing from 1-3 heteroatoms, at least one of the heteroatoms being nitrogen and further wherein a first diamine is capable of a transimidization reaction upon incorporation into the polyimide backbone, and wherein a second diamine is not capable of undergoing a transimidization reaction upon incorporation into the polyimide backbone, the first diamine being added in an amount of about 1-50 mole percent in relation to the second diamine, and capable of undergoing transimidization in the melt allowing for enhanced melt flow and the rearrangement of repeat unit sequences along the polymer backbone.

### Claim 11 (depends on 10)

The thermoplastic copolyimide of claim 10 wherein the first diamine is selected from the group consisting of 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diaminopyrimidine, 3,5-diamino-1,2,4-triazole, 4-chloro-2,6-diaminopyrimidine,2,4-diamino-s-triazine, 2-chloro-4,6-diaminotriazine and 6,6'-diamino-2,2'-bipyridine and the second diamine is selected from the group consisting of 1,4-diaminobenzene, 1,3-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)-1,1'-biphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diamino-1,1'-bipenyl, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)-2,2-diethylpropane, 1,2-bis(3-aminophenoxy)ethane, 1,2-bis(4-aminophenoxy)ethane, bis[2-(4-aminophenoxy)ethyl]ether, bis[2-(3-aminophenoxy)ethyl]ether, bis{2-[2-(4-aminophenoxy)ethoxy]ethyl}ether, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 1,3-bis(4-aminophenoxy-4'-benzoyl)benzene, 1,4-bis(4-aminophenoxy-4'-benzoyl)benzene, 4,4'-bis(4-aminophenoxy-4'-benzoyl)benzophrnone, 4,4'-bis(4-aminophenoxy-4'-benzoyl)diphenylether, and 1,4-bis(4-aminophenoxy)-2-phenylbenzene.

### Claim 12 (depends on 10)

The thermoplastic copolyimide of claim 10 wherein the dianhydride is selected from the group consisting of pyromellitic acid dianhydride, 3,6-diphenylpyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, bis(2,3-dicarboxyphenyl)-methane dianhydride, bis(2,5,6-trifluoro-3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl)-sulfone dianhydride, N,N-(3,4-dicarboxyphenyl)-N-methylamine dianhydride, bis(3,4-dicarboxyphenyl)diethylsilane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 4,4'-[4,4'-isopropylidene-di(p-phenyleneoxy)]bis bis(phthalicanhydride), 2,3,6,7-naphthalene-tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene-tetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5;8-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride and pyridine-2,3,5,6-tetracarboxylic acid dianhydride as well as esters of the above listed compounds.

### Claim 13 (depends on 10)

The thermoplastic copolyimide of claim 10 further comprising from 5-25 mole percent of a thermoplastic polyimide repeating unit of formula (IV) and the balance of the thermoplastic polyimide of repeating unit (V).

### Claim 14 (depends on 10)

The thermoplastic copolyimide of claim 10 wherein the second diamine contains from 1-2 heteroatoms, the heteroatoms selected from the group consisting of nitrogen and sulfur.

### Claim 15 (depends on 14)

The thermoplastic copolyimide of claim 14 wherein the second diamine contains at least one halogen substituent group on the aromatic rings.

### Claim 16

A thermoplastic copolyimide having a T.sub.g greater than 300.degree. C., melt-processible at a pressure less than or equal to 250 psi, comprising:
(a) from 1-50 mole percent of a thermoplastic polyimide of repeating unit formula (IV); and ##STR19## (b) a balance of the thermoplastic polyimide of repeating unit formula (V). ##STR20## where Z is a tetravalent organic radical selected from the group consisting of a carbocyclic-aromatic containing radical and a hetero-cyclic aromatic containing radical where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another, and where Q is divalent organic radical selected independently from the group consisting of a carbocyclic aliphatic radical, a carbocyclic aromatic containing radical, and a heterocyclic containing radical, the term carbocyclic aromatic containing radical and heterocyclic aromatic containing radical used to define Q includes any radical which has the anhydride groups attached to one or more aromatic ring(s) and has the amine groups attached to one or more aromatic ring(s), and where Q' is an electron-deficient divalent heterocyclic group having a 5- or a 6-membered ring containing from 1-3 heteroatoms, at least one of the heteroatoms being nitrogen.

### Claim 17 (depends on 16)

The thermoplastic copolyimide of claim 16 further comprising from 5-25 mole percent of a thermoplastic polyimide repeating unit of formula (IV) and the balance of the thermoplastic polyimide of repeating unit (V).

### Claim 18 (depends on 16)

The thermoplastic copolyimide of claim 16 wherein the second diamine contains from 1-2 heteroatoms, the heteroatoms selected from the group consisting of nitrogen and sulfur.