POLYIMIDE SOLVENT CAST FILMS HAVING A LOW COEFFICIENT OF THERMAL EXPANSION AND METHOD OF MANUFACTURE THEREOF

1 . A solvent cast film, comprising:

a polyimide comprising structural units derived from polymerization of a dianhydride component comprising a dianhydride selected from the group consisting of 3,4′-oxydiphthalic dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, and combinations thereof, with a diamine component;

wherein the polyimide has a glass transition temperature of at least 190° C.;

wherein the film has

a coefficient of thermal expansion of less than 60 ppm/° C.,

a thickness from 0.1 to 250 micrometers, and

less than 5% residual solvent by weight;

wherein the polyimide has less than 15 molar % of structural units derived from a member selected from the group consisting of biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, an ester of biphenyltetracarboxylic acid, and a combination thereof.

2 . The film of claim 1 , wherein the glass transition temperature of the polyimide is from 190° C. to 500° C.

3 . The film of claim 1 , wherein the dianhydride component further comprises a dianhydride selected from the group consisting of:

2,2′-bis(1,3-trifluromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-methyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-phenyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-trifluromethyl-2-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-trifluromethyl-3-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(1-trifluromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;

2,2-bis((4-(3,3-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride;

2,2-bis((4-(3,3-dicarboxyphenoxy)phenyl)propane dianhydride;

2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;

2,2′-dibromo-3,3′,4,4′-biphenyltetracarboxylic dianhydride;

2,3,6,7-naphthalic dianhydride;

3,3′,4,4′-benzophenonetetracarboxylic dianhydride;

3,3′,4,4′-biphenylethertetracarboxylic dianhydride;

3,3′,4,4′-biphenylsulphonictetracarboxylic dianhydride;

3,3′,4,4′-biphenyltetracarboxylic dianhydride;

3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride;

3,3′,4,4′-diphenylmethanetetracarboxylic dianhydride;

3,3′,4,4′-diphenylsulfidetetracarboxylic dianhydride;

3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride;

3,3′,4,4′-diphenylsulfoxidetetracarboxylic dianhydride;

3,3′-benzophenonetetracarboxylic dianhydride;

3,3′-oxydiphthalic dianhydride;

3,4′-oxydiphthalic dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylether dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride;

4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)diphenylether dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)diphenylsulfide dianhydride;

4,4′-bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulphone dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylether dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride;

4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride;

4,4′-bisphenol A dianhydride;

4,4′-carbonyldiphthalic dianhydride;

4,4′-oxydiphthalic dianhydride;

6,6′-bis(3,4-dicarboxyphenoxy)-2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]dianhydride;

7,7′-bis(3,4-dicarboxyphenoxy)-3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2H-1-benzopyran]dianhydride;

bis(phthalic)phenylsulphineoxide dianhydride;

bis(triphenylphthalic)-4,4′-diphenylether dianhydride;

bis(triphenylphthalic)-4,4′-diphenylmethane dianhydride;

hydroquinone diphthalic dianhydride;

m-phenylene-bis(triphenylphthalic) dianhydride;

p-phenylene-bis(triphenylphthalic) dianhydride;

pyromellitic dianhydride;

(3,3′,4,4′-diphenyl)phenylphosphinetetracarboxylic dianhydride;

(3,3′,4,4′-diphenyl)phenylphosphineoxidetetracarboxylic dianhydride;

1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride;

1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride;

1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride;

1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride; and a combination thereof.

4 . The film of claim 1 , wherein the diamine component further comprises a diamine selected from the group consisting of:

1,5-diaminonaphthalene;

2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1H-indene]-6,6′-diamine;

2,4-diaminotoluene;

2,6-diaminotoluene;

3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2H-1-benzopyran]-7,7′-diamine;

3,3′-dimethoxybenzidine;

3,3′-dimethylbenzidine;

4,4′-diaminodiphenylether(4,4′-oxydianiline);

4,4′-diaminodiphenylsulfide;

4,4′-diaminodiphenylsulfone;

4,4′-diaminodiphenylmethane(4,4′-methylenedianiline);

4,4′-diaminodiphenylpropane;

benzidine;

bis(4-aminophenyl)ether;

bis(4-aminophenyl)sulfide;

bis(4-aminophenyl)sulfone;

bis(4-aminophenyl)methane;

bis(4-aminophenyl)propane;

m-phenylenediamine;

m-xylylenediamine;

p-phenylenediamine;

p-xylylenediamine; and a combination thereof.

5 . The film of claim 1 , wherein the diamine component comprises greater than or equal to 10 mole % of 4,4′-diaminodiphenyl sulfone, based on the total moles of diamine.

6 . The film of claim 1 , wherein the diamine component comprises a diamine selected from the group consisting of 4,4′-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, 4,4′-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, and a combination thereof.

7 . The film of claim 6 , wherein the film comprises a combination of diamines sufficient to impart a CTE to the film that remains constant while the combination of diamines also imparts a Tg to the film ranging from 220° C. to 375° C.

8 . The film of claim 1 , wherein the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and a combination thereof.

9 . The film of claim 1 , wherein the film further comprises a nanoclay.

10 . The film of claim 9 , wherein the film has a lower CTE than a film of the same composition without the nanoclay.

11 . The film of claim 10 , wherein the film has a Tg that is the same as a film of the same composition without the nanoclay.

12 . The film of claim 9 , wherein the film is transparent.

13 . The film of claim 1 , wherein the film has a coefficient of thermal expansion of at least 5 ppm/° C.

14 . The film of claim 7 , wherein the film has a coefficient of thermal expansion of 5 to 60 ppm/° C.

15 . The film of claim 1 , wherein the film has a coefficient of thermal expansion of 10 to 30 ppm/° C.

16 . The film of claim 1 , wherein the film has a coefficient of thermal expansion of 10 to 20 ppm/° C.

17 . The film of claim 1 , wherein the film has a coefficient of thermal expansion that is within ±20 ppm/° C. of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer.

18 . The film of claim 1 , wherein the film has a coefficient of thermal expansion that is within ±15 ppm/° C. of the coefficient of thermal expansion of copper.

19 . The film of claim 1 , wherein the film loses less than 5% of its initial weight after storage in water for 24 hours at 25° C.

20 . The film of claim 1 , wherein the film loses less than 2% of its initial weight after storage in water for 24 hours at 25° C.

21 . The film of claim 1 , wherein the film is a dry film, and a 10 wt % solution of the dried film in dimethylacetamide or N-methylpyrolidinone has an inherent viscosity that is greater than 0.05 dl/g.

22 . The film of claim 1 , wherein after lamination to a substrate at a temperature from 250° C. to 450° C., the coefficient of thermal expansion of the laminated film is within ±10 ppm/° C. of the coefficient of thermal expansion of the film prior to lamination.

23 . The film of claim 1 , wherein the film comprises up to 50 wt % of a recycled polyimide, wherein prior to recycling the recycled polyimide has a glass transition temperature from 210° C. to 450° C.

24 . The film of claim 1 , wherein the film comprises up to 30 wt % of a recycled polyimide film, wherein prior to recycling the recycled polyimide film has a glass transition temperature from 210° C. to 450° C.

25 . The film of claim 23 , wherein the coefficient of thermal expansion of the film comprising the recycled polyetherimide is within ±10 ppm/° C. of the coefficient of thermal expansion of a film having the same composition without the recycled polyetherimide.

26 . The film of claim 1 , wherein the film is cast from a composition comprising 1 to 30 wt % solids.

27 . A composition comprising the solvent cast polyimide film of claim 1 , wherein the solvent cast polyimide film is recycled.

28 . The composition of claim 27 , wherein the recycled film is capable of being melt blended.

29 . A method of making a solvent cast polyimide film, comprising:

casting a polyamic acid composition onto a substrate to form a film;

heating the cast film for a time and at a temperature effective to remove the solvent and to form a solvent cast polyimide film having a coefficient of thermal expansion of less than 60 ppm/° C. and a thickness from 0.1 to 125 micrometers; and

processing the solvent cast polyimide film to reduce the coefficient of thermal expansion of the film to below 35 ppm/° C.

30 . The method of claim 29 , wherein processing the solvent cast polyimide film to reduce the coefficient of thermal expansion of the film comprises biaxially stretching the solvent cast polyimide film.

31 . The method of claim 29 , wherein the solvent cast polyimide film comprises a nanoclay.

32 . The method of claim 31 , wherein a nanoclay is an exfoliated nanoclay.

33 . The method of claim 32 , wherein exfoliating is carried out in a composition comprising from 10 to 90% by weight of the nanoclay and from 10 to 90% by weight of the solvent system.

34 . The method of claim 29 , wherein the nanoclay is added to the polyamic acid composition after the polyamic acid composition is formed.

35 . The method of claim 29 further comprising reacting a dianhydride component and an organic diamine component in a solvent system to form the polyamic acid composition before casting the polyamic acid composition.

36 . The method of claim 35 , comprising reacting the dianhydride component and the organic diamine component in the presence of the nanoclay.

37 . The method of claim 36 , further comprising exfoliating the nanoclay in the solvent system prior to reacting the dianhydride component and the organic diamine component in the solvent system.

38 . A method of making a polyimide film, comprising:

melt blending a polymer and a polyimide; and

forming a film from the melt blend, wherein the formed film has

a coefficient of thermal expansion of less than 60 ppm/° C.,

a thickness from 0.1 to 125 micrometers; and

a coefficient of thermal expansion of less than 60 ppm/° C.

39 . A solvent cast film, comprising:

a polyimide comprising structural units derived from

a dianhydride component comprising 3,4′-oxydiphthalic dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, or a combination thereof, and

a diamine component comprising 4,4′-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, 4,4′-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, or a combination thereof,

wherein the film has

a coefficient of thermal expansion of less than 60 ppm/° C.,

a thickness from 0.1 to 250 micrometers, and

less than 5% residual solvent by weight; and

wherein the polyimide has less than 15 molar % of structural units derived from biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, or an ester of biphenyltetracarboxylic acid.

40 . A solvent cast film, comprising:

a polyimide comprising structural units derived from 4,4′-oxydiphthalic dianhydride and 4,4′-diaminodiphenylsulfone;

wherein the polyimide has a glass transition temperature from 190° C. to 400° C.; and

wherein the film has

a coefficient of thermal expansion of less than 60 ppm/° C.,

a thickness from 0.1 to 250 micrometers, and

less than 5% residual solvent by weight; and

wherein the polyimide has less than 15 molar % of structural units derived from biphenyltetracarboxylic acid, a dianhydride of biphenyltetracarboxylic acid, or an ester of biphenyltetracarboxylic acid.

41 . A method of manufacture of a recycled polyimide composition, comprising

melting the solvent cast polyimide film of claim 1 ; and

combining the melted solvent cast polyimide film of claim 1 with a polymer composition to form a recycled polyimide composition.

42 . The method of claim 41 , further comprising extruding the composition comprising the melted film.

43 . A method of manufacture of a recycled a polyimide composition, comprising

dissolving the solvent cast polyimide film of claim 1 ; and

combining the dissolved film of claim 1 with a polymer composition to form the recycled polyimide composition.

44 . The method of claim 43 , further comprising extruding the recycled polyimide composition.

45 . An article comprising the recycled polyimide composition of claim 41 .

46 . An article comprising the recycled polyimide composition of claim 43 .

47 . A solvent cast film, comprising:

a polyimide comprising structural units derived from a dianhydride selected from the group consisting of 3,4′-oxydiphthalic dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, and a combination thereof, and a diamine selected from the group consisting of 4,4′-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, and a combination thereof, wherein

the polyimide has a glass transition temperature from 190° C. to 400° C.; wherein

the film has less than 15 molar % of a member selected from the group consisting of biphenyltetracarboxylic acid, dianhydrides of biphenyltetracarboxylic acid, esters of biphenyltetracarboxylic acid, and combinations thereof, and further wherein

the film has

a coefficient of thermal expansion of less than 60 ppm/° C., wherein the film has a coefficient of thermal expansion that is within ±20 ppm/° C. of the coefficient of thermal expansion of copper, silicon, aluminum, gold, silver, nickel, a glass, a ceramic, or a polymer,

a thickness from 0.1 to 250 micrometers, and

less than 5% residual solvent by weight; and wherein

the solvent is selected from the group consisting of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrolidinone, dimethylsulfoxide, sulfolane, tetrahydrofuran, benzophenone, cyclohexanone, phenol, o-cresol, p-cresol, m-cresol, phenol, ethylphenol, isopropylphenol, t-butylphenol, xylenol, mesitol, chlorophenol, dichlorophenol, phenylphenol, a monoalkyl ether of ethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoalkyl ether of diethylene glycol having from 1 to about 4 carbon atoms in the alkyl group, a monoaryl ether glycol, a monoaryl ether of propylene glycol, tetramethylurea, phenoxy ethanol, propylene glycol phenyl ether, anisole, veratrole, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, N-cyclohexylpyrrolidinone, ethyl lactate, an ionic liquid, and a combination thereof.