CA1274640A - Compatible self-crosslinking poly (amide-imide) polyepoxide resin blends and laminates made therewith - Google Patents
Compatible self-crosslinking poly (amide-imide) polyepoxide resin blends and laminates made therewithInfo
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- CA1274640A CA1274640A CA000519991A CA519991A CA1274640A CA 1274640 A CA1274640 A CA 1274640A CA 000519991 A CA000519991 A CA 000519991A CA 519991 A CA519991 A CA 519991A CA 1274640 A CA1274640 A CA 1274640A
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- amic acid
- polyimide
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Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a composition comprising about 5 to about 95 phr of a polyepoxide or other resinous component, about 20 to about 90% of an aprotic solvent, about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in the solvent, and sufficient water to hydrolyze the polyimide. A laminate is made from the composition by heating it until the amic acid function-ality is substantially eliminated, then impregnating a fibrous substrate with the composition, heating the impreg-nated substrate to evaporate the solvent and B-stage the composition and form a prepreg, forming a stack of the prepregs, and heating and pressing the stack of prepregs to cure the composition. A wire enamel can also be made from the composition.
Disclosed is a composition comprising about 5 to about 95 phr of a polyepoxide or other resinous component, about 20 to about 90% of an aprotic solvent, about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in the solvent, and sufficient water to hydrolyze the polyimide. A laminate is made from the composition by heating it until the amic acid function-ality is substantially eliminated, then impregnating a fibrous substrate with the composition, heating the impreg-nated substrate to evaporate the solvent and B-stage the composition and form a prepreg, forming a stack of the prepregs, and heating and pressing the stack of prepregs to cure the composition. A wire enamel can also be made from the composition.
Description
~2~fl~
1 51,321I
COMPATIBLE SELF-CROSSLINKING POLY (AMIDE-IMIDE) POLYEPOXIDE RESIN BLENDS AND LAMINATES MADE THER~'~7ITH
BACKGROUND OF THE INVENTION
Because they are B-s~ageable- and have very good properties, epoxy resins are widely used in making lami-nates. Laminates have also been made using polyimide-based laminating resins, which have many high performance charac-teristics not possessed by epoxy resins. However, poly-imide resins require msre severe curing conditions than do epoxy resins to achieve the optimum properties.
Another approach to improving laminates has been to modify the epoxy resins with imide functional adjuvants.
For example, U.S. Patent 4,244,857 teaches the use of certain bis amino imides as curing agents for polyepoxide resins. Similarly, U.S. Patent 3,978,152 discloses thermosetting compositions which are blends of certain unsaturated bisimides with adducts possessing an amino group formed from an epoxy resin and excess amine. U.S.
Patent 3,984,373 describes a thermosetting resin composi-tion based on an epoxy resin incorporated with an N, N'-unsaturated amic acid-imide containing compound.
Similarly, U.S. Patent 3,979,393 relates to the use of anhydride containing imidyl and isoimidyl compounds as curing agents for polyepoxide resins. In these examples, the imide containing adjuvants are low molecular weight material~ which are primarily utilized as polyepoxide hardeners. Therefor , the quantity of imide containing ~27~
1 51,321I
COMPATIBLE SELF-CROSSLINKING POLY (AMIDE-IMIDE) POLYEPOXIDE RESIN BLENDS AND LAMINATES MADE THER~'~7ITH
BACKGROUND OF THE INVENTION
Because they are B-s~ageable- and have very good properties, epoxy resins are widely used in making lami-nates. Laminates have also been made using polyimide-based laminating resins, which have many high performance charac-teristics not possessed by epoxy resins. However, poly-imide resins require msre severe curing conditions than do epoxy resins to achieve the optimum properties.
Another approach to improving laminates has been to modify the epoxy resins with imide functional adjuvants.
For example, U.S. Patent 4,244,857 teaches the use of certain bis amino imides as curing agents for polyepoxide resins. Similarly, U.S. Patent 3,978,152 discloses thermosetting compositions which are blends of certain unsaturated bisimides with adducts possessing an amino group formed from an epoxy resin and excess amine. U.S.
Patent 3,984,373 describes a thermosetting resin composi-tion based on an epoxy resin incorporated with an N, N'-unsaturated amic acid-imide containing compound.
Similarly, U.S. Patent 3,979,393 relates to the use of anhydride containing imidyl and isoimidyl compounds as curing agents for polyepoxide resins. In these examples, the imide containing adjuvants are low molecular weight material~ which are primarily utilized as polyepoxide hardeners. Therefor , the quantity of imide containing ~27~
2 51,321I
adjuvant blended with the epoxy resin rarely exceeds that amount which is necessary to cure the epoxy resin.
The reason the imides are added as hardeners is that until now it has not been possible to blend or allo~
polyimide resins in any quantity with epoxy resins to produce compatible resin blends suitable for laminating applications. For the most part, fully imidized pol~mers are insoluble in organic solvents, and, while some partial-ly imidized polymers are soluble in organic solvents, the polyimide ~omponent is often not soluble in the epoxy component so that a compatible resin blend cannot be formed. In those cases where a blend of epoxy and poly-imide resins can be formed which is compatible, very large amounts of organic solvent are required to achieve a blend solution viscosity which is suitable for the manufacture of prepregs. The necessity of evaporating and r~covering these large amounts of solvents renders the process uneconomical.
` UMMARY OF THE INVENTION
We have discovered that a particular type of imide oligomer will form a compatible blend with an epoxy resin, and with other types of resins, using a moderate amount of solvent. The imide oligomer of this invention is formed from an imide polymer which contains amic acid groups that can be hydrolyzed so that the products of the hydrolization become compatible with the epoxy or other resin and serve to cure the resinous blend. By incorporat-ing an imide oligomer into the resins, we have been able to achieve laminates having improved properties such as a higher glass transition temperature, better chemical resistance, and increased toughness. Wire enamels having good elongation and heat shock, and fast processing times can also be made from blends containing this imide oli-gomer. ~e have also found that a thermoplastic laminate can be made using the imide oligomer by itself.
adjuvant blended with the epoxy resin rarely exceeds that amount which is necessary to cure the epoxy resin.
The reason the imides are added as hardeners is that until now it has not been possible to blend or allo~
polyimide resins in any quantity with epoxy resins to produce compatible resin blends suitable for laminating applications. For the most part, fully imidized pol~mers are insoluble in organic solvents, and, while some partial-ly imidized polymers are soluble in organic solvents, the polyimide ~omponent is often not soluble in the epoxy component so that a compatible resin blend cannot be formed. In those cases where a blend of epoxy and poly-imide resins can be formed which is compatible, very large amounts of organic solvent are required to achieve a blend solution viscosity which is suitable for the manufacture of prepregs. The necessity of evaporating and r~covering these large amounts of solvents renders the process uneconomical.
` UMMARY OF THE INVENTION
We have discovered that a particular type of imide oligomer will form a compatible blend with an epoxy resin, and with other types of resins, using a moderate amount of solvent. The imide oligomer of this invention is formed from an imide polymer which contains amic acid groups that can be hydrolyzed so that the products of the hydrolization become compatible with the epoxy or other resin and serve to cure the resinous blend. By incorporat-ing an imide oligomer into the resins, we have been able to achieve laminates having improved properties such as a higher glass transition temperature, better chemical resistance, and increased toughness. Wire enamels having good elongation and heat shock, and fast processing times can also be made from blends containing this imide oli-gomer. ~e have also found that a thermoplastic laminate can be made using the imide oligomer by itself.
3 51,321I
DESCRIPTION OF THE INVENTION
Figure 1 is an isometric view in section sf a certain presently preferred embodiment of a laminate according to this invention.
Figure 2 is an isometric view of a filament wound tube, such as a launch tube, according to this invention, partially cut away.
In the drawing, a layer 1 of a fibrous material 2 is impregnated with a resinous matrix 3 which has been - 10 B-staged to form prepregs 4. A stack of prepregs 5 heated under pressure to cure the resinous matrix to the C-stage fo~ms laminate 6. A~co~per foil 7 has been bonded to one surface of the laminate.
In Figure 2 " filaments 8, for example, of glass, are wound and imbedded in resinous matrix 9, which has been cure~ to the C-stage,~ orming tube 10. Filament wound structures are made by passing roving through a resin bath and over a mandrill, where the resin is cured.
In the first step of preparing a laminate accord-ing to the process of this invention, a composition isprepared of a resinous component, (which can be a mixture of resinous components), an imide polymer having amic acid functionality, and a solvent. The resinous component, also called a "coreactive compound," is a monomer, oligomer, or polymer that is reactive with the imide oligomer that is formed by hydrolyzing the imide polymer. Suitable resinous components include bismaleimides and derivatives thereof, polyimides, diols and diacids, diacids and diamines, phenolic resins, capped isocyanates, and polyepcxides.
Bismaleimides are formed by reacting maleic anhydride with an aromatic polyamin~. The polyamine is a compound having at least two amine groups; preferably, it has exactly two amine groups because those compounds are more readily available. Derivatives of bismaleimides include bismaleimides that have been partially reacted with aromat-ic diamines or with unsaturated derivatives of bisphenol A.
DESCRIPTION OF THE INVENTION
Figure 1 is an isometric view in section sf a certain presently preferred embodiment of a laminate according to this invention.
Figure 2 is an isometric view of a filament wound tube, such as a launch tube, according to this invention, partially cut away.
In the drawing, a layer 1 of a fibrous material 2 is impregnated with a resinous matrix 3 which has been - 10 B-staged to form prepregs 4. A stack of prepregs 5 heated under pressure to cure the resinous matrix to the C-stage fo~ms laminate 6. A~co~per foil 7 has been bonded to one surface of the laminate.
In Figure 2 " filaments 8, for example, of glass, are wound and imbedded in resinous matrix 9, which has been cure~ to the C-stage,~ orming tube 10. Filament wound structures are made by passing roving through a resin bath and over a mandrill, where the resin is cured.
In the first step of preparing a laminate accord-ing to the process of this invention, a composition isprepared of a resinous component, (which can be a mixture of resinous components), an imide polymer having amic acid functionality, and a solvent. The resinous component, also called a "coreactive compound," is a monomer, oligomer, or polymer that is reactive with the imide oligomer that is formed by hydrolyzing the imide polymer. Suitable resinous components include bismaleimides and derivatives thereof, polyimides, diols and diacids, diacids and diamines, phenolic resins, capped isocyanates, and polyepcxides.
Bismaleimides are formed by reacting maleic anhydride with an aromatic polyamin~. The polyamine is a compound having at least two amine groups; preferably, it has exactly two amine groups because those compounds are more readily available. Derivatives of bismaleimides include bismaleimides that have been partially reacted with aromat-ic diamines or with unsaturated derivatives of bisphenol A.
4 51,321I
The reaction of the oligomer of this invention with diols and diacids will produce a partially interpenetrating network of a polyester-modified polyamide-imide. The reaction of the oligomer of this invention with diacids and diamines will produce a partially interpenetrating network of a polyamide-imide modified polyamide~imide. Since the reaction of the oligomer of this invention with diols and diacids, diacids and diamines, phenolic resins, and capped isocyanates evolves volatiles, these resin systems are ~10 limited to applications such as wire enamels and other coating applications. A polyepoxide is any type of epoxy resin having at le~st two epoxide groups. It may be cycloaliphatic, novolac, an epoxy prepared from methylene ~ dianiline, an epoxy prepared from para-aminophenol, or a brominated epoxy. The preferred epoxy resins are the r1 diglycidyl ethers of bisphenol A, however, as they are readily available.
The imide polymer which is hydrolyzed to produce the imide oligomer of this invention should have suficient ~0 amic acid groups to be soluble in the solvent. However, if too many amic acid groups are present, the product will have deficient properties, and if too few amic acid groups are present! the polymer will tend to be insoluble. About
The reaction of the oligomer of this invention with diols and diacids will produce a partially interpenetrating network of a polyester-modified polyamide-imide. The reaction of the oligomer of this invention with diacids and diamines will produce a partially interpenetrating network of a polyamide-imide modified polyamide~imide. Since the reaction of the oligomer of this invention with diols and diacids, diacids and diamines, phenolic resins, and capped isocyanates evolves volatiles, these resin systems are ~10 limited to applications such as wire enamels and other coating applications. A polyepoxide is any type of epoxy resin having at le~st two epoxide groups. It may be cycloaliphatic, novolac, an epoxy prepared from methylene ~ dianiline, an epoxy prepared from para-aminophenol, or a brominated epoxy. The preferred epoxy resins are the r1 diglycidyl ethers of bisphenol A, however, as they are readily available.
The imide polymer which is hydrolyzed to produce the imide oligomer of this invention should have suficient ~0 amic acid groups to be soluble in the solvent. However, if too many amic acid groups are present, the product will have deficient properties, and if too few amic acid groups are present! the polymer will tend to be insoluble. About
5 to about 50% of the total of amic acid plus imide groups along the polymer should be amic acid groups, and 50 to 95%
imide groups, as it is the imide groups which enhance the properties of an impregnating resin.
The solvent should be an organic compound which is highly aprotic in order to dissolve the imide polymer.
Suitable solvents include N-dimethyl formamide (DMF), N-methyl-2-p~rrolidone (NMP), and dimethyl sulfoxide. The p~eferred solvent is N~dimethyl acetamide (DMAC~ because it is easily removed during B-staging. Mixtures of solvents ca~ also be used. In addition, up to about 5% (all per-centages herein are by weight based on total compositionweight, unless otherwise indicated) of a hydrocarbon ~7~
51,321I
solvent such as xylene, toluene, or Solvesso, can be added to reduce the cost of ~he solvent. Sufficient water must also be present to hydrolyze substantially all of the amic acid groups in the imide polymer. Typically, the other 5 components in the composition contain sufficient water as an impurity to perform this function, but if they do not, additional water must b~ added so that at least about the stoichiometric amount required for hydrolysis is present.
With some resinous components, it is also possible to hydrolyze ~the imide polymer prior to its addition to the composition.
The composition comprises about 5 to about 95 phr (parts by weight per hundred parts by weight resin, where "resin" means the resinous component plus the imide poly-mer, based on total solids) of the imide polymer and aboutS to about 95 phr of the re~inous component. ~referably, the composition comprises about 50 to about 80 phr of the resinous component and about 20 to about 50 phr of the imide polymer. The actual ratio of resinous component to imide polymer used is determined by the desired glass transition temperature, since a higher imide content will result in a hiyher glass transition temperature. The total composition is preferably about 10 to about 80% by weight solids, the remainder being the solvent. The composition may also include about 0.1 to about 0.7 phr of a catalyst, if desired, to shorten the gelation time. Suitable cata-lysts for polyepoxides and bismaleimides include tertiary amines such as 2-methylimidazole, and benzyl dimethyl amine; the preferred catalyst is 2-methylimidazole (2-MI).
Catalysts, if needed, for other resinous components are well known in the art.
Other optional ingredients include about 0.1 to about 25% (based on total solids weight) of a filler such as alumina trihydrate. The filler performs the function of reducing the amount of resin required, which is expensive, and in addition, makes the composition less flammable. A
~27~
imide groups, as it is the imide groups which enhance the properties of an impregnating resin.
The solvent should be an organic compound which is highly aprotic in order to dissolve the imide polymer.
Suitable solvents include N-dimethyl formamide (DMF), N-methyl-2-p~rrolidone (NMP), and dimethyl sulfoxide. The p~eferred solvent is N~dimethyl acetamide (DMAC~ because it is easily removed during B-staging. Mixtures of solvents ca~ also be used. In addition, up to about 5% (all per-centages herein are by weight based on total compositionweight, unless otherwise indicated) of a hydrocarbon ~7~
51,321I
solvent such as xylene, toluene, or Solvesso, can be added to reduce the cost of ~he solvent. Sufficient water must also be present to hydrolyze substantially all of the amic acid groups in the imide polymer. Typically, the other 5 components in the composition contain sufficient water as an impurity to perform this function, but if they do not, additional water must b~ added so that at least about the stoichiometric amount required for hydrolysis is present.
With some resinous components, it is also possible to hydrolyze ~the imide polymer prior to its addition to the composition.
The composition comprises about 5 to about 95 phr (parts by weight per hundred parts by weight resin, where "resin" means the resinous component plus the imide poly-mer, based on total solids) of the imide polymer and aboutS to about 95 phr of the re~inous component. ~referably, the composition comprises about 50 to about 80 phr of the resinous component and about 20 to about 50 phr of the imide polymer. The actual ratio of resinous component to imide polymer used is determined by the desired glass transition temperature, since a higher imide content will result in a hiyher glass transition temperature. The total composition is preferably about 10 to about 80% by weight solids, the remainder being the solvent. The composition may also include about 0.1 to about 0.7 phr of a catalyst, if desired, to shorten the gelation time. Suitable cata-lysts for polyepoxides and bismaleimides include tertiary amines such as 2-methylimidazole, and benzyl dimethyl amine; the preferred catalyst is 2-methylimidazole (2-MI).
Catalysts, if needed, for other resinous components are well known in the art.
Other optional ingredients include about 0.1 to about 25% (based on total solids weight) of a filler such as alumina trihydrate. The filler performs the function of reducing the amount of resin required, which is expensive, and in addition, makes the composition less flammable. A
~27~
6 51,3211 final optional ingredient is about 0.1 to about 5% (based on total solids weight) of a pigment.
In preparing the composition, the resinous com-ponent, the imide polymer, the solvent, and the filler and pigment, if used, are cooked until no more amic acid functional groups are present. This can be usually accom-plished by heating a-t about 100 to about 150C, typically for about a half hour. Of course, the lower temperatures are used for longer times and the higher temperatures are used for shorter times. During hydrolysis, the water present in the composition decomposes the amic acid func-tional groups to form carboxylic acid and amine groups:
~NE1~3N / ~ N~-e3N~
n m }~2--[ N~N/ ~
\C C--rNH~>NH2 1! _ L n HOOC im The resulting imide oligomer is an aromatic compound having a molecular weight which depends upon the . ~,, .~
~7~
In preparing the composition, the resinous com-ponent, the imide polymer, the solvent, and the filler and pigment, if used, are cooked until no more amic acid functional groups are present. This can be usually accom-plished by heating a-t about 100 to about 150C, typically for about a half hour. Of course, the lower temperatures are used for longer times and the higher temperatures are used for shorter times. During hydrolysis, the water present in the composition decomposes the amic acid func-tional groups to form carboxylic acid and amine groups:
~NE1~3N / ~ N~-e3N~
n m }~2--[ N~N/ ~
\C C--rNH~>NH2 1! _ L n HOOC im The resulting imide oligomer is an aromatic compound having a molecular weight which depends upon the . ~,, .~
~7~
7 51,321l number of amic acid groups in the imide polymer. The imide oligomer necessarlly contains both amine groups and carbox-ylic acid groups, as a result of the hydrolysis, as well as at least one fully formed imide ring.
The carboxylic acid and amine groups in the imide oligomer then react with groups on the resinous component to form a new polymer containing all three groups. T~at this occurs is shown by infrared spectrographic analyses of sa~ples of the composition taken at 5 minute intervals as ~t is being heated. When the resinous component is a polyepoxide, the spectrographic analysis shows the disap-- pearance of both the amic acid peak and the epoxy peak and the growth of a new intermediate peak~for the new polymer.
Efforts to form the same new polymer by simply mixing the polyepoxide with the original imide polymer were not successful because the two polymers are not compatible and will not dissolve in each other. Nor could the new polymer be formed by first hydrolyzing the imide polymer, then adding the polyepoxide, because the imide portion of the hydrolyzed imide polymer is not soluble in the mixture.
After cooling, the optional catalyst can be added if desired. In addition, at this time, additional solvent can be added to reduce the viscosity further, if desired.
In the next step in the process of making a laminate according to this invention, a substrate is impregnated with the composition containing the new poly-mer. The substrate may be of any fibrous material includ-ing glass, cotton, quartz, polyamide, polyaramid, paper, graphite, carbon, or mixtures thereof and may be in many forms including woven cloth, mat, or rovings as used in pultrusion or filamant windings. The preferred substrate material is, of course, dependant upon laminate end use.
The amount of resin solids impregnated into the substrate depends upon the type of substrate used in the application.
Typically, about 20 to about 60% by weight resin solids are impregnated with about 40 to about 80~ by weight of the ~ 2~
The carboxylic acid and amine groups in the imide oligomer then react with groups on the resinous component to form a new polymer containing all three groups. T~at this occurs is shown by infrared spectrographic analyses of sa~ples of the composition taken at 5 minute intervals as ~t is being heated. When the resinous component is a polyepoxide, the spectrographic analysis shows the disap-- pearance of both the amic acid peak and the epoxy peak and the growth of a new intermediate peak~for the new polymer.
Efforts to form the same new polymer by simply mixing the polyepoxide with the original imide polymer were not successful because the two polymers are not compatible and will not dissolve in each other. Nor could the new polymer be formed by first hydrolyzing the imide polymer, then adding the polyepoxide, because the imide portion of the hydrolyzed imide polymer is not soluble in the mixture.
After cooling, the optional catalyst can be added if desired. In addition, at this time, additional solvent can be added to reduce the viscosity further, if desired.
In the next step in the process of making a laminate according to this invention, a substrate is impregnated with the composition containing the new poly-mer. The substrate may be of any fibrous material includ-ing glass, cotton, quartz, polyamide, polyaramid, paper, graphite, carbon, or mixtures thereof and may be in many forms including woven cloth, mat, or rovings as used in pultrusion or filamant windings. The preferred substrate material is, of course, dependant upon laminate end use.
The amount of resin solids impregnated into the substrate depends upon the type of substrate used in the application.
Typically, about 20 to about 60% by weight resin solids are impregnated with about 40 to about 80~ by weight of the ~ 2~
8 51,3~11 substrate.
In the next step in the process of making a laminate according to this invention, the impregnated substrate is heated to B-stage the resin. The time and temperature required for B-staging depends upon the partic ular resin used, but generally speaking, the impregnatPd substrate is heated to the boiling point of the solvent or slightly higher. This results in the evaporation of the solvent and the advance of the resin to the B-stage, the point at which it is non-tacky and can be handled. The resulting article is a prepreg.
In the next step of the process of making a laminate according to this invention, the prepregs are stacked and heated under pressure to form a laminate.
Copper foil may be placed on either or both surfaces of the stack to form a laminate suitable for- making printed circuit boards. The temperature, time, and pressure used depend upon the materials and the properties desired, but about 150 to about 220C for one hour at 1,000 psi is typical.
The composition can also be used to make a wire enamel. In this case, the wire is simply run through the composition after the imide polymer is hydrolyzed, excess composition is removed by dies, wiping or other means, and, in a single step, the composition is cured to the C-stage and the solvents are evaporated. In addition, the composi-tion can be used to make filament wound composite launch tubes, laminates used as components for ship propulsion room equipment, such as sub-base structures, generator covers, and gearcase components, and laminates used as electromagnetic launcher components.
The following is a description o the materials used in the examples:
"Epon 829'' - a diglycidyl ether of bisphenol-A
made by Shell Chemical Co. by reacting epichlorohydrin with bisphenol-A. In addition to the diglycidyl ether, "Epon ~2'7~
In the next step in the process of making a laminate according to this invention, the impregnated substrate is heated to B-stage the resin. The time and temperature required for B-staging depends upon the partic ular resin used, but generally speaking, the impregnatPd substrate is heated to the boiling point of the solvent or slightly higher. This results in the evaporation of the solvent and the advance of the resin to the B-stage, the point at which it is non-tacky and can be handled. The resulting article is a prepreg.
In the next step of the process of making a laminate according to this invention, the prepregs are stacked and heated under pressure to form a laminate.
Copper foil may be placed on either or both surfaces of the stack to form a laminate suitable for- making printed circuit boards. The temperature, time, and pressure used depend upon the materials and the properties desired, but about 150 to about 220C for one hour at 1,000 psi is typical.
The composition can also be used to make a wire enamel. In this case, the wire is simply run through the composition after the imide polymer is hydrolyzed, excess composition is removed by dies, wiping or other means, and, in a single step, the composition is cured to the C-stage and the solvents are evaporated. In addition, the composi-tion can be used to make filament wound composite launch tubes, laminates used as components for ship propulsion room equipment, such as sub-base structures, generator covers, and gearcase components, and laminates used as electromagnetic launcher components.
The following is a description o the materials used in the examples:
"Epon 829'' - a diglycidyl ether of bisphenol-A
made by Shell Chemical Co. by reacting epichlorohydrin with bisphenol-A. In addition to the diglycidyl ether, "Epon ~2'7~
9 51,321I
829" contains an unspecified level of a proprietary pho3-phonium halide catalyst. The material is supplied at 96 5%
solids in xylene and contains a maximum 0.03 wt.~o hydrolyzable chlorine on an as-is basis.
~- 5 "Torlon 4000T" - a low acid value, high molecular weight poly(amide-imide~ resin containing ~ome amic acid functionality, supplied at 100% solids as a free flo~"ing crumb by the Amoco Chemicals Corporation. The material ~,/as developed primarily as a high performance injec~ion molding resin and has the following generalized structure:
; U ~ CH2 ~ N-C ~ / N j "Tritherm 981" - a poly(amide-imide) wire enamel supplied at 26% total solids in 65/35 (by weight) NMP/xylene by the P D. George Company.
- 15 "MY720" - a Ciba~Geigy high performance, tetrafunctional epoxy resin with the following structure:
R R
N ~ CH2 ~ N < O
R R R = -CH~-CH-CH2.
The material has an epoxide equivalent weight of 125 gm/equiv and is supplied at lOO~o solids.
"PLYOPHEN 94-308" - a monomeric, aromatic bismaleimide sold by Reichhold Chemicals Corp., made by condensing methylene dianiline and maleic anhydride.
829" contains an unspecified level of a proprietary pho3-phonium halide catalyst. The material is supplied at 96 5%
solids in xylene and contains a maximum 0.03 wt.~o hydrolyzable chlorine on an as-is basis.
~- 5 "Torlon 4000T" - a low acid value, high molecular weight poly(amide-imide~ resin containing ~ome amic acid functionality, supplied at 100% solids as a free flo~"ing crumb by the Amoco Chemicals Corporation. The material ~,/as developed primarily as a high performance injec~ion molding resin and has the following generalized structure:
; U ~ CH2 ~ N-C ~ / N j "Tritherm 981" - a poly(amide-imide) wire enamel supplied at 26% total solids in 65/35 (by weight) NMP/xylene by the P D. George Company.
- 15 "MY720" - a Ciba~Geigy high performance, tetrafunctional epoxy resin with the following structure:
R R
N ~ CH2 ~ N < O
R R R = -CH~-CH-CH2.
The material has an epoxide equivalent weight of 125 gm/equiv and is supplied at lOO~o solids.
"PLYOPHEN 94-308" - a monomeric, aromatic bismaleimide sold by Reichhold Chemicals Corp., made by condensing methylene dianiline and maleic anhydride.
10 51,321I
"IM-AD94-394" - a two component polyimid iami-nating resin sold by Reichnh1old Chemical Corp. One compo-nent is "PLYOPHEN 94-308" and the other is an unsaturated phenolic novolac oligomer.~K~
"COMPIMIDE 183" - a totally aromatic two compo-nent polyimide impregnant sold by The Boots Compan~, PLC, Nottingham, England. It is made by reacting bismaleimides with m-aminobenzoic acid hydrazide at 100% solid~.
-~ EXAMPLE 1 ~he following four resinous reactor products based upon various polyepoxide resin/poly(amide-imide) resin combinations were prepared:
Resin ~ A B C D
Epoxy Component(s) "Epon 829" 1'MY720"- "Epon 829" "~5Y720l' "Epon 829"
Poly(Amide-Imide) "Torlon "Torlon"TrithPrm "Torlon Component 4000T" 4000T" 981" 4000T"
The following is a description of the preparation of these reactor products. A typical charge for the preparation of 20 an "Epon 829"/"Torlon 4000T" resinous reactor product (Resin A) is presented in the following table:
Weight ChargedWt. (gm) Composition Material Function(gm) NV~ Equiv.(Wt. %) 25 "Epon 829" Epoxy Resin 483.3 466.4 2.48 80.0 "Torlon 4000T" Poly(amide-116 6 116.6 -- 20.0 imide) DMAC Solvent 349.7 -- -- --Xylene* Solvent (16-9) 30 Total Charge 949.6 583.0 2.48 100.0 *-Not charged separately - I'Epon 829" solvent ** Non-volatile.
~7~
"IM-AD94-394" - a two component polyimid iami-nating resin sold by Reichnh1old Chemical Corp. One compo-nent is "PLYOPHEN 94-308" and the other is an unsaturated phenolic novolac oligomer.~K~
"COMPIMIDE 183" - a totally aromatic two compo-nent polyimide impregnant sold by The Boots Compan~, PLC, Nottingham, England. It is made by reacting bismaleimides with m-aminobenzoic acid hydrazide at 100% solid~.
-~ EXAMPLE 1 ~he following four resinous reactor products based upon various polyepoxide resin/poly(amide-imide) resin combinations were prepared:
Resin ~ A B C D
Epoxy Component(s) "Epon 829" 1'MY720"- "Epon 829" "~5Y720l' "Epon 829"
Poly(Amide-Imide) "Torlon "Torlon"TrithPrm "Torlon Component 4000T" 4000T" 981" 4000T"
The following is a description of the preparation of these reactor products. A typical charge for the preparation of 20 an "Epon 829"/"Torlon 4000T" resinous reactor product (Resin A) is presented in the following table:
Weight ChargedWt. (gm) Composition Material Function(gm) NV~ Equiv.(Wt. %) 25 "Epon 829" Epoxy Resin 483.3 466.4 2.48 80.0 "Torlon 4000T" Poly(amide-116 6 116.6 -- 20.0 imide) DMAC Solvent 349.7 -- -- --Xylene* Solvent (16-9) 30 Total Charge 949.6 583.0 2.48 100.0 *-Not charged separately - I'Epon 829" solvent ** Non-volatile.
~7~
11 51,321I
Dimethyl acetamide (349.7 gm) was charged in~o a 2,000 ml round bottom, three necked flask fitted with an agitator, nitrogen inlet tube, thermometer, reflux condens er and a means for heating. The flask was swept with N2 gas for 5 minutes and the flow rate adjusted to maintain a slight positive N2 pressure in the flask throughout the balance of the run.
The agitator was started and the DMAC was slowl~
heated to 60C wher~upon neat "Torlon 4000T" (116.6 gm) was slowly added to the hot DMAC at such a rate as ~o prevent clumping. After the addition of the "Torlon 4000T" was complete, the slurry was heated to 105C to effect complete dissolution. The uniform, smooth "Torlon 4000T"/D~AC
solution was then cooled to 100C and "Epon 829" (483.3 gm/2.48 equiv) was slowly added to the flask over a 5 minute period. After the "Epon 829" addition was complete, a small amount of the reaction mixture was removed for Gel Permeation Chromatographic (GPC) analysis and "Epon 829"/
"Torlon 4000T" compatibility testing. Compatibility testing was accomplished by casting a small amount of material on a glass slide (termed a "pill" in the following log) and driving off the DMAC. A "hazy pill" indicates that "Torlon 4000T" was not soluble in "Epon 829."
After the initial samples had been taken the flask was slowly heated to 140C and held there. Sampling was continued during the 140C hold and, when a clear pill had been attained, the reaction was cooled and the product set aside for evaluation. The product (Resin A) had a solids content of 61.4% and a viscosity of 420 cps (#2 @ 20 rpm on the Brookfield Model; RVF measured @ 25C). The significance of the GPC/IR data and other information obtained during the run will be discussed in a later section of this example.
The following is a log of the preparation of this reactor product.
~7~
Dimethyl acetamide (349.7 gm) was charged in~o a 2,000 ml round bottom, three necked flask fitted with an agitator, nitrogen inlet tube, thermometer, reflux condens er and a means for heating. The flask was swept with N2 gas for 5 minutes and the flow rate adjusted to maintain a slight positive N2 pressure in the flask throughout the balance of the run.
The agitator was started and the DMAC was slowl~
heated to 60C wher~upon neat "Torlon 4000T" (116.6 gm) was slowly added to the hot DMAC at such a rate as ~o prevent clumping. After the addition of the "Torlon 4000T" was complete, the slurry was heated to 105C to effect complete dissolution. The uniform, smooth "Torlon 4000T"/D~AC
solution was then cooled to 100C and "Epon 829" (483.3 gm/2.48 equiv) was slowly added to the flask over a 5 minute period. After the "Epon 829" addition was complete, a small amount of the reaction mixture was removed for Gel Permeation Chromatographic (GPC) analysis and "Epon 829"/
"Torlon 4000T" compatibility testing. Compatibility testing was accomplished by casting a small amount of material on a glass slide (termed a "pill" in the following log) and driving off the DMAC. A "hazy pill" indicates that "Torlon 4000T" was not soluble in "Epon 829."
After the initial samples had been taken the flask was slowly heated to 140C and held there. Sampling was continued during the 140C hold and, when a clear pill had been attained, the reaction was cooled and the product set aside for evaluation. The product (Resin A) had a solids content of 61.4% and a viscosity of 420 cps (#2 @ 20 rpm on the Brookfield Model; RVF measured @ 25C). The significance of the GPC/IR data and other information obtained during the run will be discussed in a later section of this example.
The following is a log of the preparation of this reactor product.
~7~
12 51,321I
Time Temp. (C) Remarks 11:07 RT N2, heat on DMAC, stirrer on 11:10 60 Start "Torlon 4000T" in slowly 11:15 95 "Torlon 4000T" in, hold - H20 droplets on condenser 11:16 105 Stir, hold temp. until uniform 11:27 100 Solution uniform, begin "Epon 829" addition 11:32 63 "Epon 829" in, heat to 140C, pill-l, GPC ~ample-l 11:38 75 Continue heating 11:44 100 Take pill-2 (hazy), continue heating 11:53 120 GPC sample-2, pill-3 (hazy), co~inue heating 12:05 140 Hold, GPC sample-3, pill-4 (ha~), viscosity drop 12:20 140 GPC sample-4, pill-5 (hazy), continue heating 12:35 140 GPC sample-5, pill-6 (clear), begin cooling 12:48 45 Continue cooling c 12:58 35 Pour/store for evaluation The same equipment but slightly different proce-dures wer~. utilized to prepare Resins B, C, and D. Pro-cessing parameters and reactor charges for these materials are presented in the following Tables:
Reactor Charge For Resin B
Weight Charged Wt. (gm)Composition Material Function(gm) NV Equiv. (Wt. %) "Epon 829" Epoxy Resin 342.0 330.0 1.753 55.0 "MY720" Epoxy Resin 120.0 120.0 0.960 20.0 "Torlon 4000T"Poly(amide- lS0.0 150.0 -- 25.0 imide) DMAC Solvent388.0 -- -- --1,000.0 600.0 100.0 Processing Parameters For Resin B
Reaction Temperature - 140C
Reaction Time @ 140C - 0.5 hr Wt. % Solids - 60.0%
Viscosity - 1,086 cps (#2 @ 20 rpm) ~'~7~
Time Temp. (C) Remarks 11:07 RT N2, heat on DMAC, stirrer on 11:10 60 Start "Torlon 4000T" in slowly 11:15 95 "Torlon 4000T" in, hold - H20 droplets on condenser 11:16 105 Stir, hold temp. until uniform 11:27 100 Solution uniform, begin "Epon 829" addition 11:32 63 "Epon 829" in, heat to 140C, pill-l, GPC ~ample-l 11:38 75 Continue heating 11:44 100 Take pill-2 (hazy), continue heating 11:53 120 GPC sample-2, pill-3 (hazy), co~inue heating 12:05 140 Hold, GPC sample-3, pill-4 (ha~), viscosity drop 12:20 140 GPC sample-4, pill-5 (hazy), continue heating 12:35 140 GPC sample-5, pill-6 (clear), begin cooling 12:48 45 Continue cooling c 12:58 35 Pour/store for evaluation The same equipment but slightly different proce-dures wer~. utilized to prepare Resins B, C, and D. Pro-cessing parameters and reactor charges for these materials are presented in the following Tables:
Reactor Charge For Resin B
Weight Charged Wt. (gm)Composition Material Function(gm) NV Equiv. (Wt. %) "Epon 829" Epoxy Resin 342.0 330.0 1.753 55.0 "MY720" Epoxy Resin 120.0 120.0 0.960 20.0 "Torlon 4000T"Poly(amide- lS0.0 150.0 -- 25.0 imide) DMAC Solvent388.0 -- -- --1,000.0 600.0 100.0 Processing Parameters For Resin B
Reaction Temperature - 140C
Reaction Time @ 140C - 0.5 hr Wt. % Solids - 60.0%
Viscosity - 1,086 cps (#2 @ 20 rpm) ~'~7~
13 51,321 Reactor Charge For Resin C
Weight Charged Composi~ion Mat2rial Function (gm) Equiv. (Wt. %) "Epon 829" Solids Epoxy Resin 420.0 2.Z3 70.0 "Tritherm 981"Poly(amide 180.0 -- 30.0 Solids imide) NMP-:: Solvent 370.5 -- --Xylenet: Solvent 214.7 -- --10 ~1 1,185.2 100.0 ::Not charged - "Epon 829"/"Tritherm 981" solvents.
Processing Parameters For Resin C
Reaction Temperatures - 140C, 160C
Reaction Times - 0.5 hr @ 1409C, 0.5 hr. @ 160C
Wt. % Solids - 50.6~
Viscosity - 1,680 cps (#2 @ 20 rpm) Reactor Charge For Resin D
Weight Char~ed Composition Material Function (gm) Equiv. (Wt. %) "MY720" Epoxy Resin 420.0 3.36 70.0 "Torlon 4000T"Poly(amide 180.0 -- 30.0 imide) 25 DMAC Solvent733.3 -- --l,333.3 100.0 Processin~ Parameters For Resin D
Reaction Temperature - 1~0C
Reaction Time @ 140C - 0.5 hr Wt. % Solids - 45.0%
Viscosity - 1,010 cps (~2 @ 20 rpm) Note that a 160C processing temperature is required to achiave compatibility between "Epon 829" and "Tritherm 981" in Resin C. H~ating is not required to achieve compatibility between "MN720" and "Torlon 4000T"
(Resin D) for the specified composition. However, heating ~7~
Weight Charged Composi~ion Mat2rial Function (gm) Equiv. (Wt. %) "Epon 829" Solids Epoxy Resin 420.0 2.Z3 70.0 "Tritherm 981"Poly(amide 180.0 -- 30.0 Solids imide) NMP-:: Solvent 370.5 -- --Xylenet: Solvent 214.7 -- --10 ~1 1,185.2 100.0 ::Not charged - "Epon 829"/"Tritherm 981" solvents.
Processing Parameters For Resin C
Reaction Temperatures - 140C, 160C
Reaction Times - 0.5 hr @ 1409C, 0.5 hr. @ 160C
Wt. % Solids - 50.6~
Viscosity - 1,680 cps (#2 @ 20 rpm) Reactor Charge For Resin D
Weight Char~ed Composition Material Function (gm) Equiv. (Wt. %) "MY720" Epoxy Resin 420.0 3.36 70.0 "Torlon 4000T"Poly(amide 180.0 -- 30.0 imide) 25 DMAC Solvent733.3 -- --l,333.3 100.0 Processin~ Parameters For Resin D
Reaction Temperature - 1~0C
Reaction Time @ 140C - 0.5 hr Wt. % Solids - 45.0%
Viscosity - 1,010 cps (~2 @ 20 rpm) Note that a 160C processing temperature is required to achiave compatibility between "Epon 829" and "Tritherm 981" in Resin C. H~ating is not required to achieve compatibility between "MN720" and "Torlon 4000T"
(Resin D) for the specified composition. However, heating ~7~
14 51,321I
at 140C is required to bring about the reduction in viscosity necessary for laminating applications Although no examples are provided, tetrabrominated polyepoxides such as Do~r's "DER 542," "DER
521A75," and the like would have utility in th~ practice of this invention. Similarly, multifunctional epoxy resins other than "MY720" (such as epoxy novolac resins) would have application. In like manner, nondiglycidylether bisphenol-A resins such as Union Carbide's cycloaliphatic epoxy resin line could be utilized in the preparation of the disclosed amide-imide m~dified laminating resins.
EX~MPLE 2 Compositional data along with varnish properties for a series of laminating varnishes which demonstrate the utility of our disclosure is presented in th~ table which follows. The varnishes were formulate~ by charging an appropriate amount of Resin A, B, C, or D into a stainless steel beaker fitted with a propeller type agitator. A
catalyst of 2-methylimidazole (0.28 wt.% on total resin solids) was charged and mixed until it had dissolved.
Additional solvents, filler, pigments, and/or catalysts and the like could have been added at this stage in the formu-lation scheme. The varnishes were stirred 15 minutes prior to impregnation onto style 7628 glass cloth.
25 Laminate A B C D
Resin ~ B C D
Wt.% "Epon 829" 74.77 54.83 69.80 --Wt.% "MY720" -- 19.94 -- 69.~0 Wt.% "Torlon 4000T" 19.94 24.93 -- 29.92 Wt.% "Tritherm 981" -- -- 29.90 --Wt.% 2-MI 0.2g 0.29 0.30 0.28 Impregnating Solids, 61.6 53.4 51.0 45.0 Wt.%
Impregnating Solvents DMAC DMAC/Methyl Xylene/NMP D~C/Xylene Cellosolve Varnish Viscosity, cps 350 400 1,665 1,010 Set-Time, Mins @ 153C 32.8 17.0 40.4 25.1 51,321I
Note that in the above table the indi~idual polyepoxide/poly(amide-imide) resins are presented in terms of composition. As an example, Laminate A c~ntains 74.77%
"Epon 829" and 19.94% "Torlon 4000T." The ratio of th se numbers corresponds to the composition of Resin A. The same holds true for Laminate B; i.e., the ratio of tabulat-ed "Epon 82g"/"MY720"/"Torlon 4000T" sorresponds to the composition of Resin B.
Style 7628 glass cloth was utiliized to prepare
at 140C is required to bring about the reduction in viscosity necessary for laminating applications Although no examples are provided, tetrabrominated polyepoxides such as Do~r's "DER 542," "DER
521A75," and the like would have utility in th~ practice of this invention. Similarly, multifunctional epoxy resins other than "MY720" (such as epoxy novolac resins) would have application. In like manner, nondiglycidylether bisphenol-A resins such as Union Carbide's cycloaliphatic epoxy resin line could be utilized in the preparation of the disclosed amide-imide m~dified laminating resins.
EX~MPLE 2 Compositional data along with varnish properties for a series of laminating varnishes which demonstrate the utility of our disclosure is presented in th~ table which follows. The varnishes were formulate~ by charging an appropriate amount of Resin A, B, C, or D into a stainless steel beaker fitted with a propeller type agitator. A
catalyst of 2-methylimidazole (0.28 wt.% on total resin solids) was charged and mixed until it had dissolved.
Additional solvents, filler, pigments, and/or catalysts and the like could have been added at this stage in the formu-lation scheme. The varnishes were stirred 15 minutes prior to impregnation onto style 7628 glass cloth.
25 Laminate A B C D
Resin ~ B C D
Wt.% "Epon 829" 74.77 54.83 69.80 --Wt.% "MY720" -- 19.94 -- 69.~0 Wt.% "Torlon 4000T" 19.94 24.93 -- 29.92 Wt.% "Tritherm 981" -- -- 29.90 --Wt.% 2-MI 0.2g 0.29 0.30 0.28 Impregnating Solids, 61.6 53.4 51.0 45.0 Wt.%
Impregnating Solvents DMAC DMAC/Methyl Xylene/NMP D~C/Xylene Cellosolve Varnish Viscosity, cps 350 400 1,665 1,010 Set-Time, Mins @ 153C 32.8 17.0 40.4 25.1 51,321I
Note that in the above table the indi~idual polyepoxide/poly(amide-imide) resins are presented in terms of composition. As an example, Laminate A c~ntains 74.77%
"Epon 829" and 19.94% "Torlon 4000T." The ratio of th se numbers corresponds to the composition of Resin A. The same holds true for Laminate B; i.e., the ratio of tabulat-ed "Epon 82g"/"MY720"/"Torlon 4000T" sorresponds to the composition of Resin B.
Style 7628 glass cloth was utiliized to prepare
15" x 15" prepregs from the varnishes outlined in the above table. The wet prepregs were B-staged at 160C for 10 minutes. After B-staging, the prepregs were approximatel~
40% resin and 60% glass cloth.
The B-staged prepregs were cut into 7" x 7"
s~uares and press laminated by stacking nine (9) individual pieces betw~en steel caul plates with Tedlar mold release sheets between tha caul plates and prepreg stack. The molding packs were loaded into a cold press with five layers of kraft paper between the press platens and caul plates. Individual molding packs were then heated to 180r under 1,000 psi in 45 minutes with an hour hold at 180C.
Cooldown was accomplished under pressure.
General properties for the laminates are present-ed in the following table.
25 Laminate A B C D
Glass Transition, 149.4 157.0 159.0 205.7 DSC, C
Z-Direction~ Expan- 60.6xlO 75.4xlO 75.1xlO 6 __ sion, In./In.tC
Solder Float, 60+ 60~ 60+ 60+
Sec. @ 525F
Acetone Resistance Excellent Excellent Excellent Excellent DMF Resistance Excellent Excellent Excellent Excellen~
*Z-direction expansion coefficien~ measured from 40C to Tg.
From the data in the above table, it is apparent that a
40% resin and 60% glass cloth.
The B-staged prepregs were cut into 7" x 7"
s~uares and press laminated by stacking nine (9) individual pieces betw~en steel caul plates with Tedlar mold release sheets between tha caul plates and prepreg stack. The molding packs were loaded into a cold press with five layers of kraft paper between the press platens and caul plates. Individual molding packs were then heated to 180r under 1,000 psi in 45 minutes with an hour hold at 180C.
Cooldown was accomplished under pressure.
General properties for the laminates are present-ed in the following table.
25 Laminate A B C D
Glass Transition, 149.4 157.0 159.0 205.7 DSC, C
Z-Direction~ Expan- 60.6xlO 75.4xlO 75.1xlO 6 __ sion, In./In.tC
Solder Float, 60+ 60~ 60+ 60+
Sec. @ 525F
Acetone Resistance Excellent Excellent Excellent Excellent DMF Resistance Excellent Excellent Excellent Excellen~
*Z-direction expansion coefficien~ measured from 40C to Tg.
From the data in the above table, it is apparent that a
16 51,321I
broad range of Tg values can be produced without the addition of external crosslinking agents. It is further apparent that the epoxy component as well a~ tne poly(amide-imide) component can influence laminate Tg.
Note that the utilization of "MY720" in Lamina~e B and D
results in Tg values higher than the 149.4C shown for Lamina'e A. Laminate C, based upon "Tritherm 981," pro-vides a higher Tg laminate (159.0C) than Laminate A, bas~d upon "Torlon 4~0~T" (149.4C).
10Lamina~e samples were placed in uncovered alumi-num pans and aged in a vented, forced air oven at 225C.
We~ght losses observed during thermal aging are presented in the following table. Note that a production G-10 ~r laminate was also heat aged at 225C. NEMA grade ER-4 laminate was also aged at 225C but delaminated in 2 hour~
LAMINATE
Hrs @ Wt.%Hrs @ Wt.%Hrs @ Wt.%Hrs @ Wt.%
20225C Lo 225~C Loss225C Loss 225C Loss 24 1.2924 0.9324 1.06 24 1.08 48 1.6748 1.2048 1.44 48 1.44 72 1.9272 1.4072 1.69 72 1.70 144 2.45 96 1.5596 1.89 96 1.90 25 168 2.60168 1.99168 2.39 168 2.44 384 3.44 192 2.10192 2.53 192 2.59 672 Failed 2162.22 2162.66 216 2.72 240 2.31240 2.77 240 2.83 264 2.40264 2.86 264 2.93 336 2.65336 3.14 336 3.23 360 2.73360 3.22 360 3.32 576 3.32576 3.80 576 3.98 864 3.85864 4.27 864 4.54 Thermal aging at 225~C for Laminates A, B, and C was con~inued.
~Resin content = approximately 40%.
After 864 hours at 225C all of the polyepoxide/
broad range of Tg values can be produced without the addition of external crosslinking agents. It is further apparent that the epoxy component as well a~ tne poly(amide-imide) component can influence laminate Tg.
Note that the utilization of "MY720" in Lamina~e B and D
results in Tg values higher than the 149.4C shown for Lamina'e A. Laminate C, based upon "Tritherm 981," pro-vides a higher Tg laminate (159.0C) than Laminate A, bas~d upon "Torlon 4~0~T" (149.4C).
10Lamina~e samples were placed in uncovered alumi-num pans and aged in a vented, forced air oven at 225C.
We~ght losses observed during thermal aging are presented in the following table. Note that a production G-10 ~r laminate was also heat aged at 225C. NEMA grade ER-4 laminate was also aged at 225C but delaminated in 2 hour~
LAMINATE
Hrs @ Wt.%Hrs @ Wt.%Hrs @ Wt.%Hrs @ Wt.%
20225C Lo 225~C Loss225C Loss 225C Loss 24 1.2924 0.9324 1.06 24 1.08 48 1.6748 1.2048 1.44 48 1.44 72 1.9272 1.4072 1.69 72 1.70 144 2.45 96 1.5596 1.89 96 1.90 25 168 2.60168 1.99168 2.39 168 2.44 384 3.44 192 2.10192 2.53 192 2.59 672 Failed 2162.22 2162.66 216 2.72 240 2.31240 2.77 240 2.83 264 2.40264 2.86 264 2.93 336 2.65336 3.14 336 3.23 360 2.73360 3.22 360 3.32 576 3.32576 3.80 576 3.98 864 3.85864 4.27 864 4.54 Thermal aging at 225~C for Laminates A, B, and C was con~inued.
~Resin content = approximately 40%.
After 864 hours at 225C all of the polyepoxide/
17 51,321I
poly(amide-imide) based laminates were bliste~ free and apparently retained their initial high degree of mechanical integrity.
PREPARATION OF HYDROLYZED '~TORLON 4000TF"
A typical charge and accompanying log for th~
preparation of hydrolyzed "Torlon 4000T" is shown below.
MaterialWt. Charged (Gm~Composition, Wt. %
"Torlon 4000T"600.0 29.70 10 DMF 1,400.0 69.31 Deionized H2020.0 O.g9 2,020.0 100.00 TimeTemperature (C~ Remarks 8:15 RTCharge DMF/H2O Into Reactor, Heat/N2 On 15 8:20 RT Begin Charging T-4000 8:29 58 All T-4000 Charged 9:00 139Refluxing-Gardner Vis. = Y @ 24.1C
9:30 140 Gardner Viscosity = Q-R
10:00 140 Gardner Viscosity = N-O
20 10:15 140Heat off - Cool & Store (Vis. = N-O) Dimethyl formamide (1,400.0 gm) and deionized water (20.0 gm) were charged into a 3,000 ml round bottom flask fitted with an agitator, nitrogen inlet tube, thermometer, reflux condenser and a means for heating. The flask was swept with N2 gas for 5 minutes and the flow rate adjusted to maintain a slight positive N2 pressure in the flash throughout the balance of the run. The agitator was started and the DMFfH20 solution heated while the "Torlon 4000T" was added to flask at such ~ rate as to prevent 30 clumping. After addition of the "Torlon 4000T" (58C~ the slurry was heated to 140C and held until the solution viscosity dropped from Y to N-O. The resulting hydrolyzed product had a solids content of 29.5% solids and was l Z 7 ~
poly(amide-imide) based laminates were bliste~ free and apparently retained their initial high degree of mechanical integrity.
PREPARATION OF HYDROLYZED '~TORLON 4000TF"
A typical charge and accompanying log for th~
preparation of hydrolyzed "Torlon 4000T" is shown below.
MaterialWt. Charged (Gm~Composition, Wt. %
"Torlon 4000T"600.0 29.70 10 DMF 1,400.0 69.31 Deionized H2020.0 O.g9 2,020.0 100.00 TimeTemperature (C~ Remarks 8:15 RTCharge DMF/H2O Into Reactor, Heat/N2 On 15 8:20 RT Begin Charging T-4000 8:29 58 All T-4000 Charged 9:00 139Refluxing-Gardner Vis. = Y @ 24.1C
9:30 140 Gardner Viscosity = Q-R
10:00 140 Gardner Viscosity = N-O
20 10:15 140Heat off - Cool & Store (Vis. = N-O) Dimethyl formamide (1,400.0 gm) and deionized water (20.0 gm) were charged into a 3,000 ml round bottom flask fitted with an agitator, nitrogen inlet tube, thermometer, reflux condenser and a means for heating. The flask was swept with N2 gas for 5 minutes and the flow rate adjusted to maintain a slight positive N2 pressure in the flash throughout the balance of the run. The agitator was started and the DMFfH20 solution heated while the "Torlon 4000T" was added to flask at such ~ rate as to prevent 30 clumping. After addition of the "Torlon 4000T" (58C~ the slurry was heated to 140C and held until the solution viscosity dropped from Y to N-O. The resulting hydrolyzed product had a solids content of 29.5% solids and was l Z 7 ~
18 ;1,321I
utilized to prepare laminate 211184-42. Further hsatiny would not have led to a further reduction in solution viscosity.
5 PREPARATION OF A LAMINATE FROM HYDROLYZED "TORLON 4000T"
This example is provided to show that the "Torlon" hydrolysis product is resinous and can be pro-cessed utilizing conventional techniques.
`~A 16~" x 49~2" swatch of style 7628 ~fiberglass 10 cloth was continuously impregnated with hydrol~ed "Torlon 4000T" reactor product of Example 3. The wet swatch was then cut into three 16~" x 16~2" sec'cions and B-staged 7 minutes at 175C to produce prepreg with a resin content of 32% by weight. The prepregs were cut into 15~2!J x 7 3/4"
15strips and again impregnated with 211184-40. After B-staging 10 minutes at 175C, the F~repregs ha~ a resin content of 50.1% by weight.
A molding pack was constructed by stacking nine each 7" x 7" plys of prepreg between two silicone coated 20 fiberglass bleeder plys. The molding pack was placed between steel caul plates and the whole loaded into a cold press with two layers of fiberglass cloth between the press platens and caul plates. The molding pack was then heated to 225C under 1,000 psi in one hour with an hour hold at 25 225C. Cooldown was accomplished under pressure.
After lamination under the above conditions the resulting laminate was unitary and s~uite tough. A Tg value of 185C was measured via Dynamic Mechanical Analysis (DMA). The evolution of cure volatiles during press 30 lamination was not evident.
A O.5 square inch section was cut from the laminate and placed into a sample jar containing 50 gms of DME. After approximately one hour the resin had dissolved thereby showing that the hydrolyzed "Torlon" remains 35 essentially a thermoplastic after lamination.
~2~
utilized to prepare laminate 211184-42. Further hsatiny would not have led to a further reduction in solution viscosity.
5 PREPARATION OF A LAMINATE FROM HYDROLYZED "TORLON 4000T"
This example is provided to show that the "Torlon" hydrolysis product is resinous and can be pro-cessed utilizing conventional techniques.
`~A 16~" x 49~2" swatch of style 7628 ~fiberglass 10 cloth was continuously impregnated with hydrol~ed "Torlon 4000T" reactor product of Example 3. The wet swatch was then cut into three 16~" x 16~2" sec'cions and B-staged 7 minutes at 175C to produce prepreg with a resin content of 32% by weight. The prepregs were cut into 15~2!J x 7 3/4"
15strips and again impregnated with 211184-40. After B-staging 10 minutes at 175C, the F~repregs ha~ a resin content of 50.1% by weight.
A molding pack was constructed by stacking nine each 7" x 7" plys of prepreg between two silicone coated 20 fiberglass bleeder plys. The molding pack was placed between steel caul plates and the whole loaded into a cold press with two layers of fiberglass cloth between the press platens and caul plates. The molding pack was then heated to 225C under 1,000 psi in one hour with an hour hold at 25 225C. Cooldown was accomplished under pressure.
After lamination under the above conditions the resulting laminate was unitary and s~uite tough. A Tg value of 185C was measured via Dynamic Mechanical Analysis (DMA). The evolution of cure volatiles during press 30 lamination was not evident.
A O.5 square inch section was cut from the laminate and placed into a sample jar containing 50 gms of DME. After approximately one hour the resin had dissolved thereby showing that the hydrolyzed "Torlon" remains 35 essentially a thermoplastic after lamination.
~2~
19 51,321I
EXAMPLE S
PREPARATION OF IMPREGNATING RESIN BASED UPO~T
HYDROLYZED "TORLON 4000T" AND "PLYOPHEN 94-308"
A typical charge and accompanying log for the preparation of an impregnating resin (211184-32) based upon hydrolyzed Torlon 4000T and Plyophen 94-308 is shown belsw.
Material Wt. (Gm) Wt, (Gm) NVComp~sition, Wt./D
Hydrolyzed "~orlon" 600.0 196.2 50.0 (ExamplP 3~
"Plyophen 94-308'1 196.2 196.2 50.0 796.2 392.4 100.0 c TimeTem~. ( C) Remarks 1:30RT N2, Agitator and Heat On 211082-127 and 94-308 1:4090 Reaction Mixture Clear,~ ~ Reflux 15 ~ 1 54 a~42 Refluxing - Hold. Pill - Hazy 2 10142 Pill Still Hazy 2:22143 Pill - Hazy;~_ 150C
2:55150 D~ Off, Pill Slightly Hazy 3:02153 27.1 gm DMF Off - Continue H~ating 3: 30 153 Heat Off - Pill Clear - Store Resin For Evaluation Hydrolyzed "Torlon 4000T" (600.0 gm) and "Plyophen 94-308"
(196.2 gm) were charged into a 2,000 ml round bottom, three necked flask fitted with an agitator, nitrogen inlet tube, thermometer, reflux condenser with Dean-Stark trap and a means for heating. The flask was swept with N2 gas for five minutes and the flow rate adjusted to maintain a slight positive N2 pressure in the flask throughout the balance of the run.
The agitator was started and the reaction mixture slowly heated to reflux. Compatibility testing was accom-plished by casting a small amount of material on a glass slide (termed a "pill" in t'he log) and driving off the DMF.
A "hazy pill" indicat~s that "Plyophen 94-308" is not soluble in the hydrolyzed "Torlon 4000T" solids. The reaction mixture was sampled during the 140-150C hold and 51, 3211 when a clear pill had been attained, the reaction was cooled and the product set aside for evaluation. The product had a solids content of 51.0%, a viscosity of 460 cps at 90C and a gelation tim~ of 45 minutes at 150C.
The product was impregnated without further modification.
LAMINATE PREPARATION
Approximately 400 gm of the impregnant from Example 5 was heated to 90C and utilized to impregnate a 16l~2" x 49~" swatch of style 7628 fiberglass sloth. The wet swatch was cut into three 16~2" x 16~" sections and B-stag~d 5 minutes at 170C to produce prepreg with~ a 43.3% resin content. A molding pack was constructed by stacking nine each 7" x 7" plys of prepreg between two silicone coated fiberglass cloth bleeder plys. The molding pack was placed between steel caul plates and the whole loaded into a cold press with two layers of fiberglass cloth between the press platens and caul plates. The molding pack was heated to 225C under 1,000 psi in 1 hour with a 1 hour and 15 minute hold at 225C. Cooldown was accomplished under pressure.
The resulting laminate was unitary, DMF resistant and had a Tg of 195C as measured by DMA (Figure 2). A
portion of the laminate was post-baked 16 hours at 250C.
Post-baking resulted in a 225C Tg as measured via DMA.
PREPARATION OF IMPREGNATING VARNISH BASED UPON
HYDROLYZED "TORLON 4000T" AND "IM-AD 94-394"
An impregnating varnish based upon hydrolyzed "Torlon 4000T" and "IM-AD 94-394" was prepared via a kettling operation. The charge and accompanying log is shown below.
r~
21 51,321I
Ma~erial Wt. (Gm) Wt. (Gm) NVCompo~ition, Wt. %
Hydrolyzed Torlon 291.7 87.5 2;.0 (Example 3) "IM-AD 94-394"262.5 262.5 75.0 DMF 145.8 700.0 350.0 100.0 TimeTemp. (C) Remarks 8:20 RT Charge - 40+DMF, Begin IMJAD 9h-394 Addition, N2, Heat On 8:55 60 IM-AD 94-394 Addition Complete 9:06 130 Hold, Pill Taken - Hazy 9:10 135 Mantle Down, Cool to 130 - Pill - Hazy 9:13 132 Mantle Up 9:19 130 Pill - Hazy 9:32 134 Pill - Hazy; Heat Back 9:36 130 Pill Nearly Clear 9:37 130 Gardner Viscosity - Z-l @ 25.5C, Transfer to -~ Preparing Trough ~-Prepregs and a single nine ply laminate w~re prepared utilizing techniques described in Examples 3 and 4. The prepregs ware staged 4 minutes ~t 150C followed by five additional minutes at 170C. The resulting prepreg had a resin content of 41.6% and was laminated in a nine ply array under 1,000 psi for 1 hour at 225C. Cooldown was done under pressure. The resulting laminate was unitary, DMF resistant and had a Tg value of 225C measured via DMA. Post bake would have resulted in increased Tg.
PREPARATION OF IMPREGNATING VARNISH BVASED UPON
HYDROLYZED "TORLON 4000T" AND "COMPIMIDE 183"
The resin charge and accompanying log shown below pertains to the preparation of a laminating composition based upon hydrolyzed "Torlon 4000T" and "Compimide 183."
22 ~1,32'I
Material Wt. (Gm) Wt. (Gm) NVComposition, Wt. 7/~
"Compimide 183" 225.0 225.0 75.0 (Example 3) Hydrolyzed 4000T 250.0 75.0 25.0 DMF 125.0 600.0 300.0 100.0 Time Temp. (C) Remarks o:45 ~'- RT Charge - 40+DMF; Heat, N2 On; Start 183 Addition 8:50 50 "Compimide 183" Addition Complete 8:54 80 183 Dissolved,~130C
9:02 130 Hold - Pill Taken, Slightly Hazy - 9:17 129 Slightly Hazy Pill 9:26 129 Gardner Viscosity - M ~o N (330 cps @ 25C) 9:41 130 Viscosity M-N
9:52 129 Heat Off, Cool - Hold For Evaluation Prepreging and laminating techniques previously described were utilized with this resin. The resin was impregnated at 40C and staged 3 minutes at 150C followed by 4 additional minutes B-stage time at 170C. The result-ing prepreg had a resin content of 38.0% and was laminated in a nine ply array at 225C for 1 hour under 1,000 psi pressure. Cooldown was accomplished under pressure. The resulting laminate was unitary, well cured, DMF resistant and had a Tg of 212C via DMA.
- A varnish was prepared of the following composition.
MaterialWt. (Gm) Wt. (Gm) NVGomposition, Wt. %
Hydrolyzed "Torlon 300.0 90.0 74.91 4000" (Example 3) Epon 829 31.09 30.0 24.97 2-MI 0.14 0.14 0.12 333.23 120.14100.00 23 51,321I
The varnish was submitted for evaluation as an overcoat for current low cost polyester coated wire and was indicted in a pilot wire tower. The varnish had fas~ proc~ssing characteristics, and the coating exhibited good elongation and heat shock characteristics. The following ~able gives the results of some of these experiments.
Sample A Sample B
Tow(Ftr/Spee) _ 28 32 .
10 Quick Jerk Passed Passed Elongation + 1 x (%) Passed Passed .
Electric Stress (KV) 7.9-8.0 6.5-8.3 _ _ l x heat shock 200C Passed Passed ...
220C Passed Passed lS 240C Passed Passed 260C Passed Passed
EXAMPLE S
PREPARATION OF IMPREGNATING RESIN BASED UPO~T
HYDROLYZED "TORLON 4000T" AND "PLYOPHEN 94-308"
A typical charge and accompanying log for the preparation of an impregnating resin (211184-32) based upon hydrolyzed Torlon 4000T and Plyophen 94-308 is shown belsw.
Material Wt. (Gm) Wt, (Gm) NVComp~sition, Wt./D
Hydrolyzed "~orlon" 600.0 196.2 50.0 (ExamplP 3~
"Plyophen 94-308'1 196.2 196.2 50.0 796.2 392.4 100.0 c TimeTem~. ( C) Remarks 1:30RT N2, Agitator and Heat On 211082-127 and 94-308 1:4090 Reaction Mixture Clear,~ ~ Reflux 15 ~ 1 54 a~42 Refluxing - Hold. Pill - Hazy 2 10142 Pill Still Hazy 2:22143 Pill - Hazy;~_ 150C
2:55150 D~ Off, Pill Slightly Hazy 3:02153 27.1 gm DMF Off - Continue H~ating 3: 30 153 Heat Off - Pill Clear - Store Resin For Evaluation Hydrolyzed "Torlon 4000T" (600.0 gm) and "Plyophen 94-308"
(196.2 gm) were charged into a 2,000 ml round bottom, three necked flask fitted with an agitator, nitrogen inlet tube, thermometer, reflux condenser with Dean-Stark trap and a means for heating. The flask was swept with N2 gas for five minutes and the flow rate adjusted to maintain a slight positive N2 pressure in the flask throughout the balance of the run.
The agitator was started and the reaction mixture slowly heated to reflux. Compatibility testing was accom-plished by casting a small amount of material on a glass slide (termed a "pill" in t'he log) and driving off the DMF.
A "hazy pill" indicat~s that "Plyophen 94-308" is not soluble in the hydrolyzed "Torlon 4000T" solids. The reaction mixture was sampled during the 140-150C hold and 51, 3211 when a clear pill had been attained, the reaction was cooled and the product set aside for evaluation. The product had a solids content of 51.0%, a viscosity of 460 cps at 90C and a gelation tim~ of 45 minutes at 150C.
The product was impregnated without further modification.
LAMINATE PREPARATION
Approximately 400 gm of the impregnant from Example 5 was heated to 90C and utilized to impregnate a 16l~2" x 49~" swatch of style 7628 fiberglass sloth. The wet swatch was cut into three 16~2" x 16~" sections and B-stag~d 5 minutes at 170C to produce prepreg with~ a 43.3% resin content. A molding pack was constructed by stacking nine each 7" x 7" plys of prepreg between two silicone coated fiberglass cloth bleeder plys. The molding pack was placed between steel caul plates and the whole loaded into a cold press with two layers of fiberglass cloth between the press platens and caul plates. The molding pack was heated to 225C under 1,000 psi in 1 hour with a 1 hour and 15 minute hold at 225C. Cooldown was accomplished under pressure.
The resulting laminate was unitary, DMF resistant and had a Tg of 195C as measured by DMA (Figure 2). A
portion of the laminate was post-baked 16 hours at 250C.
Post-baking resulted in a 225C Tg as measured via DMA.
PREPARATION OF IMPREGNATING VARNISH BASED UPON
HYDROLYZED "TORLON 4000T" AND "IM-AD 94-394"
An impregnating varnish based upon hydrolyzed "Torlon 4000T" and "IM-AD 94-394" was prepared via a kettling operation. The charge and accompanying log is shown below.
r~
21 51,321I
Ma~erial Wt. (Gm) Wt. (Gm) NVCompo~ition, Wt. %
Hydrolyzed Torlon 291.7 87.5 2;.0 (Example 3) "IM-AD 94-394"262.5 262.5 75.0 DMF 145.8 700.0 350.0 100.0 TimeTemp. (C) Remarks 8:20 RT Charge - 40+DMF, Begin IMJAD 9h-394 Addition, N2, Heat On 8:55 60 IM-AD 94-394 Addition Complete 9:06 130 Hold, Pill Taken - Hazy 9:10 135 Mantle Down, Cool to 130 - Pill - Hazy 9:13 132 Mantle Up 9:19 130 Pill - Hazy 9:32 134 Pill - Hazy; Heat Back 9:36 130 Pill Nearly Clear 9:37 130 Gardner Viscosity - Z-l @ 25.5C, Transfer to -~ Preparing Trough ~-Prepregs and a single nine ply laminate w~re prepared utilizing techniques described in Examples 3 and 4. The prepregs ware staged 4 minutes ~t 150C followed by five additional minutes at 170C. The resulting prepreg had a resin content of 41.6% and was laminated in a nine ply array under 1,000 psi for 1 hour at 225C. Cooldown was done under pressure. The resulting laminate was unitary, DMF resistant and had a Tg value of 225C measured via DMA. Post bake would have resulted in increased Tg.
PREPARATION OF IMPREGNATING VARNISH BVASED UPON
HYDROLYZED "TORLON 4000T" AND "COMPIMIDE 183"
The resin charge and accompanying log shown below pertains to the preparation of a laminating composition based upon hydrolyzed "Torlon 4000T" and "Compimide 183."
22 ~1,32'I
Material Wt. (Gm) Wt. (Gm) NVComposition, Wt. 7/~
"Compimide 183" 225.0 225.0 75.0 (Example 3) Hydrolyzed 4000T 250.0 75.0 25.0 DMF 125.0 600.0 300.0 100.0 Time Temp. (C) Remarks o:45 ~'- RT Charge - 40+DMF; Heat, N2 On; Start 183 Addition 8:50 50 "Compimide 183" Addition Complete 8:54 80 183 Dissolved,~130C
9:02 130 Hold - Pill Taken, Slightly Hazy - 9:17 129 Slightly Hazy Pill 9:26 129 Gardner Viscosity - M ~o N (330 cps @ 25C) 9:41 130 Viscosity M-N
9:52 129 Heat Off, Cool - Hold For Evaluation Prepreging and laminating techniques previously described were utilized with this resin. The resin was impregnated at 40C and staged 3 minutes at 150C followed by 4 additional minutes B-stage time at 170C. The result-ing prepreg had a resin content of 38.0% and was laminated in a nine ply array at 225C for 1 hour under 1,000 psi pressure. Cooldown was accomplished under pressure. The resulting laminate was unitary, well cured, DMF resistant and had a Tg of 212C via DMA.
- A varnish was prepared of the following composition.
MaterialWt. (Gm) Wt. (Gm) NVGomposition, Wt. %
Hydrolyzed "Torlon 300.0 90.0 74.91 4000" (Example 3) Epon 829 31.09 30.0 24.97 2-MI 0.14 0.14 0.12 333.23 120.14100.00 23 51,321I
The varnish was submitted for evaluation as an overcoat for current low cost polyester coated wire and was indicted in a pilot wire tower. The varnish had fas~ proc~ssing characteristics, and the coating exhibited good elongation and heat shock characteristics. The following ~able gives the results of some of these experiments.
Sample A Sample B
Tow(Ftr/Spee) _ 28 32 .
10 Quick Jerk Passed Passed Elongation + 1 x (%) Passed Passed .
Electric Stress (KV) 7.9-8.0 6.5-8.3 _ _ l x heat shock 200C Passed Passed ...
220C Passed Passed lS 240C Passed Passed 260C Passed Passed
Claims (55)
1. A composition comprising (A) a solution in an aprotic solvent of about 5 to about 95 phr of a polyimide having both a first functionality that is imide and a second functionality selected from the group consisting of amic acid functionality, hydrolyzed amic acid functionality, and mixtures thereof, where said second functionality is about 5 to about 50% of the total of said first and second functionalities, and a sufficient amount of said second functionality is present to solubilize said poly-imide;
(B) sufficient water to hydrolyze any amic acid functionality present on said polyimide and (C) about 5 to about 95 phr of a coreactive com-pound that will react with said polyimide, where said core-active compound is selected from the group consisting of monomers, polymers, and mixtures thereof.
(B) sufficient water to hydrolyze any amic acid functionality present on said polyimide and (C) about 5 to about 95 phr of a coreactive com-pound that will react with said polyimide, where said core-active compound is selected from the group consisting of monomers, polymers, and mixtures thereof.
2. A composition according to Claim 1, wherein the concentration of said aprotic solvent is about 20 to about 90%.
3. A composition according to Claim 1, wherein said solvent is selected from the group consisting of dimethyl form-amide, dimethylamine, N-methyl pyrrolidinone, dimethylsulfoxide, and mixtures thereof.
4. A composition according to Claim 1, which includes about 0.1 to about 5% of a hydrocarbon solvent.
5. A composition according to Claim 1, which includes about 0.1 to about 25% based on solids of a filler.
6. A composition according to Claim 5, wherein said filler is alumina trihydrate.
7. A composition according to Claim 1, which includes about 0.1 to about 5% based on solids of a pigment.
- 25 - 51,3211
- 25 - 51,3211
8. A composition according to Claim 1, which includes about 0.1 to about 0.7 phr of a catalyst.
9. A composition according to Claim 8, wherein said catalyst is 2-methylimidazole.
10. A composition according to Claim 1, wherein said coreactive compound is about 50 to about 80 phr and said polyimide is about 20 to about 50 phr.
11. A composition according to Claim 1, wherein said coreactive compound is selected from the group consist-ing of polyepoxides, polyimides, diols diacids, diamines, phenolic resins, capped isocyanates, and mixtures thereof.
12. A composition according to Claim 11, wherein said coreactive compound is a polyepoxide.
13. A composition according to Claim 12, wherein said polyepoxide is a diglycidyl ether of bisphenol A.
14. A composition comprising:
(A) a solution in a solvent of about 5 to about 95 phr or a polyepoxide;
(s) about 5 to about 95 phr of a polyimide hav-ing sufficient functionality selected from the group consist-ing of amic acid, hydrolyzed amic acid, and mixtures thereof to be soluble in said solvent, where said functionality is about 5 to about 50% of the total of said functionality plus imide functionality in said polyimide; and (C) sufficient water to hydrolyze all of said amic acid functionality of said polyimide.
(A) a solution in a solvent of about 5 to about 95 phr or a polyepoxide;
(s) about 5 to about 95 phr of a polyimide hav-ing sufficient functionality selected from the group consist-ing of amic acid, hydrolyzed amic acid, and mixtures thereof to be soluble in said solvent, where said functionality is about 5 to about 50% of the total of said functionality plus imide functionality in said polyimide; and (C) sufficient water to hydrolyze all of said amic acid functionality of said polyimide.
15. A composition according to Claim 14, wherein said amic acid functionality is substantially fully hydrolyzed by said water.
16. A composition comprising a solution of about 5 to about 95% of the reaction product of an oligomer, which is the reaction product of water and the amic acid groups of a polyimide, where said amic acid groups are about 5 to about 50% of the total of amic acid plus imide groups in said polyimide, and about 5 to about - 26 - 51,3211 95% of a coreactive compound selected from the group consist-ing of monomers, polymers, and mixtures thereof
17. A composition according to Claim 16, wherein said coreactive compound is a polyepoxide.
18. A method of making a laminate comprising:
(A) preparing a composition which comprises (1) a solution in an aprotic solvent of about 5 to about 95 phr of a polyimide having both a first funct-ionality that is imide and a second functionality selected from the group consisting of amic acid functionality, hyd-rolyzed amic acid functionality, and mixtures thereof, where said second functionality is about 5 to about 50% of the total of said first and seocnd functionalities, and a suff-icient amount of said second functionality is present to solubilize said polyimide;
(2) sufficient water to hydrolyze any amic acid functionality present on said polyimide; and (3) about 5 to about 95 phr of a coreactive compound that will react with said polyimide, where said coreactive compound is selected from the group consisting of monomers, polymers, and mixtures thereof;
(B) heating said composition until said amic acid functionality is substantially eliminated;
(C) impregnating a fibrous subtrate with said composition;
(D) heating said impregnated substrate to evapor-ate said solvent, B-stage said composition, and form a prep-reg;
(E) forming a stack of said prepregs; and (F) heating and pressing said stack of prepregs to cure said composition.
(A) preparing a composition which comprises (1) a solution in an aprotic solvent of about 5 to about 95 phr of a polyimide having both a first funct-ionality that is imide and a second functionality selected from the group consisting of amic acid functionality, hyd-rolyzed amic acid functionality, and mixtures thereof, where said second functionality is about 5 to about 50% of the total of said first and seocnd functionalities, and a suff-icient amount of said second functionality is present to solubilize said polyimide;
(2) sufficient water to hydrolyze any amic acid functionality present on said polyimide; and (3) about 5 to about 95 phr of a coreactive compound that will react with said polyimide, where said coreactive compound is selected from the group consisting of monomers, polymers, and mixtures thereof;
(B) heating said composition until said amic acid functionality is substantially eliminated;
(C) impregnating a fibrous subtrate with said composition;
(D) heating said impregnated substrate to evapor-ate said solvent, B-stage said composition, and form a prep-reg;
(E) forming a stack of said prepregs; and (F) heating and pressing said stack of prepregs to cure said composition.
19. A method according to Claim 18, wherein said composition is heated in step (b) at about 100 to about 150 C
for about 1/2 hour.
- 27 - 51,3211
for about 1/2 hour.
- 27 - 51,3211
20. A method according to Claim 18, wherein additional solvent is added after step (B) to lower the viscosity of said composition.
21. A method according to Claim 18, wherein said fibrous substrate is fiber glass cloth.
22. A method according to Claim 18, wherein said impregnated substrate is about 20 to about 60% resin solids and about 40 to about 80% fibrous substrate.
23. A method according to Claim 18, wherein said heating in step (F) is at about 150 to about 220 C for about l hour at about 1000 psi.
24. A method according to Claim 18, wherein said coreactive compound is a polyepoxide.
25. An enameled wire comprising an elongated conductor coated with a cured composition which comprises (1) a solution in an aprotic solvent of about 5 to about 95 phr of a polyimide having both a first function-ality that is imide and a second functionality selected from the group consisting of amic acid funtionality, hydrolyzed amic acid functionality, and mixtures thereof, where said second functionality is about 5 to about 50% of the total of said first and second functionalities, and a sufficient amount of said second funtionality is present to solubilize said polyimide;
(2) sufficient water to hydrolyze any amic acid functionality present on said polyimide; and (3) about 5 to about 95 phr of a coreactive compound that will react with said polyimide, where said coreactive compound is selected from the group consisting of monomers, polymers, and mixtures thereof.
(2) sufficient water to hydrolyze any amic acid functionality present on said polyimide; and (3) about 5 to about 95 phr of a coreactive compound that will react with said polyimide, where said coreactive compound is selected from the group consisting of monomers, polymers, and mixtures thereof.
26. A B-staged prepreg comprising a substrate imbedded within a resinous matrix which comprised, before B-staging:
- 28 - 51,3211 (A) about 5 to about 95 phr of a polyepoxide;
(B) about 20 to about 90% aprotic solvent;
(C) about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in said solvent; and (D) sufficient water to hydrolyze substantially all of said amic acid functionality of said polymer.
- 28 - 51,3211 (A) about 5 to about 95 phr of a polyepoxide;
(B) about 20 to about 90% aprotic solvent;
(C) about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in said solvent; and (D) sufficient water to hydrolyze substantially all of said amic acid functionality of said polymer.
27. A B-staged prepreg according to Claim 26, wherein said substrate is fibrous material selected from the group consisting of glass, cotton, quartz, polyamide, paper, carbon, and mixtures thereof.
28. A laminate comprising a plurality of layers of a substrate imbedded within a cured resinous matrix, said resinous matrix comprising, in an uncured state:
(A) about 5 to about 95 phr of a polyepoxide;
(B) about 20 to about 90% aprotic solvent;
(C) about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in said solvent, where about 5 to about 50% of the total of amic acid plus imide groups on said polyimide are amic acid groups, and about 50 to about 95% are imide groups; and (D) sufficient water to hydrolyze substantially all of said amic acid functionality of said polymer.
(A) about 5 to about 95 phr of a polyepoxide;
(B) about 20 to about 90% aprotic solvent;
(C) about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in said solvent, where about 5 to about 50% of the total of amic acid plus imide groups on said polyimide are amic acid groups, and about 50 to about 95% are imide groups; and (D) sufficient water to hydrolyze substantially all of said amic acid functionality of said polymer.
29. A laminate according to Claim 28, including a metal conductor bonded to at least one surface of said laminate.
30. A laminate according to Claim 29, wherein said metal conductor is copper circuitry.
31. A laminate according to Claim 29, wherein said metal conductor is copper foil.
32. A filament wound cylinder comprising roving embedded within a cured resinous matrix, said resinous matrix comprising, in an uncured state:
(A) about 5 to about 95 phr of a polyepoxide;
- 29 - 51,3211 (B) about 20 to about 90% aprotic solvent;
(C) about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in said solvent, where about 5 to about 50% of the total of amic acid plus imide groups on said polyimide are amic acid groups, and about 50 to about 95% are imide groups; and (D) sufficient water to hydrolyze said polymer
(A) about 5 to about 95 phr of a polyepoxide;
- 29 - 51,3211 (B) about 20 to about 90% aprotic solvent;
(C) about 5 to about 95 phr of a polyimide having sufficient amic acid functionality to be soluble in said solvent, where about 5 to about 50% of the total of amic acid plus imide groups on said polyimide are amic acid groups, and about 50 to about 95% are imide groups; and (D) sufficient water to hydrolyze said polymer
33. A filament wound cylinder according to Claim 32 wherein said roving is glass.
34. A method of making a laminate comprising (A) preparing a solution in an aprotic solvent of (1) a polyimide having sufficient amic acid functionality to be soluble in said solvent, where about 5 to about 50% of the total of amic acid plus imide groups on said polyimide are amic acid groups, and about 50 to about 95% are imide groups; and (2) sufficient water to hydrolyze substantially all of said amic acid functionality of said polyimide;
(B) heating said composition until said amic acid functionality is substantially eliminated.
(B) heating said composition until said amic acid functionality is substantially eliminated.
35. A laminate made according to the method of Claim 34.
36. A composition according to Claim 1, wherein said second functionality is amic acid functionality.
37. A composition according to Claim 1, wherein said second functionality is hydrolyzed amic acid function-ality.
38. A laminate according to Claim 28, wherein said solvent is selected from the group consisting of dime-thyl formamide, dimethylamine, N-methyl pyrrolidinone, dime-thyl sulfoxide, and mixtures thereof.
- 30 - 51,3211
- 30 - 51,3211
39. A laminate according to Claim 28, which includes about 0.1 to about 5% of a hydrocarbon solvent.
40. A laminate according to Claim 28 which includes about 0.1 to about 25%, based on solids, of a filler.
41. A laminate according to Claim 40, wherein said filler is alumina trihydrate.
42. A laminate according to Claim 28, which includes about 0.1 to about 5%, based on solids, of a pigment.
43. A laminate according to Claim 28, which includes about 0.1 to about 0.7 phr of a catalyst.
44. A laminate according to Claim 43 wherein said catalyst is 2-methylimidazole.
45. A laminate according to Claim 28, wherein said polyepoxide is about 50 to about 80 phr and said poly-imide is about 20 to about 50 phr.
46. A laminate according to Claim 28, wherein said polyepoxide is a diglycidyl ether of bisphenol A.
47. A filament wound cylinder according to Claim 32, wherein said solvent is selected from the group consist-ing of dimethyl formamide, dimethylamine, N-methyl pyrrolid-inone, dimethylsulfoxide, and mixtures thereof.
48. A filament wound cylinder according to Claim 32, which includes about 0.1 to about 5% of a hydrocarbon solvent.
49. A filament wound cylinder according to Claim 32, which indludes about 0.1 to about 25% based on solids, of a filler.
50. A filament wound cylinder according to Claim 49, wherein said filler is alumina trihydrate.
51. A filament wound cylinder according to Claim 32, which includes about 0.1 to about 5% based on solids, of a pigment.
- 31 - 51,3211
- 31 - 51,3211
52. A filament wound cylinder according to Claim 32, which includes about 0.1 to about 0.7 phr of a catalyst.
53. A filament wound cylinder according to Claim 52 wherein said catalyst is 2-methylimidazole.
54. A filament wound cylinder according to Claim 32, wherein said coreactive compound is about 50 to about 80 phr and said polyimide is about 20 to about 50 phr.
55. A filament wound cylinder according to Claim 32, wherein said polyepoxide is a diglycidyl ether of bis-phenol A.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/790,563 US4675350A (en) | 1984-11-13 | 1985-10-23 | Compatible self-crosslinking poly (amide-imide) polyepoxide resin blends and laminates made therewith |
| US790,563 | 1997-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1274640A true CA1274640A (en) | 1990-09-25 |
Family
ID=25151081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000519991A Expired CA1274640A (en) | 1985-10-23 | 1986-10-07 | Compatible self-crosslinking poly (amide-imide) polyepoxide resin blends and laminates made therewith |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1274640A (en) |
-
1986
- 1986-10-07 CA CA000519991A patent/CA1274640A/en not_active Expired
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