CA2055642A1 - Curable epoxy resin composition - Google Patents
Curable epoxy resin compositionInfo
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- CA2055642A1 CA2055642A1 CA 2055642 CA2055642A CA2055642A1 CA 2055642 A1 CA2055642 A1 CA 2055642A1 CA 2055642 CA2055642 CA 2055642 CA 2055642 A CA2055642 A CA 2055642A CA 2055642 A1 CA2055642 A1 CA 2055642A1
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- weight
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- composition according
- epoxy resin
- glycidyl ether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Curable epoxy resin composition Abstract of the Disclosure Curable epoxy resin compositions comprising (a) 30 to 70 parts by weight of a tetraglycidyl compound of formula
Description
2Q5i~L2 , K- 1 8~33/A/CGW 26 Curable epoxv resin composition The present invention relates to a curable epoxy resin compositi~n comprising ~m epoxy resin consisting of a mixture of a tetraglycidyl compound of a binuclear subsfituted diamine and an aromatie glycidyl ether containing at least two glycidyl ether groups in the molecule, a diaminodiphenylsulfone as hardener and, in addition, a thermopastic resin having a glass transition temperature of least 150C, and to the use of said composition, especially as matrix resin for making prepregs.
It is known that the properties of curable epoxy resin compositions can be modified by the addition of specific thermoplastic resins. For example, it is disclosed in EP-~-0 108 476 that the addition of the polyetherimide ULTEM(~) to curable epoxy resin compositions such as N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and diaminodiphen-ylsulfone is able to increase the viscosity of said mixtures and to enhance the flexibility of the moulded articles obtained.
It has now been found that, by modifying an epoxy resin composition containing two specific epoxy resins with certain thermoplastic resins, it is possible to improve the processing properties of the curable rnixture, such as goocl flow properties ov~r longer processing times. Tn addition, the rnoulcled articles prepared from the eurable mixture s)f the invention have improved flexural stren~th and, in particular, markedly enhanced flexibility, The surprisingly good compatibility of the curable epoxy resin composition with thermoplastic resins such as ULTEM~ also makes it possible to add larger amounts of thermoplastic without any demixing.
Thus the present invention relates to a curable epoxy resin composition comprising (a) 30 to 70 parts by weight of a tetraglycidyl compound of -formula I
It is known that the properties of curable epoxy resin compositions can be modified by the addition of specific thermoplastic resins. For example, it is disclosed in EP-~-0 108 476 that the addition of the polyetherimide ULTEM(~) to curable epoxy resin compositions such as N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and diaminodiphen-ylsulfone is able to increase the viscosity of said mixtures and to enhance the flexibility of the moulded articles obtained.
It has now been found that, by modifying an epoxy resin composition containing two specific epoxy resins with certain thermoplastic resins, it is possible to improve the processing properties of the curable rnixture, such as goocl flow properties ov~r longer processing times. Tn addition, the rnoulcled articles prepared from the eurable mixture s)f the invention have improved flexural stren~th and, in particular, markedly enhanced flexibility, The surprisingly good compatibility of the curable epoxy resin composition with thermoplastic resins such as ULTEM~ also makes it possible to add larger amounts of thermoplastic without any demixing.
Thus the present invention relates to a curable epoxy resin composition comprising (a) 30 to 70 parts by weight of a tetraglycidyl compound of -formula I
-2- ~ Z
~ CH2~ CH- CH2~ N ~ CH2~ N t CH2- CH- CH2) (I) wherein Rl, R2, R3 and R4 are each independently ~ one another a hydrogen atom, a halogen atom or Cl-C4alkyl, with the proviso that at least one of the substituents Rl to R~
is Cl-C~alkyl, (b) 70 to 30 parts by weight of an aromatic glycidyl ether containing on average 2.0 to 3.0 glycidyl ether groups in the molecule, SUC}I that the amount of (a) and (b) together is 100 parts by weight, (c) a diaminodiphenylsulfone in an amount such as to supply 0.6 to 1.3 equivalents of amino hydrogen atoms per I epoxide equivalent of the epoxy resin component consisting of (a) and (b), and (d) I to 50 parts by weight, based on 100 parts by weight of (a) and (b), of a thermoplastic resin dissolved therein having a glass transition temperature of at least 150C.
The composition of this invention preferably contains (a) 40 to 60 parts by weight of a tetraglycidyl compound of formula I and (b) 60 to 40 parts by weight of an aromatic glycidyl ether.
The compounds of formula I are known and are disclosed, for example, inEP-~-0 143 075 ancl in JP Kokai 84-078.
Preferrecl haiogen substitllc nts are bromo or chloro.
Preferred compounds of formula I are those wherein at least one of the substituents R1 to R~ is methyl, ethyl or isopropyl. Most preferably the compositions of this invention contain a compound of forrnula 1, wherein Rl and R3 are each hydrogen and R2 and R4 are each ethyl.
Suitable aromatic glycidyl ethers (b) are typically those epoxy compounds which are obtained by reacting compounds containing two or three phenolic hydroxyl groups per molecule with suitable epihalohydrins such as epichlorohydrin, under alkaline conditions or else in the presence of an acid catalyst, followed by tTeatment with alkali. They may be ~556~i~
derived from mon~nllclear phenols, swch as resorcinol and hydroqllinone, or frompolynuclear phenols, such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, 1,5-, 1,~-, 2,3- or 2,7-dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis-(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyyhenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and novolaks which are in turn derived from aldehydes, such as formaldehyde, acetaldehyde, chloral and furfurylaldehyde, and phenols, such as unsubstituted phenol and phenols, which are substituted at the ring by chlorine atoms or alkyl groups containing up to 9 carbon atoms, typically 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol.
The cited epoxy compounds are known and some are commercially available.
The compositions of the invention preferably contain aromatic glycidyl ethers containing on average 2.0 to 2.2 glycidyl ether groups in the molecule. More particularly, the aromatic glycidyl ether (b) of the novel composition is bisphenol A or bisphenyl F
diglycidyl ether, the diglycidyl ether of a dihydroxynaphthalene or a mixture of said glycidyl ethers.
The composition of this invention preferably contains the diaminodiphenylsulfone (c) used as hardener in an amount sufficient to provide 0.8 to 1.0 equivalent of amino hydrogen per I epoxy equivalent.
Viaminodiphenylsulfones are likewise known and some are commercially av~ailable. The composition of the invention preferably contains 4,4'-diaminodiphenyls~llfone as hardener (c).
Tllermnplastic resins (d) which may be used in the curable compositions of this invention ~are all thosc known polymers which have a sumciently high glass transition temperature (Tg), i.e. Tg > 150C, and which are miscible with the epoxy resin hardener system in question. On account of their properties, particularly suitable thermoplastic resins are polysulfones or polyethersulfones which contain amino groups in the chain, polyimides or polyetherimides and, pre~erably, polyimides and polyetherimides. Thermoplastic resins having a glass transition temperature in the range from 180 to 350C, preferably from 190 to 250C, are especially preferred. If polyetherimides are used as thermoplastic resins, polymers having a Tg in the range from 220 to 250C are especially preferred. Ifpolyimides are used, polymers having a Tg in the range f3 om 280 to 340C are preferred.
;~5~
~ CH2~ CH- CH2~ N ~ CH2~ N t CH2- CH- CH2) (I) wherein Rl, R2, R3 and R4 are each independently ~ one another a hydrogen atom, a halogen atom or Cl-C4alkyl, with the proviso that at least one of the substituents Rl to R~
is Cl-C~alkyl, (b) 70 to 30 parts by weight of an aromatic glycidyl ether containing on average 2.0 to 3.0 glycidyl ether groups in the molecule, SUC}I that the amount of (a) and (b) together is 100 parts by weight, (c) a diaminodiphenylsulfone in an amount such as to supply 0.6 to 1.3 equivalents of amino hydrogen atoms per I epoxide equivalent of the epoxy resin component consisting of (a) and (b), and (d) I to 50 parts by weight, based on 100 parts by weight of (a) and (b), of a thermoplastic resin dissolved therein having a glass transition temperature of at least 150C.
The composition of this invention preferably contains (a) 40 to 60 parts by weight of a tetraglycidyl compound of formula I and (b) 60 to 40 parts by weight of an aromatic glycidyl ether.
The compounds of formula I are known and are disclosed, for example, inEP-~-0 143 075 ancl in JP Kokai 84-078.
Preferrecl haiogen substitllc nts are bromo or chloro.
Preferred compounds of formula I are those wherein at least one of the substituents R1 to R~ is methyl, ethyl or isopropyl. Most preferably the compositions of this invention contain a compound of forrnula 1, wherein Rl and R3 are each hydrogen and R2 and R4 are each ethyl.
Suitable aromatic glycidyl ethers (b) are typically those epoxy compounds which are obtained by reacting compounds containing two or three phenolic hydroxyl groups per molecule with suitable epihalohydrins such as epichlorohydrin, under alkaline conditions or else in the presence of an acid catalyst, followed by tTeatment with alkali. They may be ~556~i~
derived from mon~nllclear phenols, swch as resorcinol and hydroqllinone, or frompolynuclear phenols, such as bis(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, 1,5-, 1,~-, 2,3- or 2,7-dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis-(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyyhenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane and novolaks which are in turn derived from aldehydes, such as formaldehyde, acetaldehyde, chloral and furfurylaldehyde, and phenols, such as unsubstituted phenol and phenols, which are substituted at the ring by chlorine atoms or alkyl groups containing up to 9 carbon atoms, typically 4-chlorophenol, 2-methylphenol and 4-tert-butylphenol.
The cited epoxy compounds are known and some are commercially available.
The compositions of the invention preferably contain aromatic glycidyl ethers containing on average 2.0 to 2.2 glycidyl ether groups in the molecule. More particularly, the aromatic glycidyl ether (b) of the novel composition is bisphenol A or bisphenyl F
diglycidyl ether, the diglycidyl ether of a dihydroxynaphthalene or a mixture of said glycidyl ethers.
The composition of this invention preferably contains the diaminodiphenylsulfone (c) used as hardener in an amount sufficient to provide 0.8 to 1.0 equivalent of amino hydrogen per I epoxy equivalent.
Viaminodiphenylsulfones are likewise known and some are commercially av~ailable. The composition of the invention preferably contains 4,4'-diaminodiphenyls~llfone as hardener (c).
Tllermnplastic resins (d) which may be used in the curable compositions of this invention ~are all thosc known polymers which have a sumciently high glass transition temperature (Tg), i.e. Tg > 150C, and which are miscible with the epoxy resin hardener system in question. On account of their properties, particularly suitable thermoplastic resins are polysulfones or polyethersulfones which contain amino groups in the chain, polyimides or polyetherimides and, pre~erably, polyimides and polyetherimides. Thermoplastic resins having a glass transition temperature in the range from 180 to 350C, preferably from 190 to 250C, are especially preferred. If polyetherimides are used as thermoplastic resins, polymers having a Tg in the range from 220 to 250C are especially preferred. Ifpolyimides are used, polymers having a Tg in the range f3 om 280 to 340C are preferred.
;~5~
Polyamide-imides are also suitable.
Mixtures of two or more thermoplastic resins can also be used as component (d).
Particularly suitable thermoplastic resins (d) are polyimides such as - the polyimides containing phenylindane units disclosed in US patent 3 856 752 and in EP-A 92 524, especially those having a glass transition temperature of about 305C and an average molecular weight of 65 000, for exan~ple Ma~imid(~ 5218 sold by Ciba-Geigy, - the homo- and copolyimides of at least one aromatic tetracarboxylic acid and at least one aromatic diamine disclosed for example in US patent 4 629 777, and - thehomo-andcopolyimidesdisclosedinEP-A 162017,EP-A 181 837andin US patent 4 629 685.
Preferred thermoplastic resins (d) are also the polyetherimides sold by General Electric under the registered trademark Ultem(~ (e.g. as Ultem(3) 1000). Further preferred therrnoplastic resins are polyethersulfones, such as Victrex PES l(X) P sold by ICI or Udel P 1800 sold by Union Carbide.
Suitable polyamide-imides are typically the compounds disclosed in US patents 3 894 114, 3 948 835; 3 926 911 and 3 950 408.
If the thermoplastic resin td) is a polysulfone or polyethersulfone containing amino groups in the chain, then it is suitably one having an inherent viscosity (rijnh) of 0.02 to 1.0, measured in a I % solution of the polymer in N-methylpyrrolidone at 25C anc'i which contains, based on the total number of structural units present in the polymer, 1(}() to 5 mol % of structural repeating unit of formula Il or III
C --Ar--O ~ (Il) or ~ ~ ~ ~3} (III) ~s~
and 95 to O mol % of a structural repeating unit of formula IV
--~ X ~3 0 - Ar- O ~ (IV) wherein X is -SO2- or-CO-, and Ar is a group of -formulae IVa to IVe IVa), wherein a is O or 1, ~3 (IVb), X~ ~IVc), (IVd), wherein b is 1 or 2, or ~3 Z ~ Z--~3 (IVe) wherein Z is -CO-, -SO2-, -SO-, -S-~ O-, -C(CH3)2, -C(CF3~2, -C~l2- or - lc-C6Hs which group is unsubstituted or substituted by one or more Cl-C4alkyl or C1-C4alkoxy groups or halogen atoms.
T hese polyarylene ethers may be prepared typically by reacting 1,3-dichloro-4-nitrobenzene or a mixture of 1,3-dichloro-4-niirobenzene and a dihalo compound which is present therein in an amount of g5 mol %, preferably 90 mol %, of formula V
~5S64~
Mixtures of two or more thermoplastic resins can also be used as component (d).
Particularly suitable thermoplastic resins (d) are polyimides such as - the polyimides containing phenylindane units disclosed in US patent 3 856 752 and in EP-A 92 524, especially those having a glass transition temperature of about 305C and an average molecular weight of 65 000, for exan~ple Ma~imid(~ 5218 sold by Ciba-Geigy, - the homo- and copolyimides of at least one aromatic tetracarboxylic acid and at least one aromatic diamine disclosed for example in US patent 4 629 777, and - thehomo-andcopolyimidesdisclosedinEP-A 162017,EP-A 181 837andin US patent 4 629 685.
Preferred thermoplastic resins (d) are also the polyetherimides sold by General Electric under the registered trademark Ultem(~ (e.g. as Ultem(3) 1000). Further preferred therrnoplastic resins are polyethersulfones, such as Victrex PES l(X) P sold by ICI or Udel P 1800 sold by Union Carbide.
Suitable polyamide-imides are typically the compounds disclosed in US patents 3 894 114, 3 948 835; 3 926 911 and 3 950 408.
If the thermoplastic resin td) is a polysulfone or polyethersulfone containing amino groups in the chain, then it is suitably one having an inherent viscosity (rijnh) of 0.02 to 1.0, measured in a I % solution of the polymer in N-methylpyrrolidone at 25C anc'i which contains, based on the total number of structural units present in the polymer, 1(}() to 5 mol % of structural repeating unit of formula Il or III
C --Ar--O ~ (Il) or ~ ~ ~ ~3} (III) ~s~
and 95 to O mol % of a structural repeating unit of formula IV
--~ X ~3 0 - Ar- O ~ (IV) wherein X is -SO2- or-CO-, and Ar is a group of -formulae IVa to IVe IVa), wherein a is O or 1, ~3 (IVb), X~ ~IVc), (IVd), wherein b is 1 or 2, or ~3 Z ~ Z--~3 (IVe) wherein Z is -CO-, -SO2-, -SO-, -S-~ O-, -C(CH3)2, -C(CF3~2, -C~l2- or - lc-C6Hs which group is unsubstituted or substituted by one or more Cl-C4alkyl or C1-C4alkoxy groups or halogen atoms.
T hese polyarylene ethers may be prepared typically by reacting 1,3-dichloro-4-nitrobenzene or a mixture of 1,3-dichloro-4-niirobenzene and a dihalo compound which is present therein in an amount of g5 mol %, preferably 90 mol %, of formula V
~5S64~
Hal ~ X ~3 Hal (V), wherein Hal is a halogen atom, preferably a chlorine or fluorine atom, and X is as defined above, with a diphenol of formula VI
HO-Ar-OH (VI), wherein Ar is as defined above, or by polycondensing 2,4-bis(4-hydroxyphenoxy)aniline or a mixture of 2,4-bis(4-hydroxyphenoxy)aniline and a diphenol of formu]a Vl contained therein in an amount of 95 mol %, preferably 90 mol %, with a halogen compound of forrnula V, in the presence of alkali and in an aprotic solvent, until the polyarylene ether so nbtained has a lli.,h of 0.02 to 1.0, and subsequently converting the nitro group containing polyarylene ether in known manner into an amino group containing polyarylene ether by complete catalytic reduction of the nitro groups.
The alkali used in this process is normally an allcali metal carbonate or alkaline earth metal carbonate, such as sodium, potasssium or calcium carbonate. However, it is also possible to use other alkaline reagents such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
Polar aprotic solvents which may be used in the process for the prepnration of the poly~rylene ether resins are typically diethyl acetamide, tetramethylurea, N-methylcaprolactam and, preferably, dimethyl acetamide or N-methylpyTroliclone.
The reaction is conveniently carried out at elevated temperature, preferably in the range up to the reflux temperature of the solvent, i.e. up to about 250C.
The composition of this invention preferably contains a therrnoplastic resin (d~ in an amount of 15 to 30 parts by weight, based on 100 parts by weight of (a) and (b).
The composi~ion of the invention preferably also contains a polyimide or polyetherimide as thermoplastic resin.
The compositions of the invention can be prepared by thoroughly mixing all components ~5~6~
HO-Ar-OH (VI), wherein Ar is as defined above, or by polycondensing 2,4-bis(4-hydroxyphenoxy)aniline or a mixture of 2,4-bis(4-hydroxyphenoxy)aniline and a diphenol of formu]a Vl contained therein in an amount of 95 mol %, preferably 90 mol %, with a halogen compound of forrnula V, in the presence of alkali and in an aprotic solvent, until the polyarylene ether so nbtained has a lli.,h of 0.02 to 1.0, and subsequently converting the nitro group containing polyarylene ether in known manner into an amino group containing polyarylene ether by complete catalytic reduction of the nitro groups.
The alkali used in this process is normally an allcali metal carbonate or alkaline earth metal carbonate, such as sodium, potasssium or calcium carbonate. However, it is also possible to use other alkaline reagents such as sodium hydroxide, potassium hydroxide or calcium hydroxide.
Polar aprotic solvents which may be used in the process for the prepnration of the poly~rylene ether resins are typically diethyl acetamide, tetramethylurea, N-methylcaprolactam and, preferably, dimethyl acetamide or N-methylpyTroliclone.
The reaction is conveniently carried out at elevated temperature, preferably in the range up to the reflux temperature of the solvent, i.e. up to about 250C.
The composition of this invention preferably contains a therrnoplastic resin (d~ in an amount of 15 to 30 parts by weight, based on 100 parts by weight of (a) and (b).
The composi~ion of the invention preferably also contains a polyimide or polyetherimide as thermoplastic resin.
The compositions of the invention can be prepared by thoroughly mixing all components ~5~6~
or dissolving them in one another, and the indiviclual components can be added in any o}der. The thermoplastic resin may be dissolved in the epoxy resin by heating and, after cooling, the other ingredients can be added. It is, however, also possible to prepare a solution of the thermoplastic resin in an inert solvent, typically methylene chloride, and to mix said solution with the epoxy resin-hardener mixture.
The compositions of the invention have many uses and are suitable for example as casting resins, laminating or impregnating resins, moulding materials, sealing compounds and insulating compounds in the electrical engineering field and, preferably, as adhesives and matrix resins for composites, especially for making prepregs for the preparation of fibre-reinforced plastics.
~f desired, especially when concurrently using modifiers, the compositions of this invention can be dissolved in an organic solvent such as ~oluene, xylene, methyl ethyl ketone, methylene chloride, or a solvent or mixture of solvents commonly ernployed in the coating industry. Such solutions are particularly suitable as impregnating or coating compositions~
The curable compositions of this invention can also be blended, prior to the cure, in any phase with conventional modifiers, such as extenders, fillers and reinforcing agents, pigments, dyes, organic solvents, plasticisers, levelling agents, thixotropic agents, flame retardants or mould release agents. Typical examples of extenders, reinforcing agents, fillers and pigments which can be used in the curable compositions of this invention are:
liquid cumene-indene resins, textile fibres, glass fibres, asbestos fibres, boron fibres, carbon fibres, polyethylene powder, polypropylene powder, quartz powcler, mineral silicates such as mica, lasbestos powder, ground shale, kaolin, powdered chalk, antimony trioxide. bentones, lithopones, barite, titanium dioxide, carbon black, oxide pigments such as iron oxide, or metal powders such as aluminium powder or iron powder. If the compositions of the invention are used for making prepregs, it is especially desirable to add ground fibres.
Levelling agents which may be added to the curable compositions, especially for surface protection, are typically silicones, liquid acrylic resins, cellulose acetobutyrate, polyvinylbutyral, waxes, stearates and the like (some of which may also be used as mould release agents).
The compositions of the invention have many uses and are suitable for example as casting resins, laminating or impregnating resins, moulding materials, sealing compounds and insulating compounds in the electrical engineering field and, preferably, as adhesives and matrix resins for composites, especially for making prepregs for the preparation of fibre-reinforced plastics.
~f desired, especially when concurrently using modifiers, the compositions of this invention can be dissolved in an organic solvent such as ~oluene, xylene, methyl ethyl ketone, methylene chloride, or a solvent or mixture of solvents commonly ernployed in the coating industry. Such solutions are particularly suitable as impregnating or coating compositions~
The curable compositions of this invention can also be blended, prior to the cure, in any phase with conventional modifiers, such as extenders, fillers and reinforcing agents, pigments, dyes, organic solvents, plasticisers, levelling agents, thixotropic agents, flame retardants or mould release agents. Typical examples of extenders, reinforcing agents, fillers and pigments which can be used in the curable compositions of this invention are:
liquid cumene-indene resins, textile fibres, glass fibres, asbestos fibres, boron fibres, carbon fibres, polyethylene powder, polypropylene powder, quartz powcler, mineral silicates such as mica, lasbestos powder, ground shale, kaolin, powdered chalk, antimony trioxide. bentones, lithopones, barite, titanium dioxide, carbon black, oxide pigments such as iron oxide, or metal powders such as aluminium powder or iron powder. If the compositions of the invention are used for making prepregs, it is especially desirable to add ground fibres.
Levelling agents which may be added to the curable compositions, especially for surface protection, are typically silicones, liquid acrylic resins, cellulose acetobutyrate, polyvinylbutyral, waxes, stearates and the like (some of which may also be used as mould release agents).
- 8- ;2Q5~6~;~
Sllitable plasticisers for modifying the curable compositions are typically diblltyl, dioctyl and dinonyl phthalate, tricresyl phosphate, trixylenyl phosphate and diphenoxyethylformal.
The compositions of the invention are preferably cured by heating them to a temperature in the range from 120 to 250C, preferably from 160 to 220C. The cure can also be effected in known manner in two or more steps, the first curing step being carried out at low temperature and the postcure at higher temperature.
If desired, active diluents may be added to the curable compositions to lower the viscosity, Exemplary of such active diluents are neopentyl glycol ether, butanediol ether or hexanediol diglycidyl ether.
The invention further relates to the use of the novel compositions for the preparation of cured articles, as well as for making prepregs for the preparation of fibre-reinforced composites. The prepregs can be made in a manner known per se, typically by the impregnating method in the presence of one of the solvents referred to above, of a halogenated solvent, typically methylene chloride, or in the hot melt process.
The moulded articles obtained in this invention are distinguished in general by high glass transition temperatures while simultaneously having high mechanical strength and, in particular, by excellent flexural strength and very high flexibility.
Only in the following Examples is the amount given in grams instead of parts by wcight.
The following compouncls are used in the Examples as epoxy resins or therrnoplastic resins.
Epoxv resin A: N,N,N',N'-tetraglycidyl derivative of 4,~'-dian~ino-3,3'-diethyldiphenyl-methane with an epoxy value of 7.95 equivalents~g and a viscosity of 9500 mPa s at 25C.
Epoxy resin B: bisphenol A diglycidyl ether with an epoxy value of 7.95 equivalents/kg and a viscosity of lo4-1.2-104 mPa-s at 25C.
Epoxy resin C: bisphenol F diglycidyl ether with an epoxy value of 5.5 to 2~S56~2 5.9 equivalents/kg and a viscosity of 3000~10 000 mPa s at 25C, Epoxy resin D: phenol-novolak epoxy resin with an epoxy value of 5.6 to5.8 equivalents/kg and a melt viscosity of 1 }00-1700 mPa s at 50C.
Polyetherimide 1: Polyetherimide Ultem~ 1000 (General Electric) with a glass transition temperature (Tg) of 219C and containing the sutructural repeating unit of formula O O
r 11 11 ~ N ~ ~ e3 ~C N ~3 Polvimide II In a 4.5 Iitre sulfonating flask equipped with stirrer, thermometer, water separator, condenser and gas inlet pipe, 261.72 g (1.2 mol) of pyromellitic dianhydride are added at 5C over 1 hour in 4 portions to a solution of 247.1 g (0.875 mol) of 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane and 66.86 g (0.375 mol) of 2,4-diethyl-6-methyl-1,3-phenylenediamine in 1.5 Iitres of N-methylpyrrolidone (NMP).
After 2 hours, the ice bath is removed and the reaction solution is stirred overnight at room temperature under nitrogen. To the reaction solution are added 750 ml of xylene and water is removed as an azeotrope under reflux in the water separator. The xylene is then removed from the reaction solution by distillation and the still warm solution is poured, with efficient stirring, into 15 litres of water. The precip;tate is isolated by filtration, mixed a second time with 5 litres of water, isolated by filtration, and dr;ed un~ler vacuum at 1()0C. Yielcl: 526 g (98 % of theory) of a yellow granulate which dissolves in me,thylene chloricle to form a clear solution and has a number average molecular weight (Mn) of 13 300 and a weight average molecular weight (Mw) of 35 380, detelmined by gel permeation chromatography in tetrahydrofuran. The amine value (titration in phenol/chloroforrn with 0.1 N HCIC)~) is 1.19 meq./g. The Tg, measured by differential scanning calorimetry (DSC), is 352C.
Example 1:
a) 30 g of polyetherimide I are dissolved in 50 ml of methylene chloride. To the solution are added 50 g (0.40 equivalent) of epoxy resin A and 50 g (0.30 eq.) of epoxy resin C.
With stirring, the methylene chloride is removed by evaporation at 50C. The mixture is ~:~S~;i69~
heated to 140C and 40 g (0.65 eq.) of 4,4'-diaminodiphenylsulfone (DDS) are addell.
After 10 minutes (min.) the DDS has dissolved. The mixture is evacuated to remove the air bubbles, poured into preheated Anticorodal moulds measuring 80x8ax4 mm and cured for 4 hours (h) at 180C.
The mixture is slightly tacky at room temperature. The cured product has the following properties:
glass transition temperature Tgo (TMA) = 197C
glass transition temperature Tg ~TMA) = 207C
flexural strength (SF) (ISO 178) = 168 MPa flexural elongation (FE) (ISO 178) = 9.0 %-Tgo= onset of glass transition Tg = temperature of maximum penetration speed TMA = thermomechanical analysis; heating up rate = 10C/min~
b) Using 20 g of polyetherimide I and otherwise repeating the procedure of Example 1 a), cured products with the following properties are obtained:
Tgo (TMA) = 182C
Tg (TMA) = 189C
FS = 169 MPa FE =7.0%
c) Using 25 ~g of polyetherimide I and 50 g (().27 eq.) of epoxy resin B in place of 50 g of epoxy resin C und otllerwise repeating the procedure of Example la), cured products with the following properties are obtained:
Tgo (TMA) = 192C
Tg (TMA) = 200C
FS = 162 MPa FE =7.8 %.
Example 2: Preparation of a carbon fibre laminate In accordance with the general procedure of Example la), a resin mixture of 100 g of ~QS56a~2 epoxy resin A, 100 g of epoxy resin D, 84 g of DDS and 50 g of polyetherimide I is prepared. The resin composition is applied with a doctor knife to a xilicone-treated paper on a preheated drum (drum take-up). A carbon fibre ("T-300 6K" sold by Toray) is wound onto the resin, while the resin film is heated locally to c. 120C by IR heating. A 2 mm thick unidirectional laminate is prepared from the prepreg by curing for 4 h al 1 80~C in an autoclave ~pressure S bar).
The laminate has the following properties:
Tgo (TMA~ = 200C
Tg (TMA) = 217C
FS (9Q in fibre direction) = 112 MPa interlaminary shear strength (ISS) (DIN 2g971) at 20C = 100 MPa at 1 20C = 69 MPa at 1 60C = 54 MPa.
After storage for 14 days in water at 71C the following properties are determined:
water absorption = 0.8 %
ISS at 20C = 95 MPa ISS at ] 20C = 54 MPa.
Example 3: Using 30 g of polyimide II, 50 g of epoxy resin A, 50 g of epoxy resin C and 35 g of DDS, and otherwise carrying out the procedure of Example 1, the following properties of the cllred product are determined:
Tgo (TMA) = 1 82C
Tg (TMA) = 1 96C
FS - 156 MPa FE = 7.8%.
Example 4: Using 35 g of a polysulfone obtained from 38.5 mol of the structural repeating unit of formula II, wherein Ar is the radical ~3 C(CH3)2~;~, and from 2.5 mol of the structural repeating unit of formula IV, wherein Ar has the givcn meaning and X is -SO2-, and having a Mn= 8 500 and Mw= 28 500 and an amine value of 0.13meq./g, sn g of epoxy resin A, 50 g of epoxy resin B as well as 40 g of DDS, and ;~5~;~4~
repeating the procedure described in Example 1, the following properties of the cured procluct are determined:
Tgo (TMA) = 198C
Tg (TMA) = 207C
FS = 149 MPa FE = 9.1%.
Sllitable plasticisers for modifying the curable compositions are typically diblltyl, dioctyl and dinonyl phthalate, tricresyl phosphate, trixylenyl phosphate and diphenoxyethylformal.
The compositions of the invention are preferably cured by heating them to a temperature in the range from 120 to 250C, preferably from 160 to 220C. The cure can also be effected in known manner in two or more steps, the first curing step being carried out at low temperature and the postcure at higher temperature.
If desired, active diluents may be added to the curable compositions to lower the viscosity, Exemplary of such active diluents are neopentyl glycol ether, butanediol ether or hexanediol diglycidyl ether.
The invention further relates to the use of the novel compositions for the preparation of cured articles, as well as for making prepregs for the preparation of fibre-reinforced composites. The prepregs can be made in a manner known per se, typically by the impregnating method in the presence of one of the solvents referred to above, of a halogenated solvent, typically methylene chloride, or in the hot melt process.
The moulded articles obtained in this invention are distinguished in general by high glass transition temperatures while simultaneously having high mechanical strength and, in particular, by excellent flexural strength and very high flexibility.
Only in the following Examples is the amount given in grams instead of parts by wcight.
The following compouncls are used in the Examples as epoxy resins or therrnoplastic resins.
Epoxv resin A: N,N,N',N'-tetraglycidyl derivative of 4,~'-dian~ino-3,3'-diethyldiphenyl-methane with an epoxy value of 7.95 equivalents~g and a viscosity of 9500 mPa s at 25C.
Epoxy resin B: bisphenol A diglycidyl ether with an epoxy value of 7.95 equivalents/kg and a viscosity of lo4-1.2-104 mPa-s at 25C.
Epoxy resin C: bisphenol F diglycidyl ether with an epoxy value of 5.5 to 2~S56~2 5.9 equivalents/kg and a viscosity of 3000~10 000 mPa s at 25C, Epoxy resin D: phenol-novolak epoxy resin with an epoxy value of 5.6 to5.8 equivalents/kg and a melt viscosity of 1 }00-1700 mPa s at 50C.
Polyetherimide 1: Polyetherimide Ultem~ 1000 (General Electric) with a glass transition temperature (Tg) of 219C and containing the sutructural repeating unit of formula O O
r 11 11 ~ N ~ ~ e3 ~C N ~3 Polvimide II In a 4.5 Iitre sulfonating flask equipped with stirrer, thermometer, water separator, condenser and gas inlet pipe, 261.72 g (1.2 mol) of pyromellitic dianhydride are added at 5C over 1 hour in 4 portions to a solution of 247.1 g (0.875 mol) of 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane and 66.86 g (0.375 mol) of 2,4-diethyl-6-methyl-1,3-phenylenediamine in 1.5 Iitres of N-methylpyrrolidone (NMP).
After 2 hours, the ice bath is removed and the reaction solution is stirred overnight at room temperature under nitrogen. To the reaction solution are added 750 ml of xylene and water is removed as an azeotrope under reflux in the water separator. The xylene is then removed from the reaction solution by distillation and the still warm solution is poured, with efficient stirring, into 15 litres of water. The precip;tate is isolated by filtration, mixed a second time with 5 litres of water, isolated by filtration, and dr;ed un~ler vacuum at 1()0C. Yielcl: 526 g (98 % of theory) of a yellow granulate which dissolves in me,thylene chloricle to form a clear solution and has a number average molecular weight (Mn) of 13 300 and a weight average molecular weight (Mw) of 35 380, detelmined by gel permeation chromatography in tetrahydrofuran. The amine value (titration in phenol/chloroforrn with 0.1 N HCIC)~) is 1.19 meq./g. The Tg, measured by differential scanning calorimetry (DSC), is 352C.
Example 1:
a) 30 g of polyetherimide I are dissolved in 50 ml of methylene chloride. To the solution are added 50 g (0.40 equivalent) of epoxy resin A and 50 g (0.30 eq.) of epoxy resin C.
With stirring, the methylene chloride is removed by evaporation at 50C. The mixture is ~:~S~;i69~
heated to 140C and 40 g (0.65 eq.) of 4,4'-diaminodiphenylsulfone (DDS) are addell.
After 10 minutes (min.) the DDS has dissolved. The mixture is evacuated to remove the air bubbles, poured into preheated Anticorodal moulds measuring 80x8ax4 mm and cured for 4 hours (h) at 180C.
The mixture is slightly tacky at room temperature. The cured product has the following properties:
glass transition temperature Tgo (TMA) = 197C
glass transition temperature Tg ~TMA) = 207C
flexural strength (SF) (ISO 178) = 168 MPa flexural elongation (FE) (ISO 178) = 9.0 %-Tgo= onset of glass transition Tg = temperature of maximum penetration speed TMA = thermomechanical analysis; heating up rate = 10C/min~
b) Using 20 g of polyetherimide I and otherwise repeating the procedure of Example 1 a), cured products with the following properties are obtained:
Tgo (TMA) = 182C
Tg (TMA) = 189C
FS = 169 MPa FE =7.0%
c) Using 25 ~g of polyetherimide I and 50 g (().27 eq.) of epoxy resin B in place of 50 g of epoxy resin C und otllerwise repeating the procedure of Example la), cured products with the following properties are obtained:
Tgo (TMA) = 192C
Tg (TMA) = 200C
FS = 162 MPa FE =7.8 %.
Example 2: Preparation of a carbon fibre laminate In accordance with the general procedure of Example la), a resin mixture of 100 g of ~QS56a~2 epoxy resin A, 100 g of epoxy resin D, 84 g of DDS and 50 g of polyetherimide I is prepared. The resin composition is applied with a doctor knife to a xilicone-treated paper on a preheated drum (drum take-up). A carbon fibre ("T-300 6K" sold by Toray) is wound onto the resin, while the resin film is heated locally to c. 120C by IR heating. A 2 mm thick unidirectional laminate is prepared from the prepreg by curing for 4 h al 1 80~C in an autoclave ~pressure S bar).
The laminate has the following properties:
Tgo (TMA~ = 200C
Tg (TMA) = 217C
FS (9Q in fibre direction) = 112 MPa interlaminary shear strength (ISS) (DIN 2g971) at 20C = 100 MPa at 1 20C = 69 MPa at 1 60C = 54 MPa.
After storage for 14 days in water at 71C the following properties are determined:
water absorption = 0.8 %
ISS at 20C = 95 MPa ISS at ] 20C = 54 MPa.
Example 3: Using 30 g of polyimide II, 50 g of epoxy resin A, 50 g of epoxy resin C and 35 g of DDS, and otherwise carrying out the procedure of Example 1, the following properties of the cllred product are determined:
Tgo (TMA) = 1 82C
Tg (TMA) = 1 96C
FS - 156 MPa FE = 7.8%.
Example 4: Using 35 g of a polysulfone obtained from 38.5 mol of the structural repeating unit of formula II, wherein Ar is the radical ~3 C(CH3)2~;~, and from 2.5 mol of the structural repeating unit of formula IV, wherein Ar has the givcn meaning and X is -SO2-, and having a Mn= 8 500 and Mw= 28 500 and an amine value of 0.13meq./g, sn g of epoxy resin A, 50 g of epoxy resin B as well as 40 g of DDS, and ;~5~;~4~
repeating the procedure described in Example 1, the following properties of the cured procluct are determined:
Tgo (TMA) = 198C
Tg (TMA) = 207C
FS = 149 MPa FE = 9.1%.
Claims (12)
1. A curable epoxy resin composition comprising (a) 30 to 70 parts by weight of a tetraglycidyl compound of formula (I), wherein R1, R2, R3 and R4 are each independently of one another a hydrogen atom, a halogen atom or C1-C4alkyl, with the proviso that at least one of the substituents R1 to R4 is C1-C4alkyl, (b) 70 to 30 parts by weight of an aromatic glycidyl ether containing on average 2.0 to 3.0 glycidyl ether groups in the molecule, such that the amount of (a) and (b) together is 100 parts by weight, (c) a diaminodiphenylsulfone in an amount such as to supply 0.6 to 1.3 equivalents of amino hydrogen atoms per I epoxide equivalent of the epoxy resin component consisting of (a) and (b), and (d) I to 50 parts by weight, based on 100 parts by weight of (a) and (b), of a thermoplastic resin dissolved therein having a glass transition temperature of at least 150°C.
2. A composition according to claim 1, wherein at least one of the substituents R1 to R4 in the tetraglycidyl compound of formula I is methyl, ethyl or isopropyl.
3. A composition according to claim I, which contains (a) 40 to 60 parts by weight of a tetraglycidyl compound of formula I and (b) 60 to 40 parts by weight of an aromatic glycidyl ether.
4. A composition according to claim I which contains a tetraglycidyl compound offormula I, wherein R1 and R3 are each hydrogen and R2 and R4 are each ethyl.
5. A composition according to claim 1, wherein the aromatic glycidyl ether (b) contains on average 2.0 to 2.2 glycidyl ether groups in the molecule.
6. A composition according to claim 1, wherein the aromatic glycidyl ether (b) is bisphenol A or bisphenyl F diglycidyl ether, the diglycidyl ether of a dihydroxynaphthalene or a mixture of said glycidyl ethers.
7. A composition according to claim 1, wherein the diaminodiphenylsulfone (c) is present in an amount sufficient to provide 0.8 to 1.0 equivalent of amino hydrogen per 1 epoxy equivalent.
8. A composition according to claim 1 which contains 4,4'-diaminodiphenylsulfone as component (c).
9. A composition according to claim 1, wherein the amount of thermoplastic resin (d) is 15 to 30 parts by weight, based on 100 parts by weight of (a) and (b).
10. A composition according to claim 1, wherein the thermoplastic resin (d) is a polyimide or polyetherimide.
11. Cured articles which are obtainable by the curing and molding a composition as claimed in claim 1.
12. Prepregs for the preparation of fibre-reinforced composites which are obtainable by the impregnation of fibres with a composition as claimed in claim 1.
FD 4.32/STA/sf*/ac*
FD 4.32/STA/sf*/ac*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3671/90-3 | 1990-11-19 | ||
| CH367190 | 1990-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2055642A1 true CA2055642A1 (en) | 1992-05-20 |
Family
ID=4261014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2055642 Abandoned CA2055642A1 (en) | 1990-11-19 | 1991-11-15 | Curable epoxy resin composition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0487452A3 (en) |
| JP (1) | JPH04268321A (en) |
| CA (1) | CA2055642A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010042369A1 (en) * | 2008-10-07 | 2010-04-15 | Hexcel Corporation | Epoxy resins and composite materials with improved burn properties |
| US8039109B2 (en) | 2008-10-07 | 2011-10-18 | Hexcel Corporation | Epoxy resins with improved burn properties |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007211254A (en) * | 1997-01-10 | 2007-08-23 | Nippon Kayaku Co Ltd | Epoxy resin composition and method for producing epoxy resin |
| JP5132036B2 (en) * | 2005-03-29 | 2013-01-30 | 日本化薬株式会社 | Liquid epoxy resin, epoxy resin composition and cured product thereof |
| RU2547506C1 (en) * | 2013-10-02 | 2015-04-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет им. Д.И. Менделеева (РХТУ им. Д.И. Менделеева) | Epoxy binding agent for reinforced plastics |
| CN110563927A (en) * | 2019-10-10 | 2019-12-13 | 杭州崇成科技有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108476A1 (en) * | 1982-09-15 | 1984-05-16 | The British Petroleum Company p.l.c. | Epoxy resin composition |
| EP0159482A3 (en) * | 1984-03-28 | 1987-02-25 | American Cyanamid Company | Resin matrix composites with controlled flow and tack |
| JPS61250021A (en) * | 1985-04-30 | 1986-11-07 | Toray Ind Inc | Matrix resin composition for prepreg |
| EP0356392A3 (en) * | 1988-08-24 | 1991-09-18 | Ciba-Geigy Ag | Curable epoxy resin mixture |
| GB9010221D0 (en) * | 1990-05-05 | 1990-06-27 | Ciba Geigy Ag | N-glycidyl compounds |
-
1991
- 1991-11-11 EP EP19910810869 patent/EP0487452A3/en not_active Withdrawn
- 1991-11-15 CA CA 2055642 patent/CA2055642A1/en not_active Abandoned
- 1991-11-19 JP JP33010691A patent/JPH04268321A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010042369A1 (en) * | 2008-10-07 | 2010-04-15 | Hexcel Corporation | Epoxy resins and composite materials with improved burn properties |
| CN102177187A (en) * | 2008-10-07 | 2011-09-07 | 赫克赛尔公司 | Epoxy resins and composite materials with improved burn properties |
| US8034453B2 (en) | 2008-10-07 | 2011-10-11 | Hexcel Corporation | Composite materials with improved burn properties |
| US8039109B2 (en) | 2008-10-07 | 2011-10-18 | Hexcel Corporation | Epoxy resins with improved burn properties |
| CN102177187B (en) * | 2008-10-07 | 2013-05-29 | 赫克赛尔公司 | Epoxy resins and composite materials with improved burn properties |
| RU2494126C2 (en) * | 2008-10-07 | 2013-09-27 | Хексел Корпорейшн | Epoxy resins and composite materials exhibiting improved combustion properties |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0487452A2 (en) | 1992-05-27 |
| EP0487452A3 (en) | 1993-04-28 |
| JPH04268321A (en) | 1992-09-24 |
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