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WO1994004582A1 - Nouveau catalyseur de durcissement de resine epoxy - Google Patents

Nouveau catalyseur de durcissement de resine epoxy Download PDF

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Publication number
WO1994004582A1
WO1994004582A1 PCT/US1993/007721 US9307721W WO9404582A1 WO 1994004582 A1 WO1994004582 A1 WO 1994004582A1 US 9307721 W US9307721 W US 9307721W WO 9404582 A1 WO9404582 A1 WO 9404582A1
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Prior art keywords
epoxy resin
carbon
accelerator
bonded
group
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Inventor
Richard D. Schile
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S/S PERFORMANCE PRODUCTS Inc
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S/S PERFORMANCE PRODUCTS Inc
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    • 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
    • C08G59/68—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 catalysts used
    • C08G59/686—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 catalysts used containing nitrogen
    • 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
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • 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

Definitions

  • An epoxy resin catalyst and accelerator composition containing the reaction product of a secondary amine and an organosulfonoxy compound and an epoxy resin composition containing the same is an epoxy resin catalyst and accelerator composition containing the reaction product of a secondary amine and an organosulfonoxy compound and an epoxy resin composition containing the same.
  • epoxy resins are noncrystalline, and the cured resins find structural applications normally below their heat-distortion or glass-transition temperature. In addition to the modulus or rigidity and strength, an important mechanical property of epoxy resin is toughness, or impact strength.”
  • Organosulfonyl compounds range from relatively neutral materials to strong acids.
  • the organosulfonyl compounds used in the invention are organosulfones. Such sulfones are not usually used as reactants where a reaction proceeds through the sulfone groups. These ma ⁇ terials are typically used as solvents because of their polar nature and their inertness. When they are employed in a reaction, the reaction is effected by other groups that are present in the compounds. Sulfone moieties are known to affect the course of a chemical reaction, oftentimes by acting to withdraw electrons from a functional group at a different site in the molecule and this is known to enhance the occurrence of a nucleophilic reaction between the functional group and another functional reactant.
  • organosulfonic compounds with amines
  • the organosulfonic compound is the acid
  • the amine salt is the usual product if amine hardeners are present.
  • Tanaka and Bauer "Curing Reactions," Epoxy Resins. Chemistry and Technology, Second Edition (Clayton A. May, Ed.), publ. by Marcel Dekker, Inc., New York, N.Y., 1988, page 299, suggest that the salt will retard epoxy cure. If it is the sulfonyl halide, then the sulfonamide is the usual product.
  • the complex is capable of acting as a latent epoxy catalyst.
  • the complex when mixed in an epoxy resin does not cause the epoxy resin to cure at room temperature, but at an elevated temperature the same epoxy formulation will undergo cure.
  • the S0 2 acts as a hydrogen bond acceptor in retarding the curing rate, see Tanaka and Bauer, supra , p.299.
  • latency exits when the epoxy resin containing the adduct has a shelf life of weeks or months (e.g., at least 6 months) and become non-latent when heated to elevated temperatures (e.g., above 50°C.. preferably above 130°C. ) and the cure is expeditious.
  • An apparent deficiency of the catalyst is that upon cure, S0 2 is expected to be released, and one would anticipate at least a portion of it to be released to the atmosphere. This, of course, introduces an environmental problem.
  • Imidazoles are a class of amines that are well recognized amine epoxy resin catalysts. Tanaka and Bauer, supra, page 308, points out that "[C]ertain imidazoles and i idazolines are known to be good curing agents or catalysts.” They state that some complexes of imidazole and i idazoline are efficient and low-exotherm latent curing agents for epoxy resins. Many amines are known hardeners of epoxy resins. In each instance, amines have fostered the polymerization of epoxy resins, even at low temperatures, such as temperatures lower than room temperature. The rate of polymerization in ⁇ creases with increased temperature. However, of the amines, imidazoles are a particular class that works effectively as a catalyst and a hardener, and in the terms of U.S. 3,839,282, it is best characterized as a curing agent.
  • DDS bis(4,4'-diaminodiphenyl)sulfone
  • the BF 3 -complex is a much better accelerator of the epoxy to epoxy reaction and when used in conjunction with DDS, because of the sluggishness of the DDS-epoxy reaction, a substantial portion of the DDS remains unreacted, acting as a plasticizer in the cured product.
  • Imidazoles and especially aIkylated imidazoles are known to provide high temperature epoxies with excellent properties. However, these formulations gel in minutes and do not provide any latency.”
  • Babayan reacts an aromatic sulfonic acid with an imidazole to form a mono-salt structure.
  • This mono-salt can be added to epoxy resins, according to the patentee, to introduce latency.
  • the mono-salt is stable up to 200 °F. (93.3°C.) and can be combined with DDS when curing the epoxy resin.
  • This invention depicts epoxy resin cure systems that rapidly homopolymerize or copolymerize epoxy resins without excessive exotherm, and that can be controlled to produce a thermoset having tensile strengths equal to or greater than the idealized tensile strength, supra .
  • this invention encompasses curing agents that accelerate the curing of epoxy resins to form thermosets that possess higher tensile strength, toughness and/or T g .
  • This invention relates to a novel epoxy resin catalyst and accelerator encompassed by the interreaction of a sulfone composition of the formula:
  • X and Y individually, are organic groups bondied to the nitrogen by a carbon to nitrogen bond, in which said carbon is bonded to oxygen to form a carbonyl moiety or is saturated;
  • X and Y individually, may be alkyl of 1 to about 14 carbon atoms, monocyclic aryl, monocyclic alkaryl in which the alkyl contains 1 to about 12 carbon atoms, monocyclic aralkyl in which the alkyl contains 1 to about 12 carbon atoms, cycloalkyl of about 5 to about 8 carbon atoms, or they may be joined to form a heterocyclic ring containing the secondary amino group as a ring member;
  • preferred secondary amines are heterocyclic amines containing a secondary amino group are compounds such as (1) an imidazole or imidazoline encompassed by the formulae:
  • (b) has a value of at least 1; n has a value of 0 or equal to or greater than (">") 1; the ratio of m to n, when n is >1, is from about 0.01 to 100, provided there is one unit B per molecule; p has a value of at least one; g has a value of 0 or >1; r has a value of 1 to about 4; o has a value of 0 or 1; g has a value of 0 or >1; R 1 and R 4 are (i) hydroxyl bonded to an aromatic carbon of an aromatic ring in units A and B or (ii) a monovalent hydroxyl substituted aliphatic organic group bonded through oxygen to an aromatic carbon of an aromatic ring in units A and B; R 2 is an ether oxygen group, a carboxylic acid ester group, a sulfone group, a divalent aliphatic hydrocarbon group, a substituted divalent aliphatic hydrocarbon group wherein the substituent is hydroxy
  • R 5 and R 6 are hydrogen and an organo group bonded to the ring carbon by a carbon to carbon bond or an oxygen to carbon bond;
  • R 3 is a carboxylic acid ester, a carbonate, a carbamate, an amide, an ether oxygen, the divalent unit of formula V.) above bonded to one of oxygen or an nitrogen to form an amide unit with the nitrogen, a divalent aliphatic hydrocarbon group, a substituted divalent aliphatic hydrocarbon group wherein the substituent is hydroxyl, alkoxy, aroxy, alkaroxy, aralkoxy, and the like; a dioxy terminally- substituted divalent aliphatic hydrocarbon group, a substituted dioxy terminally-substituted divalent aliphatic hydrocarbon group wherein the substituent is carbon-bonded hydroxyl, alkoxy, aroxy, alkaroxy, aralkoxy, and the like; R a -h are each hydrogen, alkyl, aryl and, where bonded to adjacent carbons
  • R a -h ma Y may be joined to form an aromatic fused ring group; one or more, preferably one, of R a -h ma Y be substituted by an azolyl such as an imidazolyl or an azolinyl such as imidazolinyl.
  • R a - R* 1 are individually hydrogen or an organo group bonded to the carbon of the heterocyclic ring by a carbon to carbon bond.
  • Particularly desirable organo groups are alkyl, alkoxyalkyl, aryl, alkaryl, aralkyl, cycloalkyl, and the like. Generally, the organo groups contain not greater than about 10 carbon atoms.
  • a special embodiment of the invention includes a Br ⁇ nsted or Lewis acid cationic catalyst as part of the catalyst composition of the invention.
  • the Br ⁇ nsted or Lewis acid cationic catalysts are especially preferred components of the catalyst system when the epoxy formulation that is being cured uses primary and/or secondary amines as hardeners.
  • the invention relates to the selective cure of epoxy resins by the copolymerization of a polyfunctional epoxy resin with a poly-p-amine, preferably one in which primary amino groups are bonded to carbon atoms of an aromatic ring.
  • a poly-p-amine preferably one in which primary amino groups are bonded to carbon atoms of an aromatic ring.
  • the amino groups are converted to secondary amines.
  • These are not the secondary amines that form part of the catalyst structure, but the secondary amines resulting from the reaction of the primary amino groups of polyamines with epoxy groups.
  • the secondary amine hydrogens that are formed from the reaction of the primary amino groups with the epoxy groups are retarded from entering into the crosslinking reaction. This results in cured epoxy resins that have superior tensile strengths, ductility, elongation, and the like.
  • thermoset polymer Sacrificed by this reaction is the T g of the thermoset polymer.
  • an interesting aspect of the melting characteristics of these thermoset polymers is that many of them have bimodal T g s, i.e., two glass transition temperatures.
  • the invention allows for the control of the crosslinking reaction of the formed secondary amines so that one can select a combination of properties for the thermoset epoxy resins.
  • the sulfone molecule of formula I.) may be a monomer, dimer, oligomer or higher polymer and the secondary amine of formula II.) may be one or more s_- amines.
  • the proportion of secondary amine to the sulfone is minimally at least one secondary amine or mixture of secondary amines (averaging the equivalent of a molecule) for each sulfone group in the sulfone molecule of formula I.).
  • every sulfone molecule contains two secondary amines complexed with it.
  • the novel epoxy resin catalyst of the invention is suitable for curing any of the available epoxy resins to produce cured products having one or more physical properties, such as tensile strength, flexural strength, flexural modulus, tensile modulus, elongation, lap shear strength, peel strength, and the like, that is superior or equivalent to that which is produced using any other epoxy resin catalyst otherwise comparably formulated.
  • the catalysts of the invention effect exceptionally rapid cure without damaging exothermic reaction and effect minimal to no shrinkage in the cured epoxy resin. The cure occurs quite rapidly, typically at least two times faster than other epoxy resin catalysts. This allows for rapid production of molded parts and substantial energy savings.
  • the invention also contemplates epoxy resin compositions in which the catalyst/accelerator of the invention achieves latent cure. Such latency is achieved when the epoxy resin is homopolymerized, or when copolymerized with a hardener that is free of primary amino groups, preferably free of amino groups.
  • the invention also includes an epoxy resin composition containing the catalyst of the invention.
  • the invention relates to an improvement in epoxy resin catalyst and accelerator that yields unexpectedly superior performance in handling, mechanical properties, chemical properties, and the like.
  • the resulting epoxy resins containing the epoxy resin catalyst and accelerator may be used for any of the applications in which epoxy resins are currently employed, such as, adhesives, matrix resins for composites of all sorts (reinforced by carbon fiber, glass fiber, aramide fibers, fabrics of them, fillers, and the like), prepregs, decorative or primer coatings, adhesive or adhesive primers, structural adhesives and adhesive bonding primers, and the like.
  • An optimal formulation of an epoxy resin attempts to take into account, for the ultimately cured resin, thermal and strength properties in general. Needless to say, there are many more specific properties that are evaluated, and a number of them are niche properties for a particular application.
  • Curing of an epoxy resin involves the transformation of the thermoplastic uncured epoxy resin to the three-dimensional cured thermoset state.
  • the function of an epoxy cure catalyst or curing agent is to facilitate the resin's cure and maximize the extent of the resin's cure, i.e., effect reaction-of all of the epoxy groups and as much, for desired specific properties, of the other functional groups that are present in the formulation, thereby transforming the relatively low molecular weight epoxy resin into a highly crosslinked network.
  • Facilitating the cure means effecting the cure in the shortest possible time without exothermic reaction occurring that causes the resin to blister or to undergo excessive shrinking.
  • Thermal properties take into consideration the glass transition temperature (T g ) of the cured resin. That property is dependent upon the crosslinked density per unit of reactive epoxy, of the cured resin. The higher the crosslinked density coupled with amenable structural characteristics of the resin, the higher will be the resin's T g .
  • T g glass transition temperature
  • a high T g means that the resin can be used in applications where the product is put to high use temperatures.
  • the very nature of high crosslinked density suggests the resin will tend to be brittle, which means the resin will probably be deficient in tensile strength and elongation.
  • High ductility in an epoxy resin depends on a resin that is not overly crosslinked because the properties sought, e.g., unrecoverable deformation., plastic flow, i.e., elasticity, pliability, flexibility, etc., is the opposite of brittleness which is a product of high crosslinkage.
  • Tensile strength is the resistance of the cured epoxy resin to a force tending to tear it apart.
  • a truly ductile resin will exhibit a high tensile strength. This invention provides enormous variations in such properties essentially through the selection of the catalyst/accelerator of the invention in conjunction with the selection of the epoxy resin and/or hardeners.
  • R* and R' are alkyl containing 1 to about 8 carbon atoms, aryl of up to 2 rings, and cycloalkyl of about 5 to about 8 carbon atoms. Each of ' these may be subtituted.
  • the alkyl may be substituted by aryl and cycloalkyl, as defined above; the aryl substituted by alkyl and cycloalkyl, as defined above, and the cycloalkyl substituted by alkyl and aryl, as defined above.
  • the alkyl contain at least 3 carbon atoms .
  • Illustrative of such amines are the following:
  • Suitable azoles and azolines of formula II are the following compounds:
  • the piperazines are somewhat different from the azoles and azolines in that they more spontaneously react with the epoxy resin. In the typical case, they will be used as an adjunct with other secondary amines, though they may be used in the catalyst formulation to enhance reactivity and impart toughness to the epoxy formulation. For example, they may be used to assist in raising the viscosity of a pre ix or to A-stage or B- stage an epoxy resin.
  • Suitable piperazines include the following:
  • pyrrole pyrrole
  • triazole pyrrole
  • piperidine which while not active to the extent of the imidazoles, can be used to modify the catalyst activity, control cure rate, control pot life or alter solubility.
  • the catalyst formulation of the invention, and the epoxy resin formulation of the invention may also contain acids, such as Br ⁇ nsted and Lewis acids.
  • Suitable acids include the acid halides, nitrates, sulfates, carboxylates, and the like, of metals such as Fe, Ni, Cu, Zn, Al, Ga, B, Sn, and the like.
  • suitable as a conjointly added component of the catalyst composition of the invention are the carboxylic acids and the organosulfonic acids.
  • Preferred acid salts are zinc chloride, boron trifluoride-etherate or amine salt, tin chloride, and the like. These additives are useful when using an amine hardener in the epoxy resin formulation. Absent the use of such hardeners, it is more desirable to practice the invention without the use of such acid additives.
  • the acids are typically used, when employed, in the range of about 0.01 to about 5 weight percent of the weight of the resin formulation.
  • the reaction of the secondary amine and the organic sulfone of formula 1. may be carried out at any temperature above the melting point of either -of the reactants. In some instances, it will be desirable to dissolve each of the reactants in a separate solvent. One or more solvents are suitable so long as the mixture is homogeneous
  • Suitable epoxy resin in which the catalysts of the invention may be employed include the following:
  • the epoxidized ester of the polyethylenically un- saturated monocarboxylic acids such as epoxidized linseed, soybean, perilla, oiticica, tung, walnut and - dehydrated castor oil, methyl linoleate, butyl linoleate, ethyl 1,12-octadecadienoate, butyl 9, 12, 15 - octadecatrienoate, butyl oleostearate, monoglycerides of tung oil fatty acids, monoglycerides of soybean, sunflower, rapeseed, he pseed, sardine, or cottonseed oil. and the like. 2.
  • the epoxidized esters of unsaturated monohydric alcohols and polycarboxylic acids such as, for example, di (2, 3 - epoxybutyl) adipate, di (2, 3 - - epoxybutyl) oxalate, di (2, 3 - epoxyhexyl) succinate, di (3, 4 - epoxybutyl) maleate, di (2, 3 - epoxyoctyl) pimelate, di (2, 3 - epoxybutyl) phthalate, di (2, 3 - epoxyoctyl) tetrahydrophthalate, di (4, 5 epoxydodecyl) maleate, di (2, 3 - epoxybutyl) terephthalate, di (2, 3 -epoxypentyl) thiodipropionate, di (5, 6 - epoxytetradecyl) diphenyldicaboxylate, di (3, 4 - epoxyheptyl) sulfonyl dibutyrate, tri (2, 3
  • Epoxidized esters of unsaturated alcohols and un- saturated carboxylic acids such as 2, 3 - epoxybutyl 3,
  • Epoxidized derivatives of polyethylenically unsat ⁇ urated polycarboxylic acids such as, for example dimethyl 8, 9, 12, 13 - diepoxyeicosanedioate, dibutyl 7, 8, 11, 12 - diepoxyoctadecanedioate, dioctyl 10, 11 - diethyl - 8, 9, 12, 13 - diepoxy-eicosanedioate, dihexyl 6, 7, 10, 11 - diepoxyhexadecanedioate, didecyl 9 - epoxy - ethyl 10, 11 - epoxyoctadecanedioate, dibutyl 3 - butyl 3.
  • Epoxidized polyesters obtained by reacting an unsaturated polyhydric alcohol and/or unsaturated polycarboxylic acid or anhydride groups such as for example, the polyester obtained by reacting 8, 9, 12, 13
  • Epoxidized polyethylenically unsaturated hydro ⁇ carbons such as epoxidized 2, 2 - bis (2 - cyclohexe- nyl) propane, epoxidized vinyl cyclohexene and epoxidized dimer of cyclopentadiene.
  • Epoxidized polymers and copolymers of diolefins such as butadiene.
  • diolefins such as butadiene.
  • examples of this include, among others, butadiene-acrylonitrile copolymers (nitrile rubbers) , butadiene-styrene copolymers and the like.
  • Glycidyl-containing nitrogen compounds such as diglycidyl aniline and di- and triglycidylamine.
  • Particularly useful epoxy resins for utilizing the curing agents of the invention are the glycidyl ethers and particularly the glycidyl ethers of polyhydric phenols and polyhydric alcohols.
  • the glydicyl ethers of polyhydric phenols are obtained by reacting epiehlorohydrin with the desired polyhydric phenols in the presence of alkali. Reaction products of epiehlorohydrin with 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] and bis(4-hydroxyphenyl)propane are good examples of polyepoxides of this type.
  • polyglycidyl ether of 1, 1, 2, 2-tetrakis (4- hydroxyphenyl) ethane epoxy value of 0.45 eq./lOO g. and melting point 85°C
  • polyglycidyl ether of 1, 1, 5, 5-tetrakis(hydroxyphenyl)pentane epoxy value of 0.514 eq./lOO g.
  • glycidated novolacs as ob ⁇ tained by reacting epiehlorohydrin with phenolic novolac resins obtained by condensation of formaldehyde with a molar excess of phenol or cresol.
  • Illustrative of preferred epoxy resin are those listed below. They may be used alone, as the sole epoxy resin component, or they can be mixed with another epoxy resin.
  • the epoxy resins containing aromatic and cycloaliphatic groups contribute to higher TgS, tensile strengths, toughness, and the like properties.
  • the epoxy catalyst and accelerator of the invention may be provided in an epoxy resin formulation in amounts that range quite broadly dependent upon the performance that is sought for the ultimate cured resin.
  • the amount may be as little as 0.01 to as much as 20 weight percent based on the weight of the resin formulation.
  • the amount of the catalyst/accelerator ranges from about 0.05 to about 15 weight percent based on the weight of the resin formulation.
  • the amount of the catalyst should be from about 0.1 to about 10 weight percent based on the weight of the resin formulation.
  • the epoxy resin formulation may comprise one or more epoxy resins per se and the catalyst/accelerator of the invention. It may also contain hardeners and other ingredients.
  • the catalyst/accelerators of the invention are particular good homopolymerization catalysts because the homopolymer can have especially good cured resin properties.
  • Homopolymerization means the reaction of only epoxy resin in the presence of the catalyst/accelerator of the invention even though the hydroxy substituted sulfones are believed to react with the epoxy resins.
  • Homopolymers may be made of one or more epoxy resins.
  • Copolymers means the reaction of one or more epoxy resins with one or more non-epoxy functional compounds, preferably polyfunctional compounds. Such polyfunctional compounds are typically called hardeners for the epoxy resin(s)
  • the copolymeric components cover a vast array of polyfunctional materials, ranging from polyhydroxy compounds, polyamines, polysulfides, polyamides, polyurethanes, polycarboxylic acids, polyanhydrides, and the like.
  • the copolymeric components may contain mixed functional groups.
  • the polyfunctional polyhydroxy compounds suitable for use in the practice of the invention include polyols and hydroxy-substituted aromatic compounds.
  • the polyols include hydroxy-substituted alkanes, alkylethers, alkylamines (viz., trialkanolamines) , alkylsulfides, alkyl esters, as well as polymers such as polyvinylalcohols, copolymers of vinylacetate and vinylalcohol, poly-2-hydroxyethylmethacrylate, copolymers of 2-hydroxyethylmethacrylate and styrene, and the like.
  • the aromatic hydroxy compounds include the following:
  • the epoxy resins compositions of the invention may be used to impregnate continuous filament ribbons of fibers such as carbon, aramid, glass, nylon, polyester, polypropylene, and the like, fibers, to make prepregs and composite structures.
  • the invention in epoxy resin composition may contain fillers, staple fibers, hollow microspheres, colorants, and other standard ingredients for epoxy resins.
  • the epoxy resin composition of the invention may contain other thermosetting resins, such as phenolic resins, melamine- formaldehyde resins, and urea-formaldehyde resins, as well as thermoplastic resins, such as polyamides, polyurethanes, and the like.
  • DAP 2,6-diaminopyridine
  • phenyl sulfones in the correct proportions form eutectic mixtures (and possible complexes) which are low melting, highly soluble epoxy hardeners and which produce cured epoxies having good physical and mechanical properties such as high tensile strength, high T g high toughness and low cure shrinkage.
  • Suitable partners for DAP have been found to be DHDS (di-4- hydroxydiphenylsulfone) , DDS (4,4-diamino- diphenylsulfone) , DHDS-Isophthalate and DHDS-Epoxy adducts. Procedures for the preparation of these complexes follow exactly the corresponding procedures for the preparation of the analogous Imidazole-Sulfone complexes.
  • the desired proportions are typically two molecules of DAP per sulfone group.
  • DGEBA diglycidyl bisphenol A resin
  • the appropriate hardener should be mixed with the epoxy resin in the proportion of one active hydrogen per epoxide, ignoring any contribution from the accelerator and for optimizing rapid curing and optimum physical properties, one of the Imidazole-Sulfone accelerators should be used in a typical concentration in of about 2.5 - 5.0 phr. It should be appreciated that different formulations based on the choice of epoxide, hardener and accelerator will yield different results in terms of the Tg, tensile strength and toughness obtained.
  • the solvent facilitates the generation of the resinous or crystalline complex and is desirable for shortening the preparation time. Preparation in the melt, though possible, is not favored because the rate of solution of DHDS in the mixture becomes very low near the end of its addition.
  • a catalytic amount in the range of about 0.05 to about 10 parts per weight of the catalyst per 100 parts by weight of the epoxy resin, of this material [such as 3-10 phr (parts per hundred of resin) ] is dissolved in DGEBA and the mixture heated, it turns red at approximately 125°C. and solidifies in about ten seconds without the formation of a gel.
  • DHDS-Isophthalate was prepared by adding 10.0 g. DHDS and 25 ml. MEK to a three-neck flask equipped with condenser and stir bar. Four grams of isophthaloyl chloride were dissolved in 15 ml. MEK and the solution placed in a small dropping funnel. The flask was flushed with dry N 2 and the DHDS-MEK mixture brought to reflux. The isophthaloyl chloride solution was then added dropwise to the flask with stirring, the addition being completed in about thirty minutes. The solution was then cooled to room temperature, poured into a beaker and 4.0 g. powdered, anhydrous sodium carbonate was added.
  • This material was designed as a combination epoxy resin catalytic hardener/modifier intended to reduce the crosslink density in and improve toughness of the cured epoxy.
  • DHDS (10.0 g.) and 25 ml. MEK were placed in a three-neck flask equipped with a condenser and stir bar. Cresylglycidylether (14.6 g.) diluted with 15 ml. MEK was placed in a small dropping funnel. The DHDS-MEK mixture was brought to reflux and the dilute cresylglycidylether was added dropwise over a thirty minute period. When this addition had been completed, 5.44 g. of Im was added to the mixture and the flask set up for distillation. When the MEK had been distilled off, a resinous product was obtained which was a pale amber, semi-solid at room temperature.
  • This material had a low viscosity at approximately 100°C, was very soluble in warm DGEBA and, when mixed with the epoxy resin at a concentration of 5 - 10 phr, resulted in rapid hardening at 130 - 135°C.
  • the catalyst materials of Examples 1, 2 and 3 are very effective catalytic hardeners for epoxy resins which cure very rapidly with very low exotherm. When used as homopolymerization catalylsts, these materials give very high crosslink densities and produce brittle products. Catalyst materials of Examples 1 and 2 are also very effective accelerators for mixtures of epoxies and amines or polyphenols. Cure times can be dramatically reduced by the use of these materials without producing excessive exotherm.
  • the catalyst of Example 3 is an extremely effective accelerator for epoxy-anhydride systems having all of the above cited advantages. With respect to the catalyst composition of Example 1, it was noted in the limited reactions tested that its concentration in DGEBA should be at least about 2.0 phr for rapid gelation. Excellent results have been obtained by using these accelerators at concentrations of 2.5 - 3.0 phr in combination with amines or polyphenols or, in the case of material Example 3, with anhydrides.
  • Im 2 -DHDS refers to the 2:1 molar ratio complex of Imidazole and dihydroxy diphenyl sulfone (sulfonyl diphenol) .
  • EMI2-DHDS refers to the similar complex formed from 2-ethyl,4-methyl Imidazole.
  • XU-205 is a CIBA-Geigy® product referred to in
  • DHDS/epoxy adduct refers to the material formed by the slow addition of a solution of cresylglycidylether to a solution of DHDS. This is presumed to result in

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

Catalyseur et accélérateur de résine époxy obtenu par interréaction d'une composition de sulfone aromatique hydroxylée avec une amine secondaire. La composition de résine époxy obtenue contenant le catalyseur/accélérateur peut s'utiliser dans des applications, telles que des adhésifs, des matrices de résines pour différents composites, des préimprégnés et des revêtements.
PCT/US1993/007721 1992-08-21 1993-08-16 Nouveau catalyseur de durcissement de resine epoxy Ceased WO1994004582A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US93345192A 1992-08-21 1992-08-21
US07/933,451 1992-08-21

Publications (1)

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WO1994004582A1 true WO1994004582A1 (fr) 1994-03-03

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PCT/US1993/007721 Ceased WO1994004582A1 (fr) 1992-08-21 1993-08-16 Nouveau catalyseur de durcissement de resine epoxy

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5972422A (en) * 1998-05-01 1999-10-26 Basf Corporation Method for low bake repair of composite color-plus-clear coatings, and compositions for use therein
US6045872A (en) * 1998-05-01 2000-04-04 Basf Corporation Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein
WO2019099347A1 (fr) 2017-11-20 2019-05-23 Carbon, Inc. Résines de siloxane photodurcissables pour fabrication additive
CN110498905A (zh) * 2018-05-17 2019-11-26 赢创德固赛有限公司 快速固化型环氧体系
WO2025137013A1 (fr) 2023-12-19 2025-06-26 Carbon, Inc. Compositions de résine de silicone et leurs procédés d'utilisation

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US3839282A (en) * 1972-06-14 1974-10-01 Minnesota Mining & Mfg Products from an imidazole and sulfur dioxide, compositions containing them, and methods of preparation
US4189548A (en) * 1977-09-13 1980-02-19 Mitsui Petrochemical Industries, Ltd. Epoxy resin composition
US4331582A (en) * 1980-01-14 1982-05-25 Hitco Epoxy latent catalyst
US4390664A (en) * 1981-02-27 1983-06-28 Mitsubishi Petrochemical Co., Ltd. Process for preparing a polyepoxide and composition therefrom
US4499246A (en) * 1983-02-11 1985-02-12 Societe Anonyme Dite "Manufacture De Produits Chimiques Protex" Epoxy resins containing as a latent catalyst/accelerator halogenobisphenates of tertiary amines
US4661559A (en) * 1983-05-20 1987-04-28 Union Carbide Corporation Impact resistant matrix resins for advanced composites
US4892134A (en) * 1984-02-22 1990-01-09 Swiss Aluminium Ltd. Electromagnetic mold for continuous castings

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839282A (en) * 1972-06-14 1974-10-01 Minnesota Mining & Mfg Products from an imidazole and sulfur dioxide, compositions containing them, and methods of preparation
US4189548A (en) * 1977-09-13 1980-02-19 Mitsui Petrochemical Industries, Ltd. Epoxy resin composition
US4331582A (en) * 1980-01-14 1982-05-25 Hitco Epoxy latent catalyst
US4390664A (en) * 1981-02-27 1983-06-28 Mitsubishi Petrochemical Co., Ltd. Process for preparing a polyepoxide and composition therefrom
US4499246A (en) * 1983-02-11 1985-02-12 Societe Anonyme Dite "Manufacture De Produits Chimiques Protex" Epoxy resins containing as a latent catalyst/accelerator halogenobisphenates of tertiary amines
US4661559A (en) * 1983-05-20 1987-04-28 Union Carbide Corporation Impact resistant matrix resins for advanced composites
US4892134A (en) * 1984-02-22 1990-01-09 Swiss Aluminium Ltd. Electromagnetic mold for continuous castings

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5972422A (en) * 1998-05-01 1999-10-26 Basf Corporation Method for low bake repair of composite color-plus-clear coatings, and compositions for use therein
US6045872A (en) * 1998-05-01 2000-04-04 Basf Corporation Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein
WO2019099347A1 (fr) 2017-11-20 2019-05-23 Carbon, Inc. Résines de siloxane photodurcissables pour fabrication additive
US11535714B2 (en) 2017-11-20 2022-12-27 Carbon, Inc. Light-curable siloxane resins for additive manufacturing
CN110498905A (zh) * 2018-05-17 2019-11-26 赢创德固赛有限公司 快速固化型环氧体系
WO2025137013A1 (fr) 2023-12-19 2025-06-26 Carbon, Inc. Compositions de résine de silicone et leurs procédés d'utilisation

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