WO2012015467A1 - Curable compositions - Google Patents
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- WO2012015467A1 WO2012015467A1 PCT/US2011/001281 US2011001281W WO2012015467A1 WO 2012015467 A1 WO2012015467 A1 WO 2012015467A1 US 2011001281 W US2011001281 W US 2011001281W WO 2012015467 A1 WO2012015467 A1 WO 2012015467A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
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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
- C08G59/40—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 curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2631—Coating or impregnation provides heat or fire protection
- Y10T442/2672—Phosphorus containing
- Y10T442/268—Phosphorus and nitrogen containing compound
Definitions
- Embodiments of the present disclosure are directed toward curable compositions; more specifically, embodiments are directed toward curable compositions including a phosphono-methyl-glycine.
- Epoxy systems may consist of two components that can chemically react with each other to form a cured epoxy, which is a hard, inert material.
- the first component can be an epoxy compound and the second component can be a curing agent, sometimes called a hardener.
- Epoxy compounds contain epoxide groups.
- the hardener includes compounds which are reactive to the epoxide groups of the epoxy compounds.
- the epoxy compounds can be crosslinked, also referred to as curing, by the chemical reaction of the epoxide groups and the compounds of the hardener. This curing converts the epoxy compounds into crosslinked materials by chemical reaction with the hardener.
- Epoxy systems can be used to make composite materials.
- Composite materials are materials that are made from two or more components that have distinct mechanical properties.
- a composite material may be formed of multiple layers of a reinforcing fiber having an epoxy compound that is employed as a matrix material. Each layer that makes up the composite material can be impregnated with the epoxy compound. These layers may be referred to as prepregs.
- the prepregs can then be cured by application of heat and/or pressure to form the composite material. The heat and/or pressure cause the epoxy compound to penetrate and join all layers of the prepreg together as the epoxy compound cures.
- the composite material may have flame retardation properties.
- Fire is a gas-phase reaction.
- Portions of composite materials can transition to the gas-phase by decomposition via exposure to heat. Ignition of the gas-phase can occur either spontaneously or result from an external source such as a spark or flame.
- ignition of the gas-phase if the heat evolved by the burning is sufficient to keep the decomposition rate of the composite material above that required to maintain the evolved gas-phase components within a flammability limit, then a self-sustaining combustion cycle will be established.
- composite materials have included either flame retardants that help provide a protective layer, e.g. a char, on the
- One or more embodiments of the present disclosure include a curable composition including an epoxy compound selected from the group consisting of
- aromatic epoxy compounds alicyclic epoxy compounds, aliphatic epoxy compounds, and combinations thereof; a curing agent selected from the group consisting of
- novolacs novolacs, amines, anhydrides, carboxylic acids, phenols, thiols, and combinations
- One or more embodiments of the present disclosure include a prepreg obtainable by impregnating a matrix component into a reinforcement component,
- matrix component is the curable composition as disclosed herein.
- One or more embodiments of the present disclosure include a product obtained by curing one or more of the prepregs as disclosed herein.
- Embodiments of the present disclosure provide curable compositions.
- the curable compositions can include a phosphono-methyl-glycine, an epoxy compound, and a curing agent.
- Phosphono-methyl-glycines such as glyphosate
- Glyphosate salts have been sold as an herbicide under the tradename ROUNDUP®.
- glyphosate has been used to generate phosphorous acid functional acrylic copolymers having internal pendant phosphorus acid groups that are useful as an adhesive.
- phosphono-methyl-glycines may be included in the curable compositions of the present disclosure and that products obtained by curing the curable compositions have both desirable flammability properties, such as particular flame classifications, and desirable technical properties, such as glass transition temperatures.
- Phosphono-methyl-glycines may be represented by the following
- each R is independently a hydrogen atom, an alkyl group, an aryl group, a glycidyl group, a 2-hydroxymethyl group, a 2-hydroxyethyl group, or an R'C ) group.
- alkyl groups having the formula -C n H 2n+ i > can be derived from an alkane by removal of a hydrogen atom from a carbon atom.
- Alkyl groups can include cycloalkyl groups that have the formula C n H 2n-1 .
- Cycloalkyl groups can be derived from cycloalkanes by removal of a hydrogen atom from a ring carbon atom.
- the aryl groups can be derived from arenes by removal of a hydrogen atom from a ring carbon atom.
- Arenes, including heteroarenes, are monocyclic or polycyclic aromatic hydrocarbons.
- the glycidyl groups can include methylene oxiranes, for example, that can be derived by displacement chemistry of glycidyl halides such as epichlorohydrin.
- the 2-hydroxyethyl groups can include HOCH 2 CH 2 - radicals,
- HOCH 2 CH(CH 3 )- radicals HOCH(CH 3 )CH 2 - radicals, or combinations thereof, for example, that can be derived from epoxy ring-opening reactions of ethylene oxide or propylene oxide.
- a specific phosphono-methyl-glycine, where each R is independently hydrogen, is glyphosate.
- Glyphosate may be represented by the following Formula II:
- the phosphono-methyl-glycines include salts thereof, e.g. salts of
- the phosphono-methyl-glycine can include a salt of Formula I that is a combination of a cation with an mono- or dianionic form of Formula I.
- such salts include, but are not limited to, alkyl ammonium salts such as ammonium, diammonium, isopropylammonium, trimethylsulfonium, phosphonium, potassium, sodium, magnesium, aluminum, and " combinations thereof.
- the most preferred salts are the isopropylammonium and the trimethyl sulfonium salts.
- the phosphono-methyl-glycines include anhydrides thereof that are obtainable by water removal, e.g.
- the phosphono-methyl-glycine can be from 0.5 weight percent to 50 weight percent of the curable composition; for example the phosphono-methyl-glycine can be from 1 weight percent to 40 weight percent or from 2 weight percent to 30 weight percent of the curable composition.
- the curable compositions include an epoxy compound.
- a compound is a substance composed of atoms or ions of two or more elements in chemical combination and an epoxy compound is a compound in which an oxygen atom is directly attached to two adjacent or non-adjacent carbon atoms of a carbon chain or ring system.
- the epoxy compound can be from 10 weight percent to 90 weight percent of the curable composition; for example the epoxy compound can be from 20 weight percent to 80 weight percent or from 30 weight percent to 70 weight percent of the curable composition.
- the epoxy compound can be selected from the group consisting of aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and combinations thereof.
- the curable compositions include an aromatic epoxy compound.
- aromatic epoxy compounds include, but are not limited to, glycidyl ether compounds of polyphenols, such as hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, phenol novolac, cresol novolac, trisphenol (tris-(4-hydroxyphenyl)methane), l,l,2,2-tetra(4- hydroxyphenyl)ethane, tetrabromobisphenol A, 2,2-bis(4-hydroxyphenyl)-l, 1,1,3,3,3- hexafluoropropane, 1 ,6-dihydroxynaphthalene, and combinations thereof.
- the curable compositions include an alicyclic epoxy compound.
- alicyclic epoxy compounds include, but are not limited to, polyglycidyl ethers of polyols having at least one alicyclic ring, or compounds including cyclohexene oxide or cyclopentene oxide obtained by epoxidizing compounds including a cyclohexene ring or cyclopentene ring with an oxidizer.
- Some particular examples include, but are not limited to, hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate; 3,4-epoxy-l-methylcyclohexyl-3,4-epoxy-l -methylhexane carb xylate; 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate; 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate; 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxylate; bis(3,4-epoxycyclohexylmethyl)adipate; methylene-bis(3,4-epoxycyclohexane); 2,2- bis(3,4-epoxycyclohexy
- the curable compositions include an aliphatic epoxy compound.
- aliphatic epoxy compounds include, but are not limited to, polyglycidyl ethers of aliphatic polyols or alkylene-oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl-polymerizing glycidyl acrylate or glycidyl methacrylate, and copolymers synthesized by vinyl-polymerizing glycidyl acrylate or glycidyl methacrylate and other vinyl monomers.
- Some particular examples include, but are not limited to glycidyl ethers of polyols, such as 1 ,4-butanediol diglycidyl ether; 1 ,6- hexanediol diglycidyl ether; a triglycidyl ether of glycerin; a triglycidyl ether of trimethylol propane; a tetraglycidyl ether of sorbitol; a hexaglycidyl ether of dipentaerythritol; a diglycidyl ether of polyethylene glycol; and a diglycidyl ether of polypropylene glycol; polyglycidyl ethers of polyether polyols obtained by adding one type, or two or more types, of alkylene oxide to aliphatic polyols such as propylene glycol, trimethylol propane, and glycerin; diglycidyl esters of ali
- the curable compositions include a curing agent.
- the curing agent can be selected from the group consisting of novolacs, amines, anhydrides, carboxylic acids, phenols, thiols, and combinations thereof.
- the curing agent can be from 1 weight percent to 50 weight percent of the curable composition; for example the curing agent can be from 5 weight percent to 45 weight percent or from 10 weight percent to 40 weight percent of the curable composition.
- the curing agent can include a novolac.
- novolacs include phenol novolacs. Phenols can be reacted in excess, with formaldehyde in the presence of an acidic catalyst to produce phenol novolacs.
- the curing agent can include an amine.
- Amines include compounds that contain an N-H moiety, e.g. primary amines and secondary amines.
- the amine can be selected from the group consisting of aliphatic polyamines, arylaliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, heterocyclic polyamines, polyalkoxy polyamines, dicyandiamide and derivatives thereof, aminoamides, amidines, ketimines, and combinations thereof.
- aliphatic polyamines include, but are not limited to, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), trimethyl hexane diamine (TMDA), hexamethylenediamine (HMD A), N-(2- aminoethyl)-l,3-propanediamine (N3-Amine), N,N'-l,2-ethanediylbis-l,3- propanediamine (N4-amine), dipropylenetriamine, and reaction products of an excess of these amines with an epoxy resin, such as bisphenol A diglycidyl ether, and combinations thereof.
- EDA ethylenediamine
- DETA diethylenetriamine
- TETA triethylenetetramine
- TMDA trimethyl hexane diamine
- HMD A hexamethylenediamine
- N3-Amine N,N'-l,2-ethanediylbis-l,3- propanediamine
- arylaliphatic polyamines include, but are not limited to, m-xylylenediamine (mXDA), and p-xylylenediamine.
- cycloaliphatic polyamines include, but are not limited to, 1,3-bisaminocyclohexylamine (1,3-BAC), isophorone diamine (IPDA), and 4,4'-methylenebiscyclohexaneamine.
- aromatic polyamines include, but are not limited to, m-phenylenediamine,
- DDM diaminodiphenylmethane
- DDS diaminodiphenylsulfone
- heterocyclic polyamines include, but are not limited to, N-aminoethylpiperazine (NAEP), 3,9-bis(3-aminopropyl) 2,4,8, 10-tetraoxaspiro(5,5)undecane, and
- polyalkoxy polyamines include, but are not limited to,
- JEFF AMINE® XTJ-504, JEFF AMINE® XTJ-512 poly(oxy(methyl-l,2- ethanediyl)), alpha,alpha'-(oxydi-2, 1 -etha nediyl)bis(omega-(aminomethylethoxy))
- JEFF AMINE® XTJ-511 bis(3-aminopropyl)polytetrahydrofuran 350; bis(3- aminopropyl)polytetrahydrofuran 750; poly(oxy(methyl-l,2-ethanediyl)); a-hydro-ro- (2-aminomethylethoxy) ether with 2-ethyl-2-(hydroxymethyl)- 1,3 -propanediol (JEFF AMINE® T-403); diaminopropyl dipropylene glycol; and combinations thereof.
- Examples of dicyandiamide derivatives include, but are not limited to, guanazole, phenyl guanazole, cyanoureas, and combinations thereof.
- aminoamides include, but are not limited to, amides formed by reaction of the above aliphatic polyamines with a stoichiometric deficiency of anhydrides and carboxylic acids, as described in U.S. Patent 4,269,742.
- amidines include, but are not limited to, carboxamidines, sulfinamidines, phosphinamidines, and combinations thereof. 2
- ketimines include compounds having the structure (R ) 2 C
- R 2 is an alkyl group and R 3 is an alkyl group or hydrogen, and combinations thereof.
- the curing agent can include an anhydride.
- An anhydride is a compound having two acyl groups bonded to the same oxygen atom.
- the anhydride can be symmetric or mixed. Symmetric anhydrides have identical acyl groups. Mixed anhydrides have different acyl groups.
- the anhydride is selected from the group consisting of aromatic anhydrides, alicyclic anhydrides, aliphatic anhydride, polymeric anhydrides, and combinations thereof.
- aromatic anhydrides include, but are not limited to,
- alicyclic anhydrides include, but are not limited to methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and combinations thereof.
- aliphatic anhydrides include, but are not limited to, propionic anhydride, acetic anhydride, and combinations thereof.
- Example of a polymeric anhydrides include, but are not limited to, polymeric anhydrides produced from copolymerization of maleic anhydride such as poly(styrene-co-maleic anhydride) copolymer, and combinations thereof.
- the curing agent can include a carboxylic acid.
- the curing agent can include a phenol.
- phenols include, but are not limited to, bisphenols, novolacs, and resoles that can be derived from phenol and/or a phenol derivative, and combinations thereof.
- the curing agent can include a thiol.
- thiols include compounds having the structure R 5 SH, where R 5 is an alkyl group, and combinations thereof.
- the curable compositions can include a catalyst.
- the catalyst include, but are not limited to, 2-methyl imidazole, 2-phenyl imidazole, 2-ethyl-4-methyl imidazole, 1 -benzyl-2-phenylimidazole, boric acid, triphenylphosphine, tetraphenylphosphonium-tetraphenylborate, and
- the catalyst can be used in an amount of from 0.01 to 5 parts per hundred parts of the epoxy compound; for example the catalyst can be used in an amount of from 0.05 to 4.5 parts per hundred parts of the epoxy compound or 0.1 to 4 parts per hundred parts of the epoxy compound.
- the curable compositions can include an inhibitor.
- the inhibitor can inhibit the activity of the catalyst during formation of a prepreg, e.g. B-staging.
- the inhibitor can be a Lewis acid.
- the inhibitor include, but are not limited to, boric acid, halides, oxides, hydroxides and alkoxides of zinc, tin, titanium, cobalt, manganese, iron, silicon, boron, aluminum, and
- the curable compositions can contain from 0.3 moles of inhibitor per mole of catalyst to 3 moles of inhibitor per mole of catalyst; for example the curable compositions can contain from 0.4 moles of inhibitor per mole of catalyst to 2.8 moles of inhibitor per mole of catalyst or 0.5 moles of inhibitor per mole of catalyst to 2.6 moles of inhibitor per mole of catalyst.
- the curable compositions can include a halogenated flame retardant additive, a non-halogenated flame retardant additive, and/or an inorganic flame retardant additive.
- Reactive flame retardants such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfate, sodium bicarbonate, sodium sulfate
- the curable compositions can include a halogenated flame retardant additive.
- the halogenated flame retardant additive can be from 5 weight percent to 30 weight percent of the curable
- the halogenated flame retardant additive can be from 7 weight percent to 25 weight percent or from 10 weight percent to 20 weight percent of the curable composition.
- the halogenated flame retardant additive can include a halogenated epoxy compound, such as a brominated epoxy compound, a halogenated phenolic hardener, tetrabromobisphenol A (TBBA) and its derivatives, a brominated novolac and its polyglycidyl ether, TBBA epoxy oligomers, brominated polystryrene, tetrabromobisphenol-S, and combinations thereof.
- a halogenated epoxy compound such as a brominated epoxy compound, a halogenated phenolic hardener, tetrabromobisphenol A (TBBA) and its derivatives, a brominated novolac and its polyglycidyl ether, TBBA epoxy oligomers, brominated polystryrene, tetrabromobisphenol-S, and combinations thereof.
- D.E.R.TM 542 the diglycidyl ether of TBBA
- brominated 'advanced' resins such as D.E.R.TM 560, D.E.R.TM 530, D.E.R.TM 592, which are available from The Dow Chemical Company.
- Advanced resins can be produced by reaction of a difunctional epoxy resin with a difunctional phenolic hardener.
- the curable compositions can include a non-halogenated flame retardant additive.
- the non-halogenated flame retardant additive can be from 5 weight percent to 75 weight percent of the curable composition; for example the non-halogenated flame retardant additive can be from 10 weight percent to 70 weight percent or from 15 weight percent to 65 weight percent of the curable composition.
- the non-halogenated flame retardant additive can include a
- phosphorous compound examples include, but are not limited to, phosphinates, phosphonates, phosphates, phosphazenes, metal salts of phosphorus acids, organic salts of phosphorus acids, and combinations thereof.
- phosphinates include, but are not limited to, phosphinate salts, phosphinate esters, diphosphinic acids, dimethylphosphinic acid,
- ethylmethylphosphinic acid diethylphosphinic acid
- the salts of these acids such as the aluminum salts and the zinc salts, and combinations thereof.
- Specific examples of the salts include, but are not limited to, EXOLIT® OP 910, EXOLIT® OP 930,and EXOLIT® OP 950 available from Clariant.
- Additional phosphinates include, but are not limited to, derivatives of OOP' (9,10-dihydro-9-oxa-10-phosphaphenanthren-10- oxide) as described in U.S. Patent Application Publication No. 20070221890, U.S. Patent No. 6645631, U.S. Patent Application Publication No. 20060149023, and by Wang in Polymer, Vol 39, No. 23, 5819-5826.
- Examples of phosphonates include, but are not limited to, derivatives of cyclic phosphonates such as 5,5-dimethyl-2-oxido-l,3,2-dioxaphosphorinane as described in U.S. Patent No. 6645631, and combinations thereof.
- phosphates include, but are not limited to, ammonium polyphosphate, such as EXOLIT® 700 available from Clariant, melamine
- polyphosphate and combinations thereof.
- phosphazenes include, but are not limited to,
- the non-halogenated flame retardant additive can include an antimony or boron compound or salt.
- antimony compounds include, but are not limited to antimony oxides, such as Sb 2 03 and Sb 3 0 5 .
- borates include, but are not limited to, zinc borate, zinc metaborate, barium metaborate, sodium borate, and combinations thereof.
- the curable compositions can include an inorganic flame retardant.
- inorganic flame retardants include, but are not limited to, magnesium oxide, magnesium chloride, talcum, alumina hydrate, zinc oxide, alumina trihydrate, alumina magnesium, calcium silicate, sodium silicate, zeolite, magnesium hydroxide, sodium carbonate, calcium carbonate, ammonium molybdate, iron oxide, copper oxide, zinc phosphate, zinc chloride, silica, clay, quartz, mica, sodium dihydrogen phosphate, and combinations thereof.
- the inorganic flame retardant can be from 5 weight percent to 75 weight percent of the curable composition; for example the non-halogenated flame retardant additive can be from 10 weight percent to 70 weight percent of the curable composition or from 15 weight percent to 65 weight percent of the curable composition.
- the curable compositions can have a phosphorous content of from 0.1 weight percent to 10 weight percent of the curable composition; for example the curable compositions can have a phosphorous content of from 0.5 weight percent to 9 weight percent of the curable composition, from 1.0 weight percent to 8 weight percent of the curable composition, or from 3 weight percent to 10 weight percent of the curable composition.
- the components of the curable compositions can be mixed, ground, and/or extruded by one or more processes.
- a suitable device or a combination of suitable devices may be employed for the mixing, grinding, and/or extruding. Parameters for the mixing, grinding, and/or extruding may vary from one application to another, as is known in the art.
- One example of mixing is melt-mixing. However, other types of mixing may be employed for particular applications.
- the components of the curable compositions can be ground, e.g.
- the components of the curable composition can be cryoground or ground by other grinding procedures known in the art.
- the components of the curable composition can be ground to an average particle size of 1 micrometers ( ⁇ ) to 100 ⁇ ; for example the components of the curable composition can be ground to an average particle size of 3 ⁇ to 75 ⁇ or 5 ⁇ to 50 ⁇ .
- the components of the curable composition have an average particle size of 1 ⁇ to 10 ⁇ .
- the components of the curable compositions can be extruded.
- the extrusion process may be a reactive extrusion.
- the extrusion process can be carried out in conventional processing equipment such as a single screw extruder, or a twin screw extruder, or other processing equipment.
- Embodiments of the present disclosure provide prepregs.
- the prepreg can be obtained by a process that includes impregnating a matrix component into a reinforcement component.
- the matrix component surrounds and/or supports the reinforcement component.
- the curable compositions as disclosed herein can be used for the matrix component.
- the matrix component and the reinforcement component of the prepreg provide a synergism. This synergism provides that the prepregs and/or products obtained by curing the prepregs have mechanical and/or physical properties that are unattainable with only the individual components.
- the reinforcement component can be a fiber.
- fibers include, but are not limited to, glass, aramid, carbon, polyester, polyethylene, quartz, metal, ceramic, biomass, and combinations thereof.
- the fibers can be coated.
- An example of a fiber coating includes, but is not limited to, boron.
- glass fibers include, but are not limited to, A-glass fibers,
- Aramids are organic polymers, examples of which include, but are not limited to, Kevlar®, Twaron®, and combinations thereof.
- carbon fibers include, but are not limited to, those fibers formed from polyacrylonitrile, pitch, rayon, cellulose, and combinations thereof.
- metal fibers include, but are not limited to, stainless steel, chromium, nickel, platinum, titanium, copper, aluminum, beryllium, tungsten, and combinations thereof.
- Ceramic fibers include, but are not limited to, those fibers formed from aluminum oxide, silicon dioxide, zirconium dioxide, silicon nitride, silicon carbide, boron carbide, boron nitride, silicon boride, and combinations thereof.
- biomass fibers include, but are not limited to, those fibers formed from wood, non-wood, and combinations thereof.
- the reinforcement component can be a fabric.
- the fabric can be formed from the fiber, as discussed herein. Examples of fabrics include, but are not limited to, stitched fabrics, woven fabrics, and combinations thereof.
- the fabric can be unidirectional, multiaxial, and combinations thereof.
- the reinforcement component can be a combination of the fiber and the fabric.
- the prepreg is obtainable by impregnating the matrix component into the reinforcement component. Impregnating the matrix component into the
- the reinforcement component may be accomplished by a variety of processes.
- One process for obtaining the prepreg is pressing.
- the matrix component i.e. the disclosed curable composition
- the matrix component may contact one or both of the major surfaces of the reinforcement component to form a layered article.
- the layered article may be placed into a press where it subjected to force for a predetermined time interval to obtain the prepreg.
- the press may have a temperature of 80 degrees Celsius (°C) to 140 °C; for example the press may have a temperature of 90 °C to 130 °C or 100 °C to 120 °C.
- the layered article is subjected to a pressure via the press.
- the pressure may have a value that is 20 kilopascals (kPa) to 700 kPa; for example the pressure may have a value that is 30 kPa to 500 kPa or 70 kPa to 400 kPa.
- the pressure can be applied for the predetermined time interval.
- predetermined time interval may have a value that is 30 seconds (s) to 120 s; for example the predetermined time interval may have a value that is 40 s to 1 10 s or 50 s to 100 s.
- s 30 seconds
- predetermined time interval may have a value that is 40 s to 1 10 s or 50 s to 100 s.
- One or more of the prepregs may be more fully cured to obtain a product.
- the prepregs can be layered or/and formed into a shape before being more cured.
- layers of the prepreg can be alternated with layers of a conductive material.
- An example of the conductive material includes, but is not limited to, copper foil.
- the prepreg layers can then be exposed to conditions so that the matrix component becomes more fully cured.
- One example of a process for obtaining the more fully cured product is pressing.
- the prepreg may be placed into a press where it subjected to a curing force for a predetermined curing time interval to obtain the more fully cured product.
- the press may have a curing temperature of 80 °C to 250 °C; for example the press may have a curing temperature of 90 °C to 240 °C or 100 °C to 230 °C.
- the press has a curing temperature that is ramped from a lower curing temperature to a higher curing temperature over a ramp time interval.
- the layered article can be subjected to a curing force via the press.
- the curing force may have a value that is 20 kPa to 350 kPa; for example, the curing force may have a value that is 30 kPa to 300 kPa or 70 kPa to 275 kPa.
- the curing force may be applied for a predetermined curing time interval.
- the predetermined curing time interval may have a value that is 5 s to 500 s; for example the predetermined curing time interval may have a value that is 25 s to 450 s or 45 s to 400 s.
- ramp time intervals, curing pressure values, and/or predetermined curing time intervals are possible. Additionally, the process may be repeated to further cure the prepreg and obtain the product.
- the product obtained by curing one or more prepregs can have a V-0 or V-1 flame classification according to UL-94
- the UL-94 tests can measure the propensity of a material to extinguish or spread flames once it becomes ignited and can serve as a preliminary indication of a material's acceptability with respect to flammability for a particular application.
- the V-0 and V-1 flame classifications indicate that the material was tested in a vertical position and self- extinguished within a specified time, for each respective flame classification, after the ignition source was removed.
- the V-0 flame classification indicates that burning stops within 10 seconds after two applications, of ten seconds each, of a flame to a test bar and no flaming drips are observed.
- the V-1 flame classification indicates that burning stops within 60 seconds after two applications, of ten seconds each, of a flame to a test bar and no flaming drips are observed.
- the product obtained by curing one or more prepregs can have a glass transition temperature (Tg) of at least 100 °C.
- Tg glass transition temperature
- the product obtained by curing one or more prepregs can have a glass transition temperature from 100 °C to 500 T or 110 °C to 475 °C.
- the product obtained by curing one or more prepregs can have a thermal degradation temperature (Td) of at least 310 °C.
- Td thermal degradation temperature
- the product can have a thermal degradation temperature of 310 °C to 500 °C, or 320 °C to 475 °C.
- Epoxy compound D.E.N.TM 439, available from The Dow Chemical
- Epoxy compound D.E.R.TM 6508, available from The Dow Chemical
- Curing agent DURITE® 357-D, available from Hexion.
- Curing agent REZICURE® 3020, available from the SI Group.
- Phosphono-methyl-glycine glyphosate, available from Monsanto.
- Non-halogenated flame retardant additive EXOLIT® OP 950, available from Clariant International Ltd.
- Inorganic flame retardant silica (AST 600), available from
- Reinforcement component Glass cloth (Style 7628), available from
- Melt-mixture 1 was prepared as follows. D.E.N.TM 439 (17.50 grams),
- melt-mixture 1 was poured onto aluminum foiled and cooled to 20 °C. After cooling melt-mixture 1 was cracked into a number of pieces. Melt-mixtures 2-7 were prepared similarly to melt- mixture 1. The compositions of melt-mixtures 1 -7 are shown in Table I. Melt- mixtures 2-7 were also cooled and cracked into a number of pieces.
- Example 1 The pieces of melt-mixture 1 , REZICURE® 3020 (4.75 grams), boric acid (0.13 grams), 2-methyl imidazole (0.058 grams), and glyphosate (5.13 grams) were ground to an average particle size of 1 to 10 micrometers in a PRISM Pilot grinder to form Example 1 , a curable composition.
- Examples 2-7 were formed as Example 1, with the changes: melt-mixtures 2-7 replaced melt-mixture 1 for Examples 2-7, respectively; Examples 4-6 included a flame retardant additive; and Example 8 included an inorganic filler.
- the components of Examples 1-7 are shown in Table II.
- Table III shows the phosphorous content of each of Examples 1-7 as a weight percentage of the respective curable composition.
- a 24 millimeter PRISM twin screw extruder set a 20 rotations per minute and having a first zone temperature of 15° C, a second zone temperature of 50 °C, and a third zone temperature of 75 °C was primed by adding D.E.R.TM 6508 (200 grams) to the extruder.
- Example 4 was fed to the primed extruder to provide extrusion product 1.
- Extrusion product 1 was ground by mortar and pestle and passed through a 30 mesh sieve to provide extrusion product powder 1.
- Extrusion product powders 2-3 were prepared as extrusion product powder 1 , with the changes that curable compositions prepared as Examples 5-6 replaced Example 4, respectively.
- Prepregs were obtained by impregnating a matrix component into a reinforcement component as follows.
- a layered article was prepared as follows. Two TYVEK® spacers were placed on a first metal sheet. A first release sheet was placed on the TYVEK® spacers. A 30.48 centimeter by 30.48 centimeter piece of the glass cloth was placed on the first release sheet. Five and one half (5.5) grams of Example 1 was placed on the glass cloth and spread into a circular shape. A second release sheet was placed on the glass cloth and Example 1. Two additional TYVEK® spacers were placed on the second release sheet. A second metal sheet was placed on the two additional TYVEK® spacers to form the layered article.
- Example 8 The layered article was placed in a 115 °C Tetrahedron Press Model 1401. The press was closed at 5,000 pounds for 100 seconds. The release sheets were removed from the pressed layered article to provide Example 8, a prepreg. Examples 9, 10, 12, 13, and 16, prepregs, were prepared as Example 8, with the changes that Examples 2, 3, 5, 6, and 7 replaced Example 1 for Examples 9, 10, 12, 13, and 16, respectively.
- Prepregs were obtained by impregnating a matrix component into a reinforcement component as follows.
- a layered article was prepared as follows. Two TYVEK® spacers were placed on a first metal sheet. A first release sheet was placed on the TYVEK® spacers. Seventeen and one half (17.5) grams of extrusion product powder 1 was placed in the first release sheet and spread into a square shape. A 30.48 centimeter by 35.56 centimeter piece of the glass cloth was placed on extrusion product powder 1 and the first release sheet. An additional 17.5 grams of extrusion product powder 1 was placed on the glass cloth and spread into a square shape. A second release sheet was placed on the glass cloth and the additional extrusion product powder 1.
- Example 11 Two additional TYVEK® spacers were placed on the second release sheet.
- a second metal sheet was placed on the two additional TYVEK® spacers to form the layered article.
- the layered article was placed in a 115 ° C Tetrahedron Press Model 1401. The press was closed at 5,000 pounds for 100 seconds.
- the release sheets were removed from the pressed layered article to provide Example 11, a prepreg.
- Examples 14 and 15, prepregs, were prepared as Example 11, with the changes that extrusion product powders 2 and 3 replaced extrusion product powder 1 for Examples 14 and 15, respectively.
- Prepregs were cured using the Tetrahedron Press Model 1401. .
- Example 8 was consecutively heated from about 37 °C to 140 °C at 10.8 °C per minute and held for 10 seconds while under a pressure of 8 psi; heated from 140 °C to 196 °C at 10.8 °C per minute and held for 90 minutes while under a pressure of 32 psi; and cooled from 196 °C to 38 °C at 27 °C per minute and held for 30 seconds while under a pressure of 32 psi to provide Example 16, a product obtained by curing Example 8. [0102]
- Example 9 was consecutively heated from about 37 °C to 134 °C at
- Example 17 a product obtained by curing Example 9.
- Example 10 was consecutively heated from about 37 °C to 140 °C at
- Example 18 a product obtained by curing Example 10.
- Example 11 was consecutively heated from about 37 °C to 140 °C at
- Example 19 a product obtained by curing Example 11.
- Example 12 was consecutively heated from about 37 °C to 134 °C at
- Example 20 14.4 °C per minute and held for 10 seconds while under a pressure of 7 psi; heated from 134 °C to 196 °C at 14.4 °C per minute and held for 90 minutes while under a pressure of 20 psi; and cooled from 196 °C to 38 °C at 27 °C per minute and held for 30 seconds while under a pressure of 20 psi to provide Example 20, a product obtained by curing Example 12.
- Example 13 was consecutively heated from about 37 °C to 134 °C at
- Example 21 a product obtained by curing Example 13.
- Example 14 was consecutively heated from about 37 °C to 146 °C at
- Example 18 a product obtained by curing Example 12.
- Example 15 was consecutively heated from about 37 °C to 146 °C at
- Example 23 a product obtained by curing Example 15.
- Example 16 was consecutively heated from about 37 °C to 134 °C at
- Example 24 a product obtained by curing Example 16.
- Example 16-24 flame classifications were determined using the 94V
- Example 16-24 glass transition temperatures were determined using a
- Example 16-24 thermal degradation temperatures were determined by using a thermogravimetric analyzer (TGA) on a TA instruments Q50 analyzer. For analysis, the software program Universal Analysis V3.3B data was used. The method used for analysis was a ramp rate of 10 °C/min to 600 °C in air. The 5 weight percent decomposition temperature was determined. The glass transition temperatures and thermal degradation temperatures are shown in Table V.
- Example 21 153.5 155.3 159.9 372.4
Abstract
Description
Claims
Priority Applications (6)
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EP11745591.5A EP2598573A1 (en) | 2010-07-30 | 2011-07-19 | Curable compositions |
CN2011800471818A CN103249775A (en) | 2010-07-30 | 2011-07-19 | Curable compositions |
KR20137002464A KR20130133754A (en) | 2010-07-30 | 2011-07-19 | Curable compositions |
US13/812,208 US20130122766A1 (en) | 2010-07-30 | 2011-07-19 | Curable compositions |
SG2013006028A SG187605A1 (en) | 2010-07-30 | 2011-07-19 | Curable compositions |
JP2013523146A JP2013532763A (en) | 2010-07-30 | 2011-07-19 | Curable composition |
Applications Claiming Priority (2)
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US36948610P | 2010-07-30 | 2010-07-30 | |
US61/369,486 | 2010-07-30 |
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WO2012015467A1 true WO2012015467A1 (en) | 2012-02-02 |
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PCT/US2011/001281 WO2012015467A1 (en) | 2010-07-30 | 2011-07-19 | Curable compositions |
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EP (1) | EP2598573A1 (en) |
JP (1) | JP2013532763A (en) |
KR (1) | KR20130133754A (en) |
CN (1) | CN103249775A (en) |
SG (1) | SG187605A1 (en) |
TW (1) | TW201204758A (en) |
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JP2017501265A (en) * | 2013-12-18 | 2017-01-12 | ダウ グローバル テクノロジーズ エルエルシー | Curable composition |
US9822227B2 (en) * | 2014-09-16 | 2017-11-21 | Isola Usa Corp. | High Tg epoxy formulation with good thermal properties |
CN107011536B (en) * | 2017-06-06 | 2018-11-23 | 福建师范大学 | It a kind of preparation of glyphosate melamine salt fire retardant and its is applied in polylactic acid |
CN110591624A (en) * | 2019-10-25 | 2019-12-20 | 山东益丰生化环保股份有限公司 | Mercaptan modified room temperature fast curing epoxy adhesive prepolymer and preparation method thereof |
CN113801158B (en) * | 2021-08-18 | 2023-08-29 | 厦门稀土材料研究所 | N- (phosphonic acid methyl) glycine rare earth carbonizing agent and preparation method and application thereof |
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- 2011-07-19 US US13/812,208 patent/US20130122766A1/en not_active Abandoned
- 2011-07-19 WO PCT/US2011/001281 patent/WO2012015467A1/en active Application Filing
- 2011-07-19 SG SG2013006028A patent/SG187605A1/en unknown
- 2011-07-19 KR KR20137002464A patent/KR20130133754A/en not_active Application Discontinuation
- 2011-07-19 CN CN2011800471818A patent/CN103249775A/en active Pending
- 2011-07-19 JP JP2013523146A patent/JP2013532763A/en not_active Withdrawn
- 2011-07-19 EP EP11745591.5A patent/EP2598573A1/en not_active Withdrawn
- 2011-07-22 TW TW100126001A patent/TW201204758A/en unknown
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JP2013532763A (en) | 2013-08-19 |
SG187605A1 (en) | 2013-03-28 |
US20130122766A1 (en) | 2013-05-16 |
EP2598573A1 (en) | 2013-06-05 |
TW201204758A (en) | 2012-02-01 |
KR20130133754A (en) | 2013-12-09 |
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