WO2011082211A1 - Composition for fixing wound items - Google Patents

Composition for fixing wound items Download PDF

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Publication number
WO2011082211A1
WO2011082211A1 PCT/US2010/062316 US2010062316W WO2011082211A1 WO 2011082211 A1 WO2011082211 A1 WO 2011082211A1 US 2010062316 W US2010062316 W US 2010062316W WO 2011082211 A1 WO2011082211 A1 WO 2011082211A1
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WO
WIPO (PCT)
Prior art keywords
composition
component
mbar
unsaturated
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2010/062316
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English (en)
French (fr)
Inventor
Michael Herm
Frank-Rainer Boehm
Anja Richter
Ulrike Gruene De Jong
Barbara Trappmann
Volker Rittinghaus
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EIDP Inc
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EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to BR112012015569A priority Critical patent/BR112012015569A2/pt
Priority to CN201080059979.XA priority patent/CN102791754B/zh
Priority to EP10803197.2A priority patent/EP2519551B1/en
Priority to IN5046DEN2012 priority patent/IN2012DN05046A/en
Priority to MX2012007576A priority patent/MX2012007576A/es
Publication of WO2011082211A1 publication Critical patent/WO2011082211A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/061Polyesters; Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06Unsaturated polyesters having carbon-to-carbon unsaturation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00Details of transformers or inductances, in general
    • H01F27/28Coils; Windings; Conductive connections
    • H01F27/32Insulating of coils, windings, or parts thereof
    • H01F27/327Encapsulating or impregnating

Definitions

  • the present invention refers to a composition for fixing wound items, in particular electrical windings in electrical equipment providing excellent impregnation properties into the wound items as well as extraordinarily good mechanical toughness, especially at high
  • unsaturated polymers in compositions suitable for impregnating (e.g. by techniques of immersion, dipping, trickling or casting) wound items such as electrical coils and windings, especially windings of magnet wires in electrical devices as well as for casting of electrical devices such as stators, rotors and transformers, for mechanical toughening and fixing, is well known in the art.
  • Various resins can be used for those applications, which typically provide electrical insulation, stabilization of the electrical winding against vibrations, improved aging behaviour and protection against chemical and mechanical impact.
  • the operating temperatures of especially electrical motors become higher. Impregnating materials which are used in motors with high operating temperatures have to be chemically stable at the operating temperatures and also mechanically tough to withstand mechanical forces and/or impact at these elevated temperatures.
  • Impregnation materials based on unsaturated polyesters dissolved in styrene typically show good mechanical toughness, also at elevated temperatures. They have low viscosities, so impregnation quality is typically not an issue. However, such systems show a strong loss of styrene upon curing of the impregnation material, resulting in a significant amount of volatile organic compounds (VOC). Therefore, there is a strong demand for mechanically tough impregnation materials with low to zero emissions.
  • VOC volatile organic compounds
  • binder resins with higher molecular weights and / or rigid polymer building blocks can be improved.
  • building blocks which contain rigid ring structures, e.g. di- or polycyclopentadiene as described in DE-A 3107450, EP-A 101585, EP-A 871677, EP-A 963413 or EP-A 968501.
  • the viscosities of such impregnation materials are typically high, so that the application process becomes more difficult than with standard impregnation materials, e.g. heat has to be applied. This increases the danger of premature curing of the
  • the invention provides a composition for fixing wound items comprising
  • ethylenically unsaturated component having a vapour pressure in a range of 0 to 1 mbar at 20°C, preferred 0 to 0.5 mbar at 20°C,
  • unsaturated component different from B) having a vapour pressure in a range of 0 to 10 mbar at 20°C, preferred 0 to 5 mbar at 20°C,
  • the wt% being based on the total weight of the composition.
  • composition of the present invention provides low curing emissions, low viscosities and excellent impregnation properties into the wound items. After curing, these impregnation materials show high mechanical toughness levels even at elevated temperatures.
  • (meth)acryl refers to acryl and/or methacryl in this document.
  • composition according to the invention comprises at least one a, ⁇ -unsaturated polyester resin as component A) in a range of 5 to 90 wt%, preferably 10 to 75 wt%, particularly preferred are 15 to 70 wt%, the wt% being based on the total weight of the composition.
  • the at least one polyester resin of A) may comprise also at least one ⁇ , ⁇ -unsaturated polyester imide resin comprising at least one imide having 5-membered cyclic imide moieties.
  • the polyester resin of component A) may have a hydroxyl value of 0 to 120 mg KOH/g, preferably 0 to 80, an acid value of 0 to 70 mg KOH/g, preferably 0 to 50 mg KOH/g, as well as a urethane group concentration of 0 to 0.1 mol per 100g resin A).
  • the acid value is defined as the number of mg of potassium hydroxide (KOH) required to neutralise the carboxylic groups of 1 g of the resin, according to DIN EN ISO 21 14.
  • hydroxyl value in this description is defined as the number of mg of potassium hydroxide (KOH) which is equal to the number of mg acetic acid for acetalizing of 1 g of the resin, determined according to DIN 53240.
  • the polyester component A) can be obtained by reaction of (a) at least one ⁇ , ⁇ - ethyl en ically unsaturated dicarboxylic acid, its anhydride and/or an ester of the ⁇ , ⁇ - ethylenically unsaturated dicarboxylic acid, and
  • R 2 is an aliphatic, aromatic or cycloaliphatic moiety with 2 to 20 carbon atoms that may also contain oxygen or nitrogen atoms
  • R 3 is an aliphatic, cycloaliphatic or aromatic moiety in which at least 2 of 4 carbonyl groups in R 3 are in a 1 ,2-position
  • X is a hydroxyl or carboxy functionality
  • the ratio of the reaction components (a) to (g) is chosen in such a way, known to a person skilled in the art, that 100g of component A) contain 0.05 to 0.50 mol of polymerizable, ⁇ , ⁇ - ethylenically unsaturated groups from component (a), in case of a polyester imide the amount of imidically bonded nitrogen in A) is at least 0.5 wt%, preferably at least 1.5 wt% on the resin, and the ratio of the reaction components (a) to (g) is chosen in such amounts that the aforementioned hydroxyl value, acid value and urethane group concentration are achieved, as known by a person skilled in the art.
  • the number average molecular mass (Mn) of component A) is in a range of, for example, 400 to 8000 g/mol, preferably in a range of 500 to 5000 g/mol.
  • Typical ⁇ , ⁇ - ethylenically unsaturated dicarboxylic acids (a) are, for example, those with 4 or 5 carbon atoms, or their anhydrides or esters. Examples are maleic anhydride, fumaric acid, itaconic acid or anhydride, methylene malonic acid, citraconic anhydride or mesaconic acid.
  • maleic anhydride and fumaric acid are used.
  • Typical alcohols of (b) are, for example, mono-, di- or trifunctional alcohols with 2 to 18 carbon atoms like 8(9)-hydroxytricyclo[5.2.1.0 26 ]dec- 3-en, 1 ,4-bis-hydroxymethyl cyclohexane, 2,2-bis-(4-hydroxycyclohexyl)- propane, ethylene glycol, propylene glycol, 1,3-propane diol, neopentyl glycol (NPG), trimethylol propane (TMP), glycerol,
  • TBEIC tris(hydroxyethyl)isocyanurate
  • pentaerythritol pentaerythritol.
  • Preferred alcohols of (b) are 1 ,3-propane diol, neopentyl glycol, THEIC and trimethylol propane.
  • Typical imide group containing moieties (c) are the reaction products of tricarboxylic acids or their anhydrides, like trimellitic anhydride, 3,3',4-benzophenone tricarboxylic acid anhydride, tricarballylic acid or unsaturated cycloaliphatic, aromatic or aliphatic dicarboxylic acid anhydrides like tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, endo-methylene tetrahydrophthalic anhydride or maleic anhydride with aliphatic, cycloaliphatic, heterocyclic or aromatic aminoalcohols or aminocarboxylic acids.
  • tricarboxylic acids or their anhydrides like trimellitic anhydride, 3,3',4-benzophenone tricarboxylic acid anhydride, tricarballylic acid or unsaturated cycloaliphatic, aromatic or aliphatic dicarboxylic acid anhydrides like
  • aminoalcohols are e.g. ethanolamine, propanolamine, butanolamine, their higher homologues, 4-aminocyclohexanol, 4-aminobenzyl alcohol or aromatically ami no-substituted phenyl ether alcohols.
  • aminocarboxylic acids are e.g. aminoacetic acid, aminopropionic acid, aminocapronic acid and 4-aminobenzoic acid.
  • substances (c) are reaction products of tetracarboxylic acids or their anhydrides like pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride with aliphatic, cycloaliphatic, hetereocyclic or aromatic aminoalcohols or aminocarboxylic acids, and/or reaction products of 2 mols of tricarboxylic acids or their anhydrides like trimellitic anhydride, tricarballylic acid or 3,3',4-benzophenone tricarboxylic acid anhydride with 1 mol aromatic diamines like 4,4'-diamino diphenylmethane, 4,4'-diamino diphenylether or aliphatic and/or cycloaliphatic diamines like 4,4'-diamino
  • dicyclohexylmethane ethylene diamine, propylene diamine or aliphatic etheramines.
  • diamines also the respective diisocyanates can be used.
  • Preferred imide group containing substances (c) are the reaction products of tetrahydrophthalic anhydride or trimellitic anhydride with ethanolamine.
  • Typical examples for the (meth)acryl functional components (d) are functional polyester (meth)acrylates, functional polyether (meth)acrylates, functional silicone (meth)acrylates, functional (meth)acrylated
  • poly(butadiene) or functional urethane (meth)acrylates in which the functional group can be, for example, a hydroxy, carboxy, epoxy and/or isocyanate group.
  • the functional group can be, for example, a hydroxy, carboxy, epoxy and/or isocyanate group.
  • carboxy (meth)acrylates and their derivatives such as acid halides, hydroxy (meth)acrylates, epoxy
  • (meth)acrylates and amino (meth)acrylates for example, hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, trimethylol propane
  • di(meth)acrylate pentaerythritol tri(meth)acrylate
  • (meth)acrylic acid chloride Preferred are glycidyl (meth)acrylate, (meth)acrylic acid chloride and hydroxyethyl (meth)acrylate.
  • Typical carboxylic acids (e) different from a) can be saturated and/or unsaturated aliphatic, cycloaliphatic and/or aromatic mono-, di-, tri- and/or tetracarboxylic acids, anhydrides and/or esters, especially alkyl esters having 1 to 4 carbon atoms in the alkyl chain.
  • Examples are dicyclopentadiene dimaleinate, tetrahydrophthalic acid anhydride, endo- methylene tetrahydrophthalic anhydride, trimellitic anhydride, terephthalic acid, isophthalic acid, tetrachlorophthalic acid, hexachlorophthalic acid, adipic acid, glutaric acid, sebacinic acid, oligo- and/or polymeric fatty acids, carboxyfunctional polyolefins.
  • Typical examples for (f) different from b) are polyethylene glycol, polypropylene glycol, polytetrahydro furane, reaction products of the addition of ethylene oxide or propylene oxide to polyfunctional alcohols with 2 to 4 hydroxy groups like glycerol, trimethylol ethane, trimethylol propane, triethanolamine or pentaerythritol or with polyfunctional phenols with 2 to 4 hydroxyl groups like catechol, hydroquinone, bisphenol A or bisphenol F, further examples are hydroxyfunctional homo- or copolymers obtained by radical polymerization, hydroxyfunctional polycarbonates or hydroxyfunctional polyester with weight average molar masses between 400 and 10000 g/mol or polyolefinic polyols such as hydroxyfunctional polymers of ethylene, propylene, butylene, octene, isoprene, butadiene, chloroprene or combinations thereof.
  • the polyisocyanates (g) are preferably polyisocyanates containing 2 or more isocyanate groups, for example, aliphatic, cycloaliphatic or aromatic diisocyanates with 6 to 18 carbon atoms like 1 ,6-hexamethylene diisocyanate, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate, 3- lsocyanatomethyl-3,5,5-trimethyl cyclohexylisocyanate, 2,2,3- and 2,4,4- trimethyl hexamethylene diisocyanate, cyclohexanone 1 ,3- and 1 ,4- diisocyanate, 2,4- and 2,6-toluylene diisocyanate, 2,4'- and 4,4'- diphenylmethane diisocyanate, polyisocyanates that are obtained by reaction of a polyisocyanate with a substoichiometric amount of polyols, or trimerization products of above
  • the component (g) is preferably used in such an amount that the urethane group content of the unsaturated polyester or polyester imide A) is in the range of 0 to 0,1 mol per lOOg of A).
  • polyester imides or polyesters A may be prepared by methods well known to a person skilled in the art, for example, by polyesterification by heating the components, e.g. to temperatures of 120 to 240°C in a melt process under inert gas or in an azeotropic process, possibly in the presence of polyesterification catalysts.
  • the ratios of the amounts of the components (a) to (g) are chosen in such a way, known to a person skilled in the art, that the number average molar mass of the resulting resin A) is in the range of 400 to 8000 g/mol, preferably 500 to 5000 g/mol.
  • composition according to the invention comprises 2 to 80 wt%, preferably 4 to 65 wt%, of at least one monomeric and/or oligomeric ethylenically unsaturated component (B) characterized by ethylenically unsaturated structures having one or more vinylic or allylic double bonds, which are radically polymerizable.
  • Component (B) has a vapour pressure in a range of 0 to 1 mbar at 20°C, preferred 0 to 0.5 mbar at 20°C.
  • Component (B) may be also (meth)acrylic acid esters like hydroxyethyl (meth)acrylate,
  • dicyclopentadiene (meth)acrylate, butane diol di(meth)acrylate, hexane diol (meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylol propane di- and tri(meth)acrylate, pentaerythritol di- and tri(meth)acrylate, epoxy resin (meth)acrylates, (meth)acrylates of reaction products of a polyaddition of ethylene or propylene oxide with polyols such as trimethylol propane or pentaerythritol, and (meth)acrylates of oligo(ethylene glycol) or oligo(propylene glycol).
  • Preferred examples for (B) are hexane diol dimethacrylate, butane diol dimethacrylate and (meth)acrylates of reaction products of a polyaddition of ethylene oxide with trimethylol propane or mixtures thereof.
  • preferred 0 to 10 wt% of the component (B) can consist of monomers with polymerizable groups like maleic or fumaric bis- alkyl esters, in which the alkyl groups contain 1 to 4 carbon atoms, or like mono- or bis-maleic imides (see also DE-A-2040094, DE-A-2719903, DE- A-3247058 and EP-A-0255802).
  • composition according to the invention comprises 0.1 to 40 wt%, preferably 1 to 40 wt%, of at least one monomeric and/or oligomeric unsaturated component (C) different from component (B) characterized by ethylenically unsaturated structures having one or more vinylic or allylic double bonds, which are radically polymerizable.
  • Examples are styrene, vinyl toluene, p-methyl styrene, tert.-butyl styrene, divinyl benzene, N-vinyl pyrrolidone, hydroxybutyl vinyl ether, butane diol vinyl ether, triethylene glycol divinyl ether, phthalic acid diallyl ester, fumaric acid diallyl ester, triallyl phosphate, triallyl isocyanurate, diallyl benzene, diallyl bisphenol A, pentaerythritol tri or tetra allyl ether.
  • Component (C) may be also (meth)acrylic acid esters like hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentadiene
  • (C) tri(meth)acrylate, pentaerythritol di- and tri(meth)acrylate, epoxy resin (meth)acrylates, (met )acrylates of reaction products of a polyaddition of ethylene or propylene oxide with polyols such as trimethylol propane or pentaerythritol, and (meth)acrylates of oligo(ethylene glycol) or oligo(propylene glycol).
  • Preferred examples for (C) are styrene, vinyl toluene, hexane diol dimethacrylate, butane diol dimethacrylate and (meth)acrylates of reaction products of a polyaddition of ethylene oxide with trimethylol propane or mixtures thereof.
  • Component (C) has a vapour pressure in a range of 0 to 10 mbar at 20°C, preferred 0 to 5 mbar at 20°C.
  • preferred 0 to 10 wt.-% of the component (C) can consist of monomers with polymerizable groups like maleic or fumaric bis- alkyl esters, in which the alkyl groups contain 1 to 4 carbon atoms, or like mono- or bis-maleic imides (see also DE-A-2040094, DE-A-2719903, DE- A-3247058 and EP-A-0255802).
  • composition according to the invention comprises 0 to 15 wt%, preferably 0 to 10 wt%, more preferably 0.1 to 10 wt%, of at least one customary additive as component (D) which are additives as known to a person skilled in the art, for example, extenders, plasticising components, accelerators, for example metal salts, substituted amines; initiators, for example photo initiators such as chorine containing photoinitiators, aromatic ketones, hydroxyalkyl phenones, initiators such as peroxides, hydroperoxides, ketone peroxides, heat-responsive initiators such as C-C- labile 1 ,2-substituted tetraphenyl ethanes having, for example, the formula YPh 2 C-CPh 2 Y with Ph: phenyl, Y: -OH, -OCH 3 , -OC 6 H 5 , -CH 3 , -CN, -NH 2 , -CI or -
  • alkylphenols alkylphenols, alkylphenol ethers, defoamers and flow control agents.
  • Further additives may be fiber-like reinforcement agents like carbon, glass, polyamide, polyester, polyacrylnitrile, polyaramide, polyamideimide or polycarbonate fibers or fillers like chalk, talc, aluminium hydroxide, quartz flour, slate flour, clay or microdolomite; organic and inorganic pigments, dyes, thixotropy agents and shrinkage reducing agents.
  • composition according to the invention comprises 0 to 30 wt%, preferably 0 to 20 wt%, more preferably 0.1 to 20 wt%, of at least one monomer and/or polymer containing epoxy or glycidyl ether or ester moieties as component (E), comprising monomers or polymers containing epoxy or glycidyl ether or ester moieties such as bisphenol A
  • diglycidylether bisphenol F diglycidylether and/or the appropriate oligomers and polymers, glycidol, aliphatic and/or aromatic epoxides such as styrene oxide, glycidyl methacrylate, versatic acid glycidyl ester, epoxidized poly(butadiene)s, poly(chloroprenes) and poly(isoprenes).
  • the components (A), (B), (C), (D) and (E) of the composition according to the invention may be mixed as readily prepared materials in any sequence.
  • the components (A), (B) and/or D) and/or (E) may also be dissolved in (C) and afterwards mixed together, and the components (A), (C) and/or (D) and/or (E) may also be dissolved in (B) and afterwards mixed together. It is also possible to pre-mix components (B) and (C), and then dissolve components (A) and/or (D) and/or (E) in this mixture.
  • composition according to the invention may be proceeded by processes known in the art, for example, by dip
  • the substrates are dipped into the composition for a certain time or pulled through the composition.
  • the substrate may be heated to temperatures below the curing temperature of the composition before dipping.
  • the substrates are placed into a closed container, vacuum is applied, then the composition of the invention can be flushed into the container.
  • the composition according to this invention can be trickled with e.g. a nozzle onto a rotating substrate.
  • the heating may be provided by methods known in the art, for example, by electrical current or in an oven, for example, during or before impregnation process.
  • the composition according to this invention can be cured.
  • This can be proceeded, for example, by radical polymerization, and for this radical polymerization it is useful to add radical initiators as part of component D) to the composition of the invention.
  • the curing may be carried out by heating the impregnated substrate and/or by irradiation the impregnated substrate with high-energy radiation.
  • the heat for curing can be produced, for example, by passing an electrical current through the windings; it is also possible to use an oven or an infrared (IR) or a near infrared radiation (NIR) source.
  • the heating temperature (object temperature) may be in the range of 80 to 180°C. Typical curing times are, for example, 1 minute to 180 minutes, in case of NIR radiation the curing time may be shorter, for example, below 1 minute.
  • the composition according to this invention can also be cured at temperatures below 80°C, for example at ambient temperatures, under the use of additives such as aromatic amines or salts of cobalt, copper, cerium or vanadium.
  • the coating according to this invention can also be cured by the application of high-energy radiation, e.g. ultraviolet (UV) light or electron beam.
  • high-energy radiation e.g. ultraviolet (UV) light or electron beam.
  • UV curing adequate initiators can be used, for example, photoinitiators that absorb in a wavelength range of 190 to 450 nm.
  • thermoinitiators with thermally labile initiators is possible, e.g. for a combination of heat curing and UV curing.
  • the high-energy radiation may be used for the acceleration of the curing process, but also for the through-curing of the applied composition, depending on the impregnation layer thickness.
  • UV- and electron beam radiation can also be used to cure only the surface of the impregnation composition of the invention applied on the substrate, in order to reduce emission of volatile monomers of the composition in a thermal curing step afterwards.
  • compositions according to this invention can be used in several fields of applications. They are especially useful for fixing of wound items, for example, coiled substrates, especially of coiled wires like magnet wires in electrical devices like rotors, stators or transformers, or of coiled metal foils in the electrical sector, or coiled substrates on the basis of glass fibers, plastic fibers or plastic foils, and may also be used for the impregnation of fabrics.
  • coiled substrates especially of coiled wires like magnet wires in electrical devices like rotors, stators or transformers, or of coiled metal foils in the electrical sector, or coiled substrates on the basis of glass fibers, plastic fibers or plastic foils, and may also be used for the impregnation of fabrics.
  • Composition of prior art a) is the commercial DuPont impregnating resin Voltatex ® 4012, which is a resin based on an unsaturated polyester different from the polyester according to this invention, dissolved in styrene (viscosity at 25°C: 240mPas).
  • Composition of prior art b) is the commercial DuPont impregnating resin Voltatex ® 4302, which is a resin based on an unsaturated polyester different from the polyester according to this invention, dissolved in the acrylate of the reaction product of a polyaddition of ethylene oxide with trimethylol propane (viscosity at 25°C: 7300mPas).
  • Component (A) is an unsaturated polyester based on 57 parts by weight of maleic anhydride, 28 parts by weight of tetrahydrophthalic anhydride, 14 parts by weight of trimethylol propane, 32 parts by weight of neopentyl glycol and 11 parts by weight of ethanolamine, which is further reacted with 13 parts by weight of a methacrylic acid derivative.
  • Component (A) has the following properties: acid value 17mgKOH/g, double bond equivalent weight 210g/mol.
  • component (A) 55 parts by weight of component (A) are heated to 100°C and dissolved in a mixture of 20 parts by weight of the acrylate of the reaction product of a polyaddition of ethylene oxide with trimethylol propane (component (B)) and 13 parts by weight of vinyl toluene (component (C)). After cooling to ⁇ 40°C, 1.4 parts by weight of a C-C radical initiator (benzpinakol ether, component (D)) are added and mixed well (viscosity at 25°C: 3500mPas).
  • a C-C radical initiator benzpinakol ether, component (D)
  • Curing loss 1 - (net sample weight before cure / net sample weight after cure)
  • the impregnation material according to this invention exhibits extraordinary mechanical properties especially at elevated temperatures while delivering low emissions upon curing and maintaining good impregnation properties due to medium viscosities.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Epoxy Resins (AREA)
PCT/US2010/062316 2009-12-30 2010-12-29 Composition for fixing wound items Ceased WO2011082211A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BR112012015569A BR112012015569A2 (pt) 2009-12-30 2010-12-29 composição para a fixação de itens quebrados e item quebrado fixado com a composição
CN201080059979.XA CN102791754B (zh) 2009-12-30 2010-12-29 用于固定卷绕物体的组合物
EP10803197.2A EP2519551B1 (en) 2009-12-30 2010-12-29 Composition for fixing wound items
IN5046DEN2012 IN2012DN05046A (https=) 2009-12-30 2010-12-29
MX2012007576A MX2012007576A (es) 2009-12-30 2010-12-29 Composicion para preparar articulos dañados.

Applications Claiming Priority (2)

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US29112809P 2009-12-30 2009-12-30
US61/291,128 2009-12-30

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WO2011082211A1 true WO2011082211A1 (en) 2011-07-07

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EP (1) EP2519551B1 (https=)
KR (1) KR20120110140A (https=)
CN (1) CN102791754B (https=)
BR (1) BR112012015569A2 (https=)
IN (1) IN2012DN05046A (https=)
MX (1) MX2012007576A (https=)
WO (1) WO2011082211A1 (https=)

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JP5611182B2 (ja) * 2011-12-07 2014-10-22 株式会社日立製作所 ドライマイカテープ、並びにそれを用いた電気絶縁線輪及び回転電機
DE112014000568B4 (de) 2013-01-25 2023-09-07 Axalta Coating Systems Gmbh Zusammensetzung zum Fixieren von bewickelten Gegenständen, Verfahren zu deren Herstellung, Verfahren zum Fixieren von bewickelten Gegenständen und bewickelter Gegenstand
US10767075B2 (en) * 2017-09-15 2020-09-08 Nanoshield Technology Co., Ltd. Coating composition comprising nano-sol, and preparation method thereof
EP4281506A1 (en) * 2021-01-21 2023-11-29 PPG Industries Ohio, Inc. A coating composition

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DE2040094A1 (de) 1969-08-12 1971-03-11 Rhone Poulenc Sa Verfahren zur Herstellung von Bismaleinimiden
DE2719903A1 (de) 1976-05-05 1977-11-24 Du Pont Verfahren zur herstellung von maleinimiden und dimaleinimiden
FR2401946A1 (fr) * 1977-09-05 1979-03-30 Ucb Sa Polyesters acryliques radiodurcissables
DE3107450A1 (de) 1981-02-27 1982-10-21 Basf Ag, 6700 Ludwigshafen Ungesaettigte polyester
DE3247058A1 (de) 1981-12-23 1983-07-28 CIBA-GEIGY AG, 4002 Basel Lagerstabile, waermehaertbare, polymerisationskatalysatoren enthaltende mischungen auf polyimidbasis
EP0101585A2 (de) 1982-08-20 1984-02-29 BASF Aktiengesellschaft Verfahren zur Herstellung von ungesättigten Polyesterharzen
EP0255802A2 (de) 1986-08-06 1988-02-10 Ciba-Geigy Ag Copolymere aus N-Hydroxyphenylmaleinimid(derivaten) und Allylverbindungen
US5096938A (en) * 1987-02-11 1992-03-17 Basf Aktiengesellschaft Radiation-curable acrylates
EP0350730A2 (de) * 1988-07-13 1990-01-17 Bayer Ag Verfahren zur Herstellung von Acryloylgruppen enthaltenden Polyestern und ihre Verwendung als Lackbindemittel
WO1992001015A1 (de) * 1990-07-12 1992-01-23 Herberts Gesellschaft mit beschränkter Haftung Verfahren und vorrichtung zur fixierung von wickelgütern und verwendung von radikalisch polymerisierbaren massen hierfür
CA2119206A1 (en) * 1993-03-18 1994-09-19 David G. Leppard Curing compositions containing bisacylphosphine oxide photoinitiators
EP0871677A1 (de) 1996-01-04 1998-10-21 Dr.Beck & Co. Aktiengesellschaft Tränk-, verguss- und überzugsmassen
EP0963413A1 (de) 1997-02-25 1999-12-15 BASF Coatings Aktiengesellschaft Verfahren zum beschichten von formkörpern mit polyesterharzmassen oder -lösungen
EP0968501A1 (de) 1997-03-19 2000-01-05 Altana Electrical Insulation Gmbh Tränk-, verguss- und überzugsmassen für elektrotechnische und/oder elektronische bauteile sowie für trägermaterialien für flächige isolierstoffe
WO2000046297A1 (en) * 1999-02-02 2000-08-10 Ashland Inc. Unsaturated polyester resin compositions
WO2003101918A2 (en) * 2002-05-29 2003-12-11 Valspar Sourcing, Inc. Low-hap and zero-hap polyester systems and articles

Also Published As

Publication number Publication date
IN2012DN05046A (https=) 2015-10-09
CN102791754B (zh) 2015-10-07
CN102791754A (zh) 2012-11-21
EP2519551B1 (en) 2017-08-02
US20110160341A1 (en) 2011-06-30
MX2012007576A (es) 2012-07-23
KR20120110140A (ko) 2012-10-09
EP2519551A1 (en) 2012-11-07
BR112012015569A2 (pt) 2016-03-22

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