WO2014147072A1 - Masse de scellement, utilisation de la masse de scellement et composite durci par voie thermique obtenu à partir de la masse de scellement - Google Patents

Masse de scellement, utilisation de la masse de scellement et composite durci par voie thermique obtenu à partir de la masse de scellement Download PDF

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Publication number
WO2014147072A1
WO2014147072A1 PCT/EP2014/055414 EP2014055414W WO2014147072A1 WO 2014147072 A1 WO2014147072 A1 WO 2014147072A1 EP 2014055414 W EP2014055414 W EP 2014055414W WO 2014147072 A1 WO2014147072 A1 WO 2014147072A1
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Prior art keywords
filler
particle diameter
fraction
filler fraction
range
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PCT/EP2014/055414
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German (de)
English (en)
Inventor
André GRÜBEL
Matthias ÜBLER
Jürgen Huber
Bernhard Klaussner
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Siemens Aktiengesellschaft
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Publication of WO2014147072A1 publication Critical patent/WO2014147072A1/fr

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Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present invention relates to a potting compound, a use of the potting compound, and a thermally cured composite obtainable from the potting compound.
  • Electrical machines that convert electricity into mechanical energy to produce rotating and / or translational motion typically consist of a fixed stator and a rotating rotor.
  • the stator is often traversed with grooves in which mutually insulated, specially interconnected, metallic conductors (usually copper conductors) in the form of stacked turns (so-called. Form coils) are introduced, which by energizing a circulating in the circle, the centrally mounted rotor penetrating Induce magnetic field.
  • the drawn from the so-called coil fish form coil is wound manually or automatically or semi-automatically in defined overlap with mica paper on train and fixed.
  • These so prepared coils are manually inserted into the grooves, fixed, electrically connected by soldering and the whole stator in a so-called Global-VPI process with a thermally highly stressable impregnating resin (usually based on polyester and / or silicone) impregnated as possible without defects and then cured with heat, creating a mica tape resin composite as the main insulation.
  • This composite material is characterized by a high continuous ⁇ use temperature and currently, considered as an overall system, a permissible use under "thermal class H" conditions according to the requirements of IEC 60034-18-31 and -32.
  • WO 97/11831 A1 describes a process for extruding a thermoplastic material into a complex mold, which is preferably a stator bar, wherein (a) the complex shape having a length and more than one side is fed into a center bore of a die, the center bore having a configuration sufficient to move the die along the complex shape (b) extruding at least one thermoplastic material through the die so as to deposit it simultaneously on each side of the complex die; and (c) moving the die along the entire length of the complex die.
  • DE 696 01 623 T2 relates to a method for producing an electric motor in which a rotor assembly is constructed on a rotor shaft, wherein the rotor assembly has La ⁇ ger, which are arranged near the ends of the rotor shaft; a stator stator assembly is formed by assembling a stack of stator laminations with stator poles; isolating the stator poles and winding the stator poles with stator windings; the intermediate stator is inserted into a mold ⁇ holding device, having an inner cavity which is shaped so that it defines a rear end ⁇ cap for the stator assembly and a mandrel projecting through the center of the intermediate stator, to form a central bore ; the stator assembly is injection molded under pressure into the mold holder by injecting molten thermoplastic resin, thereby forcing the molten plastic into the intermediate stator assembly to embed the stator windings, fill internal cavities, and fill the mold cavity Fill molds of a rear end cap; the assembly is cooled
  • an electric machine which has a plurality of winding wires, wherein the winding ⁇ wires with at least one applied in the predeterminable layer thickness insulating layer pore-free ⁇ layers are coated, the insulating layer of at least one thermoplastic and / or high temperature thermoplastic is, the Ther ⁇ Moplast and / or high temperature thermoplastic has a good bond to impregnation, the thermoplastic and / or high temperature thermoplastics, an amorphous or partially crystalline
  • Has structure and / or fillers are admixed.
  • WO 2001/48897 Al describes a method for producing high-quality insulation on a conductor or conductor bundle of rotating electrical machines, in which inner corona, insulation andparticularlyglimmschutz be applied with respective layer thicknesses of ⁇ 0.2 mm in successive immersion in a vortex sinter , The sintering and the curing are carried out at temperatures of about 200 ° C, so that materials can be used, wel ⁇ che meet the demands made on the isolation of such conductors or conductor bundles of rotating electrical machines requirements.
  • a faultlessness of the individual layers is ensured by the manufacturing process, in particular by the selected layer thickness of the Ein ⁇ zellagen so that no partial discharges may occur that would otherwise lead to damage to the insulation.
  • WO 2001/48895 A1 has a method for producing a high-quality insulation for conductors or conductor bundles, wherein a conductor or conductor bundle to be coated is mounted on a turning and holding device, an insulation with a desired layer thickness profile on the preheated conductor or Conductor bundles by means of a spray gun arranged on an adjustable positioning unit. is introduced, wherein in the applying a combinatorial ⁇ ned movement of spray gun and conductor or conductor bundle by means of the moving part and the turn and Garvorrich ⁇ processing or a movement of the spray gun alone is effected either by means of the traversing unit, and the deposited layers are cured.
  • the Ver ⁇ drive for producing the magnetic coil for an electromagnetic rotor comprises a) providing a magnetic coil comprising a plurality of layers of copper bars; b) coating the plurality of layers of the magnetic coil with a powder resin having a dielectric strength of at least about
  • DE 100 23 207 A1 describes a method for applying the main insulation of Spulenurformen, in particular for stator windings, wherein the Spulenurform has a rectangular cross-section and the main insulation consists of elastomer. In a preferred manner, the jacket is made with a silicone elastomer.
  • DE 100 23 208 A1 has a method for applying the
  • Main insulation of conductor bars to the object in particular of conductor bars for stator windings, wherein the conductor bars have a rectangular cross-section.
  • a finite conductor bar is placed in an injection mold centering the conductor bar in the injection mold such that a cavity for receiving an insulating material remains between the conductor bar and the injection mold, and the cavity is filled with an elastomer to form the main insulation.
  • DE 10 2008 003 784 A1 describes a method and a device for casting stators for electric motors with internal runners.
  • the device comprises an axis of rotation, a driving means for rotationally driving the rotation axis and attached to the axis of rotation ⁇ brought holding means for longitudinal axial clamping a stator.
  • the stator is clamped in the holding device and set for the casting with flowable potting compound by means of the drive device in rotation.
  • the method is based on that the stator is rotated about its longitudinal axis during and / or after the introduction of flowable potting compound in such a way that the potting compound is cavity-filling and evenly distributed during the Rotationsgussvorgangs. This makes it possible to completely shed egg ⁇ nen stator without a subsequent stator through hole must be attached.
  • the potting compound reliably fills the stator winding and cavities and forms a smooth surface facing the rotor.
  • Forming winding heads which are embedded in a potting compound, insbesonde ⁇ re resin, wherein the laminated core has at its ra ⁇ dial outer region at least one axially extending Ausneh ⁇ tion with a circumferentially closed contour up.
  • a molding compound with a Harzkompo ⁇ component wherein the resin component is a mixture of at least one bisphenol diglycidyl ether, at least one constitutional isomers of diphenylmethane diisocyanate or a mixture of a plurality of structural isomers of diphenylmethane diisocyanate and homologues having 3, 4 or more phenyl groups, wherein the proportion of Bisphenol diglycidyl ether on the resin component 7 wt .-% to 30 wt .-%, preferably
  • 9 wt .-% to 27 wt .-% is, as well as a reaction accelerator with a content of 0.5 wt .-% to 15 wt .-%, preferably 3 wt .-% to 10 wt .-%, based on the weight of the filler-free resin component.
  • the sealing compound is characterized in that it includes a filler component, wherein the proportion of the filling ⁇ material component in the total weight of the sealing compound 50 wt .-% to 95 wt .-%, preferably 60 wt .-% to 90 wt .-%, particularly preferably 60% by weight to 80% by weight, and the filler component comprises a first filler fraction, wherein the first filler fraction is native and / or epoxy-functional, amorphous fused silica having a mean particle diameter value in the range of 10 nm to 1000 ⁇ m, and
  • the filler component comprises at least one second Golfstofffrak ⁇ tion, wherein the second filler fraction is selected from at least one member of the group consisting of native amorphous fused silica, epoxy-functionalized amorphous fused silica, quartz powder, alumina, dolomite, chalk, Glasper ⁇ len, boron nitride, wollastonite, zeolite, and polysiloxane ym with egg ⁇ nem value for the mean particle diameter in the range of 10 nm to 1000,
  • mean particle diameter of the second filler fraction is smaller by at least a factor of 2.5 than the mean particle diameter of the first filler fraction.
  • LCTE linear coefficient of thermal expansion
  • the dynamic processing viscosities of the prepolymers potting compound is at 80 ° C advantageously below about 1000 cp and 1 Pa * s.
  • Herge ⁇ presented molding materials have exceptionally good part ⁇ discharge resistance, high contact resistances, low Water absorption capacity, high rigidity, acceptable fracture mechanics and thermophysical properties as well as excellent hydrolysis properties.
  • the potting compound contains as bisphenol diglycidyl ether
  • Bisphenol A diglycidyl ether bisphenol F diglycidyl ether or a mixture thereof.
  • a finished potting compound should have a dynamic viscosity in the range of 1000 mPa ⁇ s ("milliPascal seconds") or lower at about 80 ° C.
  • Such a viscosity range can be achieved in a particularly advantageous manner by using bisphenol F diglycidyl ether or a mixture of bisphenol F diglycidyl ether with bisphenol A diglycidyl ether.
  • the mean particle diameter of the first filler fraction has a value in the range from 1 .mu.m to 1000 .mu.m.
  • the average particle diameter of the second filler fraction has a value from the range of 1 ym to 1000 ym comprising, it is smaller in accordance with an advantageous wide Erbil ⁇ dung to the invention by a factor of 2.5 to 15 than the average particle diameter of the first filler fraction ,
  • Casting compound produced shaped body, which is very desirable in the context of the present invention.
  • the first te and the second filler fraction in a range of 80 vol .-% to 20 vol .-% up to 60 vol .-% to 40 vol .-% enthal ⁇ th, wherein the first filler fraction in the filler component with the higher specified Vol. -% - Share is included.
  • the filler component of the sealing compound at least one third filler fraction to the third filler fraction is selected from at least one of ⁇ member of the group consisting of native amorphous fused silica, epoxy-functionalized amorphous fused silica, alumina, zeolite, and polysiloxane having a Value for the average particle diameter from the range of 10 nm to 1000 ym, wherein the mean particle diameter of the third filler fraction is at least a factor of 2.5 smaller than the mean particle diameter of the second filler fraction.
  • ge ⁇ means that the factor within the permissible ranges of values for the average particle diameter of any value, ie 2.5 or greater can accept.
  • the average particle diameter of the third filler fraction has a value in the range from 1 .mu.m to 1000 .mu.m, the average particle diameter of the third filler fraction is smaller by a factor of 2.5 to 15 than that of the average particle diameter the second filler fraction.
  • a packing coefficient-optimized filling ⁇ fuel fraction with a packing coefficient of up to more than 75 vol .-% can, preferably more than 77 vol .-%, particularly forthcoming more than 80% by volume (as determined by Lee ID, Journal of Paint Technology 42, No. 550 (1970), 579). The higher the degree of filling of the potting compound, the stiffer and more resistant to fracture becomes the composite produced from it.
  • the potting compound can be used as a reaction accelerator at least one catalytically active compound and / or a (sensitive and / or latent-acting) accelerator having a content of 0.5 wt .-% to 15 wt .-%, preferably 3 wt .-% to 10 wt .-%, based on the weight of the filler-free resin component added.
  • the present invention also encompasses the use of the potting compound according to the invention for potting a stator coil and / or a winding head for an electrical machine.
  • the present invention comprises a thermally cured composite obtainable from a potting compound according to the invention by polymerizing the resin component contained in the potting compound.
  • the present invention includes, inter alia, a molding compound comprising a resin component containing a mixture of at least one bisphenol diglycidyl ether and at least one constitutional isomers of diphenylmethane diisocyanate or a mixture of several Konstituti ⁇ onsisomeren of diphenylmethane diisocyanate and homologues having 3, 4 and more phenyl groups, wherein the proportion of bisphenol diglycidyl ether on the resin component is 7 wt .-% to 30 wt .-%, preferably 9 wt .-% to 27 wt .-%, and a reaction onsbevant with a content of 0.5 wt .-% to 15 wt .-%, preferably 3 wt .-% to 10 wt .-%, based on the weight of the filler-free resin component includes.
  • Bisphenol A diglycidyl ether bisphenol F diglycidyl ether or a mixture thereof.
  • Diphenylmethanediisocyanate are chemical compounds from the group of aromatic isocyanates Diphenylmethane diisocyanates are a mixture of several constitutional isomers, which differ in the position of the isocyanate groups.
  • Technical diphenylmethane diisocyanate also referred to as PMDI or Polymeric MDI is a mixture of 30 to 80% MDI and homologues with 3, 4 and more phenyl groups with decreasing concentration with increasing the chain length. Also PMDI can be used in the resin component of it ⁇ inventive sealing compound.
  • the filler ⁇ free resin component contains a proportion of bisphenol Diglycidy- ether to the filler-free resin component in the range of 7 wt .-% to 30 wt .-%, preferably 9 wt .-% to 27 wt .-%.
  • Anat (groups) content (NCO content) in an advantageous manner Be ⁇ range between 15 wt .-% to 30 wt .-%, preferably 19 wt .-% to 27 wt .-% ( determined according to 2011-0506601-95D).
  • reaction accelerator any suitable compound or mixture of compounds by which the crosslinking reaction for forming a composite can be accelerated can be used. All compounds or mixtures of compounds can be used as a reaction accelerator, therefore, which are known as suitable catalysts or Accelerat ⁇ niger (reactive curing agent) for the crosslinking reaction.
  • suitable catalysts or Accelerat ⁇ niger (reactive curing agent) for the crosslinking reaction Tertiary amines and imidazoles are known as suitable catalytically active compounds. Examples of tertiary amines are tetramethylethylenediamine, dimethyloctylamine,
  • Suitable imidazoles are, for example, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 1, 2, 4, 5-tetramethylimidazole, 1-benzyl-2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4- methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (4,6-diamino-s-triazinyl-2-ethyl) -2-phenylimidazole.
  • onium salts preferably onium salts with N or P as the central atom.
  • onium salts are: tetraethylammonium chloride, tetraethylammonium bromide, octyltrimethylammonium bromide,
  • Benzyltrimethylammonium chloride tetrabutylphosphonium bromide, N-ethylmorpholinium bromide, 2-ethyl-4-methylimidazolium bromide, N-ethylmorpholinium tetraphenylborate, 1, 2-dimethylimidazolium tetraphenylborate and
  • Tetrabutylammonium tetraphenylborate Tetrabutylammonium tetraphenylborate.
  • Suitable reactive curing agents are, for example, those based on one or more (aliphatic, cycloaliphatic, heterocyclic) amine derivatives having two or more primary and / or secondary amine groups, such as one or more
  • Polyamine s
  • modified polyamine s
  • polyamidoamine s
  • amine reaction accelerators e.g., based on tertiary amines
  • amine reaction accelerators are used for instant gelation or latent catalysts. This allows gelation at temperatures between 60 ° C and 120 ° C (eg at 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C , 100 ° C, 105 ° C, 110 ° C, 115 ° C, 201 ° C).
  • latent (curing) catalysts are meant those which ensure a sufficient service life at low temperatures.
  • catalysts also referred to as latent reaction accelerators
  • addition complexes of boron trihalides are suitable with tertiary amines and imidazoles, eg.
  • arylaliphatic radicals which may be in pairs of heterocyclic rings. Also suitable are the analogous complexes of boron trifluoride of the formula
  • BF 3 • NR 1 R 2 R 3 where R 1 , R 2 and R 3 have the abovementioned Be ⁇ meanings.
  • suitable tertiary amides ne of the BF 3 and BCl 3 complexes are octyldimethylamine and dimethylbenzylamine.
  • N-methylmorpholine N-ethylmorpholine, 1, 2-dimethylimidazole and l-benzyl-2-phenylimidazole are suitable for the formation of BCI3- and / or BF 3 complexes.
  • An extension of the service life can also be achieved if tertiary amines or imidazoles are used as latent catalysts ⁇ ren, which are deactivated by the addition of electron acceptors.
  • Suitable electron acceptors are, for example, 7,7,8,8-tetracyanoquinodimethane, 2, 3-dichloro-5,6-dicyanobenzoquinone and 2, 3, 5, 6-tetrachlorobenzoquinone.
  • Blendurkat 3-4523 (contains dibenzylmethylamine; Bayer AG) as commercially available examples of suitable Reakti ⁇ onsbevanter mentioned Blendurkat 901 K may be mentioned here 33rd
  • the reaction accelerator may preferably be incorporated at a level of from 0.5% to 15%, preferably from 3% to 10% by weight, based on the weight of the filler-free resin component.
  • the filler-free Harzkompo ⁇ nente is thus preferably from 7 wt .-% to 30 wt .-%, preferably 9 wt .-% to 27 wt .-% bisphenol-diglycidyl ether, 0.5 wt .-% to 15 wt. %, preferably 3 wt .-% to 10 wt .-% reaction accelerator, and 55 wt -.% To 92.5 wt. ⁇ 6 of at least one constitutional isomer of
  • the potting compound of the invention comprises a filler component, wherein the proportion of the filler component in the total weight of the potting compound 50 wt .-% to 95 wt .-%, preferably 60 wt .-% to 90 wt .-%, particularly preferably
  • the filler be ⁇ tains a first filler fraction, the first filler material fraction native and / or epoxy-functionalized, amor ⁇ PHEs fused silica with a value for the mean
  • Particle diameter is in the range of 10 nm to 1000 ym.
  • the first filler fraction thus has an average particle diameter (d 5 o%) selected from a value comprised in the range of 10 nm to 100 ym.
  • the lower limit of the stated range may also be 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm or 1000 nm.
  • the upper limit of angege ⁇ surrounded region may also ym 900, 800 ym, 700 microns, 600 ym, 500 ym, 400 ym, 300 ym, 200 ym or 100 ym amount.
  • the ranges encompassed by the present invention can be formed by a combination of any of the lower and any of the upper limits given.
  • epoxy-functionalized amorphous silica is preferred.
  • a filler is prepared by the oxide surface of the filler particles ⁇ is saturated with a coupling reagent to Epoxysilanbasis.
  • the surface of the filler ⁇ particles covalently reacts with the Silanteil of the coupling reagent.
  • the result is usually a free, pointing away from the surface of the filler oxirane per Kupplungsmole ⁇ kül.
  • These oxirane units can then react with the (P) MDI.
  • the filler particles disperse significantly better into the resin.
  • LCTE linear thermal expansions
  • LCTE which corresponds to that of steel, ie about 12 ppm / ° C, ideal. Since the unfilled polymer usually has a LCTE of 60-100 ppm / ° C ⁇ , a filler having a particularly low LCTE must be ⁇ be introduced. Commercial and cheap fillers are quartz. A distinction is made here between crystalline quartz (so-called quartz powder) and amorphous quartz (fused silica, fused silica). The latter has an LCTE of 0.6 ppm / ° C, while quartz flour 12-14 ppm / ° C. Are you, for example, 61 wt.
  • the invention provides for advantageously combining two or three filler fractions having different particle diameters.
  • fillers are combined with one another in such a way that a filler fraction of smaller diameter fills the gussets of a type which is larger in the particle diameter.
  • the average particle diameter of the first, second and third filler fraction lies in the microscale range, ie has a value in the range from 1 .mu.m to 1000 .mu.m
  • a filler particle diameter optimization is advantageous. It is therefore provided according to an advantageous development of the invention that in the case of a bimodal filler component, wherein the first and second filler fraction each have a value for the average particle diameter from the range of 1 ym to 1000 ym, the average particle diameter of the particles of the second Filler fraction by a factor of 2.5 to 15 is smaller than the average particle ⁇ diameter of the first Grestofffr syndrome.
  • the mean particle diameter of the second filler fraction is preferably smaller by a factor of 6-8 (factor 6, 7 or 8) than the mean particle diameter of the first filler fraction.
  • filler particle diameter is achieved when the filler component contains the first and second filler fractions in a range of from 80% by volume to 20% by volume to 60% by volume to 40% by volume, with the first Filler fraction in the filler component with the higher specified vol. -% - Share is included.
  • Such a powder mixture could then at ⁇ example as 61 wt .-% strength in admixture 39 wt .-% filler material ⁇ clear resin matrix disperse, wherein nied- significantly complicated viscosities would be obtained than with a monomodal filler.
  • the casting compound according to the invention a third filler fraction having a value for the average particle diameter from the range of 10 nm to 1000 ym, preferably 100 nm to 150 ym.
  • a trimodal (three-component) filler component is realized.
  • the third filler fraction s a value for the mean particle diameter in the range of 1 ym to 1000 ym, it is advantageous when the mitt ⁇ sized particle diameter of the third filler fraction by a factor of 2.5 to 15, preferably the factor 6-8 (factor 6, 7 or 8) is smaller than the mean particle diameter of the second filler fraction.
  • a filling Material particle diameter optimization be advantageous in which the average particle diameter of the second filler component by a factor of 2.5 to 15 (preferably by a factor of 6 to 8) is smaller than the average particle diameter of the first Grestofffr syndrome, and the average particle diameter of the third filler third by a factor of 2.5 to 15 (preferably by a factor of 6 to 8) is smaller than the mean ⁇ re particle diameter of the second filler fraction.
  • each of the filler fractions should have an average particle diameter in the range from 1 .mu.m to 1000 .mu.m
  • powders with suitable mean particle diameters are selected for the individual filler components.
  • a first filler fraction having a mean particle diameter must be selected by dividing by the factor for the second filler ⁇ fraction remains a value of at least 1 ym for the mean particle diameter.
  • the average particle diameters for a trimodal filler component must be chosen.
  • a mean particle diameter of not smaller than 6.25 ym can be selected.
  • a trimodal filler filling the first ⁇ material fraction is preferably in a range of 60 vol .-% to 80 vol .-% in the filler component included.
  • the second and third filler fraction are present in their total with up to 100 vol .-% missing share.
  • the trimodal filler component may be about 70% by volume of a powder having a mean particle diameter of 700 ⁇ m, about 21% by volume of a powder having a mean particle diameter of 100 ⁇ m powder and about
  • Another example of a trimodal filler may comprise about 67 vol .-% of a powder having an average Parti ⁇ kel penmesser of 105 ym, about 10 vol .-% of a powder having an average particle diameter of about 38 .mu.m and about 23 vol .-% of a Powder with a mean particle diameter of 1.4 ym included.
  • the mean particle diameter of the first filler fraction is in the range of 1 ⁇ m and 1000 ⁇ m
  • the second or third filler fraction has particles with a mean particle diameter in the nanoscale range, that is in the range from 10 nm to 999 nm, 10 nm to 900 nm, 10 nm to
  • 800 nm, 20 nm to 700 nm, 20 nm to 600 nm, 20 nm to 500 nm, 20 nm to 400 nm, 20 nm to 300 nm, 20 nm to 200 nm or 20 nm to 100 nm, is basically not a particle diameter Server optimization required.
  • the mean particle diameter of "nanoparticles" in the specified range and given size ratio can be chosen practically arbitrary, since nanoparticles always fit in the gussets of the larger particles, ie by the addition of nanoparticles can always be achieved a lowering of the viscosity.
  • powder fractions always have a certain particle size distribution, so that the proportions can vary depending on the powder fractions used.
  • a total together it is desirable to provide a packing coefficient-optimized te filler component with a packing coefficient min ⁇ least 77 vol .-%, preferably of more than 80 vol .-% (ermit ⁇ telt by Lee ID; Journal of Paint Technology 42, no. 550 (1970), 579). The higher the degree of filling of the powder mixture, the stiffer and more resistant to fracture the Automatkomposit.
  • the second filler fraction and the third filler fraction may each be selected from any suitable powder or powder mixture.
  • the second filler fraction is selected from at least one member of the group consisting of native amorphous fused silica, epoxy-functionalized amorphous fused silica, quartz flour, alumina, dolomite, chalk, glass beads, boron nitride, wollastonite (acicular), zeolite and polysiloxane, and is the third filler fraction selected from at least a member of the group consisting of native amorphous fused silica, epoxy-functionalized amorphous fused silica, alumina, zeolite and polysiloxane.
  • amorphous native or epoxy-functional fused silica is preferred.
  • the use of one or more zeolites in the second and / or third filler fraction is also advantageous. It is possible to use expansive fillers (such as e.g.
  • Fused silica with thermally contracting fillers (such as zeolites).
  • thermally contracting fillers such as zeolites.
  • the inventors of the present invention were able to produce epoxy resin composites having an LCTE of about 16 ppm / ° C, which corresponds to the expansion of copper, through a combination of one or more thermally contracting fillers and one or more thermally expanding fillers. As a result, the risk of cracking due to thermal shock can be significantly reduced or even eliminated.
  • a temperature-stable polymeric filling ⁇ material is used as the second and / or third filler fraction, for example a temperature-stable polysiloxane in powder form.
  • the viscosity of the mixture decreases and at the same time the fracture resistance of the finished composite ⁇ increased.
  • the reason could be that the relatively "soft" polysiloxane particles (compared to other, “harder” particles) have a positive effect on the crack resistance.
  • an addition amount of about 0.1 wt% to 15 wt%, preferably 1 wt% to 10 wt% based on the total mass of the filler component may be sufficient.
  • the inventive molding compound can be a fused silica for example, in an advantageous manner as the first filler fraction, preferably an epoxy-functionalized fused silica, with ei ⁇ nem value for the mean particle diameter of the loading range from 100 ym to 200 ym, as the second filler fraction is a polysiloxane powder having an Value for the average particle diameter from the range of 30 ym to 65 ym, and as a third filler fraction a fused silica, preferably an epoxy-functional fused silica, be used with a value for the average particle diameter in the range of 12 ym to 25 ym.
  • the first filler fraction (fused quartz, preferably an epoxy-functionalized fused silica, with a value for the mean particle diameter in the range of 100 ym to 200 ym) with a proportion of about 60 vol .-% to 70 vol .-%
  • the second filler fraction (polysiloxane powder having a value for the mean particle diameter from the range of 30 ym to 65 ym) in a proportion of about 5 vol .-% to 10 vol.
  • a multimodal filling ⁇ material component comprises at least a first filler fraction native and / or epoxy-functionalized amorphous fused silica, and as a second filler fraction is a member selected from the group consisting of native amorphous fused silica, epoxyfunk- tionalinstrumentem amorphous fused silica, quartz powder, alumina, dolomite, Chalk, glass beads, boron nitride and wollastonite.
  • the particles in the first and second filler fractions preferably have a substantially spherical (globular) form.
  • SILBOND 126 EST is Quarzwerke GmbH.
  • This epoxy-functionalized quartz powder has an upper grain size d 95 % of 94 ym and a mean grain size dso % of 22 ym.
  • the multi-modal filler component according to this example comprises a third filler fraction comprising polysiloxane particles having a particle diameter of about 100 nm to 150 ⁇ m.
  • the third filler fraction may also be formed from such a micro-scale and a nanoscale portion.
  • the proportion of the polysiloxane filler fraction in the total amount of the filler component is according to this preferred example between 0.1 wt .-% and 15 wt .-%, preferably between 1 wt .-% and 10 wt .-%, more preferably between 1 wt .-% and 5 wt .-%.
  • the multimodal filler component according to this preferred example has a maximum packing coefficient (determined by Lee ID) of 77 vol.% Or higher, about 78 vol.%, 79 vol.%, 80 vol.%, 81 vol. %, 82 vol.% Or 83 vol.%.
  • the proportion of the filler component in the total amount of potting compound is in this preferred example of 60 wt .-% to 80 wt .-%.
  • polysiloxane particles to the resin component can be accomplished in any suitable manner. For example, with the help of one or more epoxy batches
  • deagglomerated polysiloxane particles are introduced.
  • suitable example of this is mentioned KANE ACE ® MX 960 from Kaneka Texas Corporation.
  • polysiloxane particles may suitably be accomplished by incorporation of dry polysiloxane powder.
  • suitable example is the impact-modified additive is RES IN MODIFIER 4-7081 ® DOW CORNING Corporation mentioned.
  • thermoset test pieces sattgel ⁇ ben appearance The specimens were examined for electrical, fracture and thermomechanical characteristics. The results are shown in the table below.
  • Prepolymer encapsulants with different filler content were characterized viscometrically by Searle geometry at 80 ° C. The dynamic viscosities of these quartz-filled, prepolymeric potting compounds are shown in the figure.
  • the usable for the inventive molding compound resin ⁇ components, curing components and fillers are either commercially available or can be easily prepared even by mixing appropriate commercially available starting materials by a skilled artisan.
  • Thermal class H / 200 ° C (thermal class N) materials are known to the person skilled in the art and have been used for a long time to prepare highly heat-resistant laminate composites, in particular in traction machines. These include, for example, the additive-crosslinking, thermosetting silicone resins and / or polyester resins for the mentioned impregnation and impregnation applications. These materials have the disadvantage that they are not tempering ⁇ bar in thick layers without generating cracks. Polyester resins, for example, show pronounced brittleness due to their reaction shrinkage and are therefore only usable for drizzling and impregnation of mica laminates.
  • Silicone resins are characterized by the fact that they possess na ⁇ hezu no reaction shrinkage. Due to the high thermal expansion, however, they are unusable for the casting of large components. For acceptable gelling Tempe ⁇ temperatures are to be applied of at least 160 ° C, followed by a 12 to 16 hour curing period. When cooled to room temperature, the encapsulated insulation shrinks to considerable extent according to the zugrun ⁇ de roofing, thermal expansion coefficient. Since silicone resins also have only low resistance to fracture mechanics, this process of cooling at steps and edges, eg at the groove exit or end winding area, leads to mechanical stresses which lead to the material being torn off and thus render the insulation at the field-concentrated part electrically unusable.
  • filler-enriched silicone resins have (linear) thermal expansion coefficients LCTE in the range of
  • thermosetting silicone resin with 50% by weight amorphous fused silica (LCTE about 0.6 ppm / ° C) in the cured state still shows a total LCTE of about 100 ppm / ° C. With a stator slot length of 500 mm, this corresponds to a thermal contraction of approx. 8 mm.
  • the LCTE values are much higher for the same filler loading, so that filling ratios of 80% by weight and / or higher are required for comparable composite expansions.
  • an in Tempe ⁇ ratur Scheme is the formulation of 60 to 80 ° C very good castable prepolymer provided that can be used as a sealing compound for a round and / or flat wire form coil Statorvollverguß in electrical machinery and after the thermal Curing represents an insulation material that has a classification in the thermal class 200 ° C according to IEC
  • a composite is re ⁇ alrote by the casting compound according to the invention, which has a glass transition temperature of 250 ° C or higher with low thermal expansion and is thus prevented that when heated to typical Be ⁇ operating temperatures (short-term up to 270 ° C) of the encapsulation - NEN, electrical machine, the dimensional stability of Isolati ⁇ onstechnikstoffs is lost. This is particularly important for ensuring the gap between Statornutausgang and rotor to avoid contacts during operation.
  • the potted coils must be permanently embedded to form an optimal, magnetic field at a defined distance of about 0.85 mm to the laminated core.
  • a potting compound which comprises a mixture of epoxy resins based on
  • formulations can be contacted with generally nitrogen-based reaction accelerators, in particular based on tertiary amines and / or latent catalysts for the reaction, with highly heat-resistant Formstof ⁇ fe result. Due to the relatively high content of filler, the thermal expansion of the cured composites with LCTE values of 30 ppm / ° C or less is very low, the dynamic processing viscosities of the prepolymers
  • Such prepared molding materials possess extraordinary part ⁇ discharge resistance, high volume resistance, low water absorption, high stiffness, acceptable fracture-mechanical and thermo-physical property characteristics such as excellent hydrolysis ⁇ .
  • the present invention provides a new and advantageous thermally cured composite obtainable from a potting compound according to the invention by polymerizing the resin component contained in the potting compound. Due to the invention available, thermally hardened ⁇ th composite new and advantageous electrical Ma ⁇ machines can be provided, which have at their stator and / or its end winding one invention shown SEN, thermally cured composite.

Abstract

L'invention concerne une masse de scellement, une utilisation de la masse de scellement, et un composite durci par voie thermique obtenu à partir de ladite masse de scellement. La masse de scellement comprend un composant à base de résine contenant un mélange composé au moins d'un éther de diglycidyle de bisphénol, au moins d'un isomère de constitution de diphénylméthane-diisocyanate ou d'un mélange de plusieurs isomères de constitution de diphénylméthane-diisocyanate et similaires à 3, 4 groupes phényles ou plus. La masse de scellement contient un composant de matière de charge présentant une première fraction de matière de charge. La première fraction de matière de charge étant un produit en quartz natif et/ou amorphe à fonction époxy, la valeur de la granulométrie moyenne de ce dernier étant comprise dans la plage allant de 10 nm à 1000 µm. Le composant de matière de charge présente au moins une deuxième fraction de matière de charge. Cette dernière est choisie parmi au moins un élément du groupe comprenant le produit en quartz natif amorphe, le produit en quartz amorphe à fonction époxy, la poudre de quartz, l'oxyde d'aluminium, la dolomite, la craie, les perles de verre, le nitrure de bore, la wollastonite, la zéolite et le polysiloxane, dont la granulométrie moyenne présente une valeur comprise dans la plage allant de 10 nm à 1000 µm. La granulométrie moyenne de la deuxième fraction de matière de charge est inférieure d'un facteur de 2,5 à la granulométrie moyenne de la première fraction de matière de charge.
PCT/EP2014/055414 2013-03-22 2014-03-18 Masse de scellement, utilisation de la masse de scellement et composite durci par voie thermique obtenu à partir de la masse de scellement WO2014147072A1 (fr)

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US10224779B2 (en) 2014-10-02 2019-03-05 Regal Beloit America, Inc. Electric machine, barrier and associated kit
WO2020174009A1 (fr) 2019-02-27 2020-09-03 Covestro Intellectual Property Gmbh & Co. Kg Matériaux de polyisocyanurate comme masses de scellement électriques
WO2020193323A1 (fr) * 2019-03-27 2020-10-01 Siemens Aktiengesellschaft Résine de coulée, matériau de moulage obtenu à partir de cette dernière, son utilisation et une isolation électrique
CN113583390A (zh) * 2021-09-08 2021-11-02 深圳先进电子材料国际创新研究院 一种环氧基封装材料增韧改性的方法

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US10224779B2 (en) 2014-10-02 2019-03-05 Regal Beloit America, Inc. Electric machine, barrier and associated kit
WO2020174009A1 (fr) 2019-02-27 2020-09-03 Covestro Intellectual Property Gmbh & Co. Kg Matériaux de polyisocyanurate comme masses de scellement électriques
CN113631545A (zh) * 2019-02-27 2021-11-09 科思创知识产权两合公司 作为电灌封料的聚异氰脲酸酯材料
WO2020193323A1 (fr) * 2019-03-27 2020-10-01 Siemens Aktiengesellschaft Résine de coulée, matériau de moulage obtenu à partir de cette dernière, son utilisation et une isolation électrique
CN113583390A (zh) * 2021-09-08 2021-11-02 深圳先进电子材料国际创新研究院 一种环氧基封装材料增韧改性的方法

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