Classifications

• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/06—Unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/06—Unsaturated polyesters
  • C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
  • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• the present invention relates to a impregnating resin formulation for electric machines.
• the impregnation of electrical windings is a standard process in the manufacture of electric machines.
• the hardened impregnating resin has the task of mechanically fixing the winding, protecting it against aggressive chemicals and environmental influences, dissipating the heat formed and electrically insulating it.
• EP 0 968 501 describes liquid comonomer-free curable unsaturated polyester-containing formulations which are also UV-curable.
• the unsaturated polyester contains dicyclopentadiene and maleic acid structures.
• these formulations have a relatively high viscosity (higher than 2600 mPas). This is an obstacle for processing on common systems.
• EP 1 122 282 also describes comonomer-free curable unsaturated polyester resin-containing formulations. They consist of unsaturated polyesters based on maleic acid and dicyclopentadiene and is used. The viscosities of the resin mixtures are sometimes very high.
• the formulations have the disadvantage that resins and polymers crosslinkers can not be mixed arbitrarily, since the polymeric crosslinker is not curable by itself.
• the present invention has for its object to develop a low-viscosity, a comonomer-free unsaturated polyester resin-containing formulation which is free from solely non-curing polymeric crosslinkers and which is suitable for impregnating electrical windings.
• component B containing a dicyclopentadiene terminated unsaturated from component A, unsaturated polyester resin
• Low-viscosity impregnating resin formulations in the context of the present invention preferably have a viscosity of less than or equal to 1500 mPas, measured at 25 ° C.
• Particularly preferred impregnating resin formulations have a viscosity of between 600 and 1300 mPas inclusive, more preferably between 850 and 1200 mPas measured at 25 ° C.
• the present in component A allylether restroomn unsaturated polyester resins preferably contain an unsaturated polyester resin or a mixture of unsaturated polyester resins, which are composed of Trimethylolpropanmono- and / or Trimethylolpropandiallylether, glycols, maleic acid, and other known from unsaturated polyester resin chemistry components.
• the so constructed Polyester resins may be modified according to the invention with imide structures, dicyclopentadiene structures, with isocyanates and / or melamine resins.
• These resins are known (see, for example, Brochure No. 0207 by Perstorp, DE 2645657, DOS 2113998) and can be prepared by the reaction of allyl ethers, polyols, carboxylic acids and also monofunctional molecules as chain terminators.
• the preparation of these resins is also well known.
• the components are usually heated to temperatures between 160 and 200 ° C with or without esterification catalyst.
• the reaction is usually carried out under protective gas.
• an azeotrope and / or vacuum can be used.
• the control of the condensation process is usually carried out by the determination of the acid number and / or the condensation viscosity.
• Trimethylolpropanmono-, Trimethylolpropandi-, Pentaerythrittriallyether can be used. All three are preferred, alone or in different mixtures.
• polyols are ethylene glycol, di- and triethylene glycol, neopentyl glycol, 1, 3- and 1, 6-hexanediol, perhydrobisphenol-A, glycerol, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, penaterythritol, dipentaerythritol.
• Preference is given to di- and triethylene glycol, neopentyl glycol and trimethylolpropane.
• carboxylic acids are used alpha.beta-unsaturated dicarboxylic acids or derivatives such as maleic acid and fumaric acid and their mixtures with modifying dicarboxylic acids such as adipic acid, succinic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid. Preference is given to maleic anhydride and adipic acid.
• chain terminators monofunctional carboxylic acids and / or monofunctional alcohols are used, for example, tall oil fatty acid, benzoic acid, 2-ethylhexanoic acid, hexanol, 2-ethylhexanol, benzyl alcohol, tert-butanol, isoprenol (3-methyl-3-buten-1-ol), the reaction product of tetrahydrophthalic anhydride with ethanolamine.
• Preference is given to hexanol, isoprenol and the reaction product of tetrahydrophthalic anhydride with ethanolamine.
• the component B can consist of at least one binder other than component A, which is described in EP 0 968 501 and / or in EP 1 122 282.
• the unsaturated polyester resin having dicyclopentadiene structures other than component A present in component B may be e.g. by the addition of maleic acid and dicyclopentadiene, glycols, maleic acid and other components known from unsaturated polyester resin chemistry.
• the component C may contain a commercially available unsaturated polymer.
• These polymers are commercially available under trade names such as Laromer PO 33F, Sartomer SR 9045 or Sartomer CD 9021 or polyethylene glycol divinyl ethers.
• the unsaturated polymer present in component C can be prepared by functionalizing existing polymers with double bond containing molecules, such as the reaction product of a carboxylic acid terminated polyacrylate with glycidyl methacrylate, or a polyether polyol with an unsaturated isocyanate.
• polymeric vinyl ethers such as, for example, polyethylene glycol divinyl ethers of different molecular weight can be used.
• the impregnating resin formulation according to the invention may comprise 1. 40-95% by weight of allyether-containing unsaturated polyester resin (component A), preferably 50.0-90% by weight, particularly preferably 60-80% by weight 2. 5.0-60% by weight. % dicyclopentadiene-terminated unsaturated polyester resin (component B), preferably 8.0-40% by weight, particularly preferably 10-30% by weight 3. 1, 0-30% by weight unsaturated polymer (component C), preferably 1 , 0 - 20% by weight, particularly preferably 1, 0 - 10 wt .-% 4. 0.1 - 5 wt .-% hardeners, accelerators, stabilizers, additives, rheology additives, preferably 0.5 -4 wt. %, particularly preferably 1 to 3 wt .-%, wherein the percentages are in each case based on the complete Tränkharzformulmaschine. consist.
• the three components A, B, C are preferably first mixed and formulated with the usual hardeners, accelerators, stabilizers and additives. This gives formulations which, depending on the composition, have low viscosity, good curing behavior and cured homogeneous moldings with excellent mechanical, electrical and thermal properties.
• the impregnating resin formulation according to the invention is accordingly preferably prepared by mixing components A, B and C, while the additives to curing agents, accelerators, stabilizers, additives, rheology additives are preferably added at the end.
• peroxides As hardeners, peroxides have proven useful, e.g. Dicumyl peroxide and tert-butyl perbenzoate as well as silylated benzpinacols.
• photoinitiators such as phosphine oxides and ketals
• the formulation can be UV-cured.
• Accelerators are metal soaps, e.g. Cobalt, vanadium and zirconium octoates or naphthenates.
• alkylated phenols As stabilizers, alkylated phenols, hydroquinones and benzoquinones, e.g. 2,4-di-tert-butylphenol or methylhydroquinone.
• Additives are the course and surface additives known to the person skilled in the art. Fumed silicas, bentones and polymeric ureas have proven to be useful as rheological additives. It is hereby referred to the paint manuals.
• the impregnating resin formulation according to the invention is liquid at room temperature, low viscosity and free from comonomers. It can be processed on the usual processing equipment, for. As by dipping, trickling, Tauchrollieren, casting and by vacuum and vacuum pressure impregnation of electrical windings.
• the impregnating resin formulation is cured.
• This may be a thermal cure. This can be achieved either in an oven or by the current heat of the winding or by the combination of these possibilities.
• the curing can also be achieved by means of radiation, preferably by means of UV radiation.
• the impregnating resin formulation is provided with a photoinitiator, it can be cured on the laminated core by means of UV light.
• the combination of thermal curing and UV light curing in particular if curing is provided directly on the laminated core. This also allows the simultaneous use of current heat and UV light for curing.
• the impregnating resin formulation according to the invention can also be used for the coating of printed circuit boards in electronics, hybrids, SMD modules, and assembled printed circuit boards, or be used as a base material for flat insulating materials.
• Example 3 Preparation of an allyl ether-modified unsaturated polyester resin 3 First, 271 g of maleic anhydride, 17 g of water and 130 g of dicyclopentadiene are reacted in a standard three-necked flask apparatus. Then, the precursor is reacted analogously to Example 1 with 208 g of triethylene glycol, 48 g of neopentyl glycol, 120 g of 2-ethylhexanol and 197 trimethylolpropane diallyl ether at 190 ° C. The resulting resin has an acid number of 24 mg KOH / g and a viscosity of 12 Pas.
• stator size 90, immersed and cured at 150 ° C for 1 hour.
• the dripping loss during oven curing was exceptionally low.
• the stator is then sawed and visually inspected for resin absorption and impregnation quality.
• the stator was perfectly impregnated and the winding was saturated with resin.
• the formulation has a viscosity of 1200 mPas, a gel time of 3 minutes at 120 ° C.
• drill rods are impregnated according to IEC 61033 (method A) and after hardening (1 hour at 160 ° C.) the caking strength is determined. It is at 155 ° C 51 N.
• Example 4 The resin of Example 4 is activated with 2% dicumyl peroxide. The viscosity is 8 Pas. A size 90 stator is dipped therein and cured at 160 ° C for 1 hour. The stator is then sawed and visually inspected for resin absorption and impregnation quality. The resin absorption is significantly lower than that in Examples 5 to 7.
• Example 1 The resin of Example 1 is tert with 3%. Butyl perbenzoate activated. The viscosity is 20 Pas. A size 90 stator is dipped therein and cured at 160 ° C for 1 hour. The stator is then sawed and visually inspected for resin absorption and impregnation quality. The resin absorption is significantly lower than that in Examples 5 to 7.
• Laromer PO 33 F is tert with 2%. Butyl perbenzoate activated and a stator of size 90 is impregnated with it and cured at 130 ° C for 1 hour. The stator is then sawed and visually inspected for resin absorption and impregnation quality. The resin bursts from the winding heads and breaks in the winding.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Dental Preparations (AREA)
• Reinforced Plastic Materials (AREA)
• Polymerisation Methods In General (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Pens And Brushes (AREA)
• Secondary Cells (AREA)
• Organic Insulating Materials (AREA)
• Insulation, Fastening Of Motor, Generator Windings (AREA)

Priority Applications (10)

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Citations (7)

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• 2004
  • 2004-06-11 DE DE102004028417A patent/DE102004028417A1/de not_active Ceased
• 2005
  • 2005-06-08 EP EP05754530A patent/EP1753820B1/de not_active Expired - Lifetime
  • 2005-06-08 CN CN2005800117476A patent/CN1942520B/zh not_active Expired - Lifetime
  • 2005-06-08 JP JP2007526436A patent/JP2008501841A/ja active Pending
  • 2005-06-08 SI SI200530647T patent/SI1753820T1/sl unknown
  • 2005-06-08 WO PCT/EP2005/052703 patent/WO2005121246A1/de not_active Ceased
  • 2005-06-08 US US11/629,155 patent/US20080064809A1/en not_active Abandoned
  • 2005-06-08 DK DK05754530T patent/DK1753820T3/da active
  • 2005-06-08 PL PL05754530T patent/PL1753820T3/pl unknown
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  • 2005-06-08 KR KR1020067022895A patent/KR101198565B1/ko not_active Expired - Lifetime
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