WO1998032138A1 - Compositions electriques isolantes a base de resines hybrides contenant de l'epoxyde et du silicone - Google Patents
Compositions electriques isolantes a base de resines hybrides contenant de l'epoxyde et du silicone Download PDFInfo
- Publication number
- WO1998032138A1 WO1998032138A1 PCT/HU1998/000007 HU9800007W WO9832138A1 WO 1998032138 A1 WO1998032138 A1 WO 1998032138A1 HU 9800007 W HU9800007 W HU 9800007W WO 9832138 A1 WO9832138 A1 WO 9832138A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- epoxy
- composition according
- resin based
- based composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 title abstract description 20
- 239000011347 resin Substances 0.000 title abstract description 20
- 238000009413 insulation Methods 0.000 title description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000004971 Cross linker Substances 0.000 claims abstract description 15
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000654 additive Substances 0.000 claims description 27
- 230000000996 additive effect Effects 0.000 claims description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 11
- 230000003628 erosive effect Effects 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000010428 baryte Substances 0.000 claims description 2
- 229910052601 baryte Inorganic materials 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- XPXMKIXDFWLRAA-UHFFFAOYSA-N hydrazinide Chemical compound [NH-]N XPXMKIXDFWLRAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims 2
- 229920002379 silicone rubber Polymers 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000005266 casting Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 238000001879 gelation Methods 0.000 abstract 1
- 238000009472 formulation Methods 0.000 description 12
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- -1 dimethyl siloxane Chemical class 0.000 description 7
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 2
- 238000005102 attenuated total reflection Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920006301 statistical copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UOCIZHQMWNPGEN-UHFFFAOYSA-N dialuminum;oxygen(2-);trihydrate Chemical compound O.O.O.[O-2].[O-2].[O-2].[Al+3].[Al+3] UOCIZHQMWNPGEN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002188 infrared transmission spectroscopy Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators 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
- H01B3/46—Insulators 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 silicones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators 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
- H01B3/40—Insulators 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 epoxy resins
Definitions
- the invention relates to an insulating composition the resin component of which contains reactive silicone oligomers besides epoxy resin and other, known components, so it unites the advantageous properties of both insulating materials.
- silicones and silicone rubber based composite insulators gradually gain leading role in outdoor insulation.
- the main reason for this is the hydrophobicity of silicone rubber, which prevents the formation of a continuous water film on the insulator surface, thus reducing the leakage current, and the erosion caused by dry band arcing.
- One of the advantages of silicone rubbers is that this hydrophobic property is stable for a long time, moreover, if it is destroyed temporally due to weather circumstances or to discharges, it gradually recovers afterwards.
- the reason for this hydrophobic recovery is in part the migration (diffusion) of low molecular silicone oils to the surface, and in part the re-orientation of the silicone chains located at the surface.
- JP 05271518 e.g. uses a mixture of alkyphenol-polysiloxane block copolymers with bisphenol- A type epoxy resins.
- JP 05301931 proposes a mixture of siloxane grafted vinyl polymers in combination with cresol- or novolak type epoxy resins.
- JP 05160173 reacts maleimide end-functionalized siloxane with epoxidized polybutadiene.
- JP 05105778 combines carboxyl end functionalized nitrile rubber with amine end- functionalized siloxane and epoxy, and there are further examples. All these compositions use special, commercially not available components.
- thermoset resins can unite the advantageous properties of both components (see e.g. the urethane - unsaturated polyester hybrids). These are not physical mixtures, as e.g. the blends of thermolpastics, but copolymers (block or statistical copolymers).
- R' is a saturated hydrocarbon chain.
- R' is a saturated hydrocarbon chain.
- other structures can also be easily synthesized which contain the epoxy group in the side chain, such as: Q'-0-[SiR-0] n -[SiR 2 -0] m -Q"
- R is an alkyl group
- Q' and Q" can be trimethyl silyl group (-SiMe 3 ) or an -R'-X group, where R' is a saturated hydrocarbon chain and X is a glycidoxyl group:
- the invention proposes a group of hybrid resins characterized by mixture of traditional epoxy resins with siloxane oligomers containing epoxy functional groups and with a calculated amount of crosslinker.
- the invention relates to epoxy resin based insulating composition with improved hydrophobicity and electrical erosion resistance that comprises a cycloaliphatic or aliphatic (or aromatic) epoxy resin, a cycloalpihatic (or aromatic) anhydride (perhaps amine or poly amino-amide) crosslinker comprising a silicone additive containing epoxy groups, occasionally in combination with polymeric active diluent (flexibilizer), reinforcing (Aerosil, wollastonite, chopped glassfiber) and/or non-reinforcing (silica, ATH, calcium carbonate, baryte) fillers and a mobile silicone oil, not bound to the network.
- a cycloaliphatic or aliphatic (or aromatic) epoxy resin a cycloalpihatic (or aromatic) anhydride (perhaps amine or poly amino-amide) crosslinker comprising a silicone additive containing epoxy groups, occasionally in combination with polymeric active diluent (flexibilizer), reinforcing (Aerosil, wo
- the siloxane oligomer containing epoxy functional groups is preferably a polysiloxane (wherein R may be methyl or phenyl) with the glycidyl group attached in the following way:
- R' is a saturated hydrocarbon chain with 1-10, preferably with 3- 4 carbon atoms and n, the degree of polymerization is between 1 and 50, preferably between 5 and 15, or a polysiloxane having the following formula:
- R is methyl or phenyl, m+n, the degree of polymerization is between 1 and 50, preferably between 5 and 15, m is between 1 and 5, preferably 1 or 2,
- Q' or Q" may be trimethyl silyl group (-SiMe 3 ) or an - R'-X group, where R' is a saturated hydrocarbon chain with 1-10, preferably with 3-4 carbon atoms and X is the glycidoxyl group: -0-CH 2 -CH-CH 2
- the resin and the crosslinker components are miscible with the siloxane oligomer.
- the selection of such components is by no means trivial, as, due to the extremely low cohesion energy density of polysiloxanes, they are not miscible with all organic liquids. If the siloxane oligomer is miscible with the crosslinker but not with the epoxy resin then the siloxane phase may crosslink separately from the epoxy matrix. This is called macroscopic phase separation (two layers of separated materials appear), which results in a technically unacceptable product. One has to distinguish this situation sharply from micro phase separation, which occurs during block copolymer synthesis.
- the epoxy component is advantageously cycloaliphatic epoxy and the crosslinker is a cycloaliphatic anhydride (both low viscosity liquids at room temperature).
- the crosslinker is a cycloaliphatic anhydride (both low viscosity liquids at room temperature). If the epoxidized siloxane is mixed with the cycloaliphatic epoxy in a ratio of 1 :9 and is crosslinked with a calculated amount of crosslinker, then a polymer with siloxane-like surface properties is obtained.
- the electrical erosion resistance can be improved by the addition of aluminum oxide trihydrate (ATH) filler and the flexural modulus and the tensile strength can be substantially increased by anisometric fillers (chopped glassfiber, wollastonite or other, whiskerlike filler).
- Cheap, extender fillers (as e.g.
- silica or calcium carbonate can reduce the price.
- This composition can be a competitor of traditional, silica filled cycloaliphatic casting resins.
- the hybrid resin is a load-bearing component, which can be fixed onto the electrical network through embedded metal fittings.
- the advantage of this composition over the traditional casting resins is the silicone rich, hydrophobic surface, which can recover its hydrophobicity after oxidation.
- compositions containing both epoxidized silicone oligomer (immobile silicone component) and a low molecular silicone oil (mobile silicone component) are also possible.
- the immobile silicone component by itself ensures the required surface properties and the hydrophobic recovery after surface oxidation, but, if a mobile silicone component is also present then the even the inorganic deposit (dust etc.) on the insulator surface becomes hydrophobic.
- the immobile silicone component plays an important role even in such compositions for two reasons.
- the mobile silicone component can be added to the epoxy resin only in a very limited amount, as, due to incompatibility problems it is easily exuded to the surface.
- B.) mobile silicone can be gradually depleted in the sample due to migration, but the immobile silicone content is stable.
- compositions which, in principle, could be used to replace silicone rubber in the manufacture of composite outdoor insulators.
- rigidity of the epoxy resin component can be reduced by the addition of active diluents (advantageously polymeric active diluents).
- Active diluents are special plasticizers, which are incorporated into the epoxy network and reduce its rigidity. Flexibilization is achieved either by reducing the degree of crosslinking (low molecular, monofunctional epoxy compounds) or by incorporating soft segments into the rigid network.
- polymeric active diluents is a glycidoxyl end functionalized polyether oligomer.
- polymeric active diluents are necessary for two reasons: a.) the siloxane network by itself is not too strong (although it can be considerably reinforced by the addition of silica gel of pyrolytic origin, e.g. Aerosil or Cab-O-Sil), therefore the increase of the siloxane/epoxy resin ratio does not yield a system of advantageous mechanical properties; b.) the siloxane oligomer is usually more expensive than the polymeric active diluent.
- the active diluent shall be chosen so that it is miscible with the siloxane oligomer and the other initial, liquid components.
- x is the weight of the epoxy resin
- ei is the specific epoxy content of the resin (mole epoxy group/100 g resin, which can be calculated from the epoxy equivalent, E by the following formula: 100 E)
- y is the weight of the epoxidized silicone
- e 2 is its specific epoxy content
- z is the weight of the active diluent
- e 3 is its specific epoxy content
- A is the specific functional group content of the crosslinker (e.g. anhydride) in mol/100 g units.
- Attenuated total reflectance (ATR) IR spectra which probe the top 0.1 ⁇ m thick layer of the sample, the ratio of the band intensities (baseline corrected peak absorbance values) attributable to the ester (1740 cm “1 ) and to the Si-Me (1260 cm “1 ) groups is roughly identical for all three compositions (a change of 20-30% can be observed), while the molar ratio of the ester/dimethyl silicone groups changes almost tenfold. This proves the 12 -
- composition of the 1 :1 mixture is identical with composition 3. of Example 2.
- the table also indicates the mode of failure (overcurrent without carbonization /tracking/, overcurrent with carbonization, overcurrent with fire).
- the basic, silica filled composition without silicone additive is not acceptable even at 3.5 kV. Dramatic improvement can be observed on addition of the silicone additive. The overcurrent appearing at 4.5 kV does not cause carbonization or fire, therefore it cannot be regarded as serious damage.
- An improvement can be observed if no silicone additive is used but ATH is added instead of silica as filler. In this latter case the arc-suppression ability of ATH is observed, not the effect of surface hydrophobicity. Both additives together are also effective, but from these formulations No. 9 proved to be the best.
- compositions described below contain the following components: CY184 cycloaliphatic epoxy resin (Ciba Geigy), HY1102 cycloaliphatic anhydride (Ciba Geigy), DY062 accelerator (Ciba Geigy), Tegomer ESi2130 epoxidized silicone (TH Goldschmidt AG), Eurepox RV-F polymeric active diluent (flexibilizer, Schering/WITCO), W12EST silica filler (Quarzwerke GmbH), ATH filler (methyl silane treated, Solem GmbH).
- Table 5. a shows the compositions of the compounds, while Table 5.b shows some physical quantities.
- Formulations 19 and 21 contain 0.1 wt% mobile silicone oil (polydimethyl siloxane with 100 cP viscosity). The 0.1 wt% is calculated for the organic components without mineral filler.
- Formulation 17 is the reference, formulation 18 contains the same amount, but mixed filler, formulation 19 contains mobile silicone oil but no epoxidized silicone additive, formulation 20 contains the epoxidized additive but no mobile silicone oil, while formulation 21 contains both types of silicones.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
La présente invention concerne une composition dont la particularité est la combinaison de matières présentant d'excellentes propriétés isolantes. Le coût plus faible et la facile transformabilité des résines d'époxyde s'associent à des propriétés de surface intéressantes (hydrophobie, récupération après la formation d'arcs électriques sur bande sèche) et à une bonne résistance aux intempéries des caoutchoucs silicone. La nouvelle composition peut être fabriquée par moulage à faible pression ou par gélification sous pression. En raison de sa faible viscosité, la résine de base peut supporter des charges importantes. Le composant silicone modifiant la résine d'époxyde n'est pas seulement un plastifiant, il est incorporé à l'intérieur de la structure en réseau et son effet est permanent. Les composants principaux de la composition sont de la résine d'époxyde cycloaliphatique, aliphatique (ou aromatique); un agent de réticulation cycloaliphatique (ou aromatique) anhydre (soit amine, soit polyamino-amide); un accélérateur, et un oligomère silicone contenant un groupe terminal époxy. Parmi les autres composants, on peut trouver un diluant (assouplissant) actif faiblement moléculaire ou macromoléculaire et une charge. En modifiant le rapport des composants, on peut produire plusieurs compositions allant d'une structure rigide et porteuse jusqu'à des structures molles à consistance de caoutchouc.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98902143A EP0896723A1 (fr) | 1997-01-21 | 1998-01-21 | Compositions electriques isolantes a base de resines hybrides contenant de l'epoxyde et du silicone |
| JP10534022A JP2001502470A (ja) | 1997-01-21 | 1998-01-21 | エポキシ―シリコーンハイブリッド樹脂ベース電気絶縁組成物 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU9700191A HU217112B (hu) | 1997-01-21 | 1997-01-21 | Epoxi-szilikon hibrid gyanta alapú villamos szigetelőkompozíciók |
| HUP9700191 | 1997-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998032138A1 true WO1998032138A1 (fr) | 1998-07-23 |
Family
ID=89994659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/HU1998/000007 WO1998032138A1 (fr) | 1997-01-21 | 1998-01-21 | Compositions electriques isolantes a base de resines hybrides contenant de l'epoxyde et du silicone |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0896723A1 (fr) |
| JP (1) | JP2001502470A (fr) |
| HU (1) | HU217112B (fr) |
| WO (1) | WO1998032138A1 (fr) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1176611A1 (fr) * | 2001-02-13 | 2002-01-30 | The Furukawa Electric Co., Ltd. | Fil isole |
| US6734361B2 (en) | 2000-02-10 | 2004-05-11 | The Furukawa Electric Co., Ltd. | Insulated wire |
| US6764616B1 (en) | 1999-11-29 | 2004-07-20 | Huntsman Advanced Materials Americas Inc. | Hydrophobic epoxide resin system |
| EP1303567B2 (fr) † | 2000-07-14 | 2007-09-05 | Abb Research Ltd. | Masse de remplissage a modification de volume a base de resine a matrice polymere |
| WO2008009560A1 (fr) * | 2006-07-20 | 2008-01-24 | Abb Research Ltd | Composition de résine époxy durcissable |
| WO2010112272A1 (fr) * | 2009-04-02 | 2010-10-07 | Huntsman Advanced Materials (Switzerland) Gmbh | Surmoulage direct |
| WO2010127693A1 (fr) * | 2009-05-05 | 2010-11-11 | Abb Research Ltd | Composition sol-gel durcissable |
| CN103319925A (zh) * | 2013-06-04 | 2013-09-25 | 常熟市九洲电器设备有限公司 | 一种高韧性和耐高低温电机用绝缘漆 |
| DE102018202058A1 (de) * | 2018-02-09 | 2019-08-14 | Siemens Aktiengesellschaft | Formulierung zur Herstellung eines Isolationssystems, elektrische Maschine und Verfahren zur Herstellung eines Isolationssystems |
| WO2019154933A1 (fr) * | 2018-02-09 | 2019-08-15 | Siemens Aktiengesellschaft | Isolation, machine électrique et procédé de réalisation de l'isolation |
| FR3091406A1 (fr) * | 2018-12-31 | 2020-07-03 | Centre National De Recherche Scientifique (Cnrs) | Matériau pour l’isolation électrique et procédé de fabrication |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306747A (en) * | 1988-04-05 | 1994-04-26 | Mitsubishi Denki Kabushiki Kaisha | Flexibilizers of hydroxyphenyl silicone oil-epoxy resin product and epoxy silicone oil-phenol resin product |
| US5358904A (en) * | 1988-09-20 | 1994-10-25 | Hitachi, Ltd. | Semiconductor device |
| EP0673957A2 (fr) * | 1994-03-04 | 1995-09-27 | Mitsubishi Denki Kabushiki Kaisha | Masse à mouler de résine époxyde |
-
1997
- 1997-01-21 HU HU9700191A patent/HU217112B/hu not_active IP Right Cessation
-
1998
- 1998-01-21 EP EP98902143A patent/EP0896723A1/fr not_active Withdrawn
- 1998-01-21 JP JP10534022A patent/JP2001502470A/ja active Pending
- 1998-01-21 WO PCT/HU1998/000007 patent/WO1998032138A1/fr not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306747A (en) * | 1988-04-05 | 1994-04-26 | Mitsubishi Denki Kabushiki Kaisha | Flexibilizers of hydroxyphenyl silicone oil-epoxy resin product and epoxy silicone oil-phenol resin product |
| US5358904A (en) * | 1988-09-20 | 1994-10-25 | Hitachi, Ltd. | Semiconductor device |
| EP0673957A2 (fr) * | 1994-03-04 | 1995-09-27 | Mitsubishi Denki Kabushiki Kaisha | Masse à mouler de résine époxyde |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6764616B1 (en) | 1999-11-29 | 2004-07-20 | Huntsman Advanced Materials Americas Inc. | Hydrophobic epoxide resin system |
| US6734361B2 (en) | 2000-02-10 | 2004-05-11 | The Furukawa Electric Co., Ltd. | Insulated wire |
| EP1303567B2 (fr) † | 2000-07-14 | 2007-09-05 | Abb Research Ltd. | Masse de remplissage a modification de volume a base de resine a matrice polymere |
| US7268181B2 (en) | 2000-07-14 | 2007-09-11 | Abb Research Ltd | Volume-modified casting compounds based on polymeric matrix resins |
| EP1176611A4 (fr) * | 2001-02-13 | 2002-09-25 | Furukawa Electric Co Ltd | Fil isole |
| EP1176611A1 (fr) * | 2001-02-13 | 2002-01-30 | The Furukawa Electric Co., Ltd. | Fil isole |
| WO2008009560A1 (fr) * | 2006-07-20 | 2008-01-24 | Abb Research Ltd | Composition de résine époxy durcissable |
| US8999433B2 (en) | 2009-04-02 | 2015-04-07 | Huntsman International Llc | Direct overmolding |
| WO2010112272A1 (fr) * | 2009-04-02 | 2010-10-07 | Huntsman Advanced Materials (Switzerland) Gmbh | Surmoulage direct |
| CN102388096A (zh) * | 2009-04-02 | 2012-03-21 | 亨斯迈先进材料（瑞士）有限公司 | 直接重叠注塑 |
| WO2010127693A1 (fr) * | 2009-05-05 | 2010-11-11 | Abb Research Ltd | Composition sol-gel durcissable |
| CN103319925A (zh) * | 2013-06-04 | 2013-09-25 | 常熟市九洲电器设备有限公司 | 一种高韧性和耐高低温电机用绝缘漆 |
| DE102018202058A1 (de) * | 2018-02-09 | 2019-08-14 | Siemens Aktiengesellschaft | Formulierung zur Herstellung eines Isolationssystems, elektrische Maschine und Verfahren zur Herstellung eines Isolationssystems |
| WO2019154933A1 (fr) * | 2018-02-09 | 2019-08-15 | Siemens Aktiengesellschaft | Isolation, machine électrique et procédé de réalisation de l'isolation |
| WO2019154932A1 (fr) * | 2018-02-09 | 2019-08-15 | Siemens Aktiengesellschaft | Formulation pour la fabrication d'un système d'isolation, machine électrique et procédé de fabrication d'un système d'isolation |
| CN111684545A (zh) * | 2018-02-09 | 2020-09-18 | 西门子股份公司 | 用于制造绝缘体系的配制物、电机和用于制造绝缘体系的方法 |
| RU2756232C1 (ru) * | 2018-02-09 | 2021-09-28 | Сименс Акциенгезелльшафт | Композиция для изготовления системы изоляции, электрическая машина и способ изготовления системы изоляции |
| US11424654B2 (en) | 2018-02-09 | 2022-08-23 | Siemens Aktiengesellschaft | Insulation, electrical machine, and method for producing the insulation |
| FR3091406A1 (fr) * | 2018-12-31 | 2020-07-03 | Centre National De Recherche Scientifique (Cnrs) | Matériau pour l’isolation électrique et procédé de fabrication |
| WO2020141280A1 (fr) | 2018-12-31 | 2020-07-09 | Supergrid Institute | Matériau pour l'isolation électrique et procédé de fabrication |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9700191A2 (hu) | 1998-08-28 |
| EP0896723A1 (fr) | 1999-02-17 |
| HU217112B (hu) | 1999-11-29 |
| HUP9700191A3 (en) | 1999-04-28 |
| JP2001502470A (ja) | 2001-02-20 |
| HU9700191D0 (en) | 1997-03-28 |
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