EP0896723A1 - Electric insulation compositions based on epoxy-silicone hybrid resins - Google Patents
Electric insulation compositions based on epoxy-silicone hybrid resinsInfo
- Publication number
- EP0896723A1 EP0896723A1 EP98902143A EP98902143A EP0896723A1 EP 0896723 A1 EP0896723 A1 EP 0896723A1 EP 98902143 A EP98902143 A EP 98902143A EP 98902143 A EP98902143 A EP 98902143A EP 0896723 A1 EP0896723 A1 EP 0896723A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- epoxy resin
- epoxy
- composition according
- resin based
- based composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 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
-
- 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
The essence of the disclosed composition is the combination of materials of excellent insulating properties. The cheaper price and the easy processability of epoxy resins are combined with the advantageous surface properties (hydrophobicity, recovery after dry band arcing) and good weather resistance of silicone rubbers. The new composition can be processed by low pressure casting or by pressure gelation. Due to its low viscosity the base resin can take up a large amount of fillers. The silicone component modifying the epoxy resin is not simply a plasticizer, but it is built into the network structure and its effect is permanent. The main components of the composition are cycloaliphatic, aliphatic (or aromatic) epoxy resin, cycloaliphatic (or aromatic) anhydride (perhaps amine or polyamino-amide) cross-linker, accelerator, and a silicone oligomer containing epoxy end-group. Further components may be low molecular or macromolecular active diluent (flexibilizer) and filler. By changing the ratio of the components one can produce several compositions from a rigid, load-bearing structure up to the soft, rubber-like structures.
Description
Electric insulation compositions based on epoxy- silicone hybrid resins
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.
The application of epoxy resins for electrical insulation has been known for a long time. Besides their advantageous properties (as high mechanical and electrical strength, heat and chemical resistance) they have some disadvantages as well (as cracking, and disappearance of surface hydrophobicity after long term outdoor exposure or after dry band arcing etc.). It is also known that for outdoor applications cycloalpihatic resin and anhydride is preferable to aromatic ones due to their better weather and electrical erosion resistance. Cycloaliphatic resins are less prone to tracking in the case of dry band arcing.
In the past years 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.
Because of the advantageous properties of these materials there have been attempts to unite them in various compositions. The patented combinations frequently emphasize the good electrical insulation, the heat- and weather resistance of the compositions. 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.
Other patents, as e.g. JP 62243649, CS 217338, US 4537803, JP 60112814, JP 52068248, US 3843577 describe compositions containing low molecular (mobile) silicone oil additive in order to improve hydrophobicity, weather resistance or partial discharge properties, but these oils are not built into the network of the epoxy resin.
Our goal with this invention was to develop epoxy resin compositions from commercially available components, which:
1) contain the silicone component incorporated into the network, thus it cannot be removed from the system, its effect is permanent;
2) are cheaper than the HTV (high temperature vulcanizing) or LSR (liquid silicone rubber) materials used in insulator production;
3) can be processed by low- or medium pressure liquid technology even with high filler content.
During the development the following ideas were utilized
1) A proper combination of thermoset resins (so called hybrid 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).
2) In the past few years several reactive silicone oligomers appeared on the market in which the reactive group (hydroxyl, amine, acrylate, epoxy etc.) is not attached directly to the silicon atom, but through a saturated propylene [-(CH2)3-] or butylene [-(CH2)4-] bridge. These intermediates are chemically stabile, can be stored for a long time. Their functional end- groups enable them to be incorporated as dimethyl siloxane blocks into other, thermoset resins. The chemical composition of commercially available epoxy-modified silicone oligomers is as follows:
CH2-CH-CH2-0-R,-[SiR2-0-]n-SiMe 2-(R,)-0-CH2-CH-CH2
\ / \ / o o
where R' is a saturated hydrocarbon chain. At a laboratory scale other structures can also be easily synthesized which contain the epoxy group in the side chain, such as:
Q'-0-[SiR-0]n-[SiR2-0]m-Q"
R'-X
where R is an alkyl group, Q' and Q" can be trimethyl silyl group (-SiMe3) or an -R'-X group, where R' is a saturated hydrocarbon chain and X is a glycidoxyl group:
-0-CH2-CH-CH2
\ / O
3) If a statistical or block copolymer contains about 10% siloxane units, then the surface energy of the copolymer will be similar to that of typical siloxane polymers (i.e. it will be hydrophobic), as the surface will become rich in the low surface energy siloxane component.
Based on the above ideas 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.
Accordingly, 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.
In the compositions according to the invention 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:
CH2-CH-CH2-0-R'-[SiR20-]n-SiMe2-R'-0-CH2-CH-CH2
\ / \ / o o
where 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:
Q'-0-[SiR2-0]n-[SiR-0]m-Q"
R'-X
where 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 (-SiMe3) 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-CH2-CH-CH2
\ / 0
It is advantageous if 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. In this process the monomers or oligomers, which are miscible at the molecular level in the original state, become separated during the polymerization due to the decrease of mixing entropy. As, however, the blocks are linked chemically to each other phase separation remains microscopic. Micro phase separation contributes to the special set of properties of block copolymers.
In the case of outdoor insulations the epoxy component is advantageously cycloaliphatic epoxy and 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. In this case 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. A.) 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.
Based on the above system it is possible to construct softer, more flexible compositions which, in principle, could be used to replace silicone rubber in the manufacture of composite outdoor insulators. In these compositions the 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. One example of polymeric active diluents is a glycidoxyl end functionalized polyether oligomer. The application of polymeric active diluents is 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. Similarly to the previous system, it is advantageous to use cycloaliphatic resin and additives improving the electrical erosion resistance (e.g. ATH). The advantage of this system over silicone rubber is its lower price and (at a similar filled loading level) the significantly lower viscosity.
The amount of the crosslinker, which is applied in a stoichiometric quantity, can be calculated by the following formula:
T = (xei + ye2 +ze3)/A
where 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, e2 is its specific epoxy content, z is the weight of the active diluent, e3 is its specific epoxy content and A is the specific functional group content of the crosslinker (e.g. anhydride) in mol/100 g units.
The invention is illustrated by the following examples.
Example 1
Proof of the reaction between the epoxidized silicone and the cycloaliphatic anhydride
Calculated amounts (see Table 1) of cycloaliphatic anhydride (Lekutherm Harter M, Bayer AG, anhydride equivalent 168 g) and a silicone oligomer containing epoxy end- group (Tegomer ESi-2130 and ESi-2330, TH Goldschmidt AG, epoxy equivalents 514 and 1254 respectively) are mixed together. The components are fully miscible. These mixtures consolidate within 1 day at room temperature and yield a rubbery mass. The transmission IR spectrophotometric investigation of the reactants and of the products proves unambiguously the reaction between the components. (The doublet, characteristic of cyclic anhydrides, appearing at 1780 and at 1860 cm"1 disappears and an ester carbonyl, which is the result of the reaction between the anhydride and
10 -
the epoxy group, appears at 1740 cm"1.) The reaction of the anhydride group can be regarded as complete.
Table 1 Weight portions of the components
Example 2
Synthesis of epoxy-silicone hybrids
Calculated amounts of cycloaliphatic epoxy resin (Lekutherm X100 of Bayer AG, epoxy equivalent 170-180), epoxidized silicone oligomer (Tegomer ESi-2130 or ESi-2330 of TH Goldschmidt AG) and cycloaliphatic anhydride crosslinker (Lekutherm Harter M, Bayer AG) are mixed so that the weight ratio of the components containing epoxy group is 1 :1. The mixture of the reactants is in both cases homogeneous. In order to accelerate the reaction DMP-30 accelerator is added (0.5 wt% of the XI 00 epoxy component). The gel time is measured at 100 °C by Gelnorm instrument, which determines the time required reaching a certain viscosity. Table 2 shows the formulations and the corresponding gel times. In the case of Tegomer ESi-2130 a solid product is obtained, while in the case of ESi-2330 macroscopic phase separation occurs.
11 -
Table 2 Compositions and gel times
Example 3
Variation of hybrid component composition, proof of the appearance of silicone rich surface
Calculated amounts of cycloaliphatic epoxy resin (Lekutherm XlOO of Bayer AG, epoxy equivalent 170-180), epoxidized silicone oligomer (Tegomer ESi-2130 of TH Goldschmidt AG) and cycloaliphatic anhydride crosslinker (Lekutherm Harter M, Bayer AG) are mixed so that the weight ratio of the components containing epoxy group is 3:1, 1 : 1 and 1 :3 (see Table 3). The mixture of the reactants is homogeneous in every case. If the epoxidized silicone component is in majority, a translucent, rubber-like material is obtained, while in the other two cases opaque, solid resins are obtained. Attenuated total reflectance (ATR) IR spectra, which probe the top 0.1 μm 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 -
fact, known also from the literature, that the low surface energy silicone units mainly determine the surface properties of copolymers containing dimethyl siloxane monomers (especially blocks).
Table 3 Weight ratios of the components
(The composition of the 1 :1 mixture is identical with composition 3. of Example 2.)
Example 4
The effect of silicone additive and of mineral fillers on the electrical erosion properties of hybrid resins
In order to check the effect of epoxidized silicone additive and of fillers on the compound properties 4 formulations were prepared (see Table 4. a.), where the amounts of the epoxidized silicone additive and of the fillers (silica and/or ATH) was varied. The mixtures containing fillers were thoroughly mixed in a Molteni type vacuum mixer, evacuated, then poured into a casting mold and cured at 100 °C. Test samples were cut from the sheets and the inclined plane electrical erosion test (LEC 587) was performed on them. The results are summarized in Table 4.b. 5 parallel samples were investigated. At a given voltage level all 5 samples must survive for at least 6 hours. The
13
measurement of a given sample is terminated if the leakage current measured on it exceeds 60 mA. The table also indicates the mode of failure (overcurrent without carbonization /tracking/, overcurrent with carbonization, overcurrent with fire). As shown by the table that 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.
Table 4a Weight ratios of the components
Table 4b
Lifetimes of the compositions described in the previous table as measured by IEC 587 inclined plane test
Example 5
Compositions containing various fillers, flexibilizers and epoxidized silicone
The 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. If the overcurrents not leading to carbonization (tracking) or to burning are neglected, then all compositions pass the IEC 587 inclined plane test at 3.5 kV, only the average weight losses are somewhat different. Taking into account the standard deviation, however, even these differences are not significant. In the case of compositions 14-16 no weight loss, but weight increase was observed after the inclined plane test, which is the result of erosion loss (negative) and water uptake (positive). One can see from Table 5.b that the epoxidized silicone additive decreases the hardness of the resin but it does not improve the impact properties. This disadvantage can be compensated for by the addition of polymeric active diluents. This latter additive can also modify the resin composition to be more similar to hard rubbers.
16 -
Table 5a Weight ratios of the components
Table 5b Some physical characteristics of the compositions shown in the previous table
Example 6
Physical properties of various hybrid resin compositions containing various fillers, mobile and immobile silicone additives
Several physical properties (Table 6b) of five different formulations (see Table 6a) containing silica and other fillers with and without mobile and immobile silicone additives were compared. The cycloaliphatic epoxy component was CY184 (Ciba Geigy), the crosslinker was a cycloaliphatic anhydride (HY1102 of Ciba Geigy), the accelerator was DY062 (Ciba Geigy), the epoxidized silicone additive was Tegomer ESi-2130 (TH Goldschmidt AG), the active diluent was Eurepox RV-F (Schering/WITCO), silica filler was W12 EST (Quarzwerke GmbH), ATH was methyl silane treated grade of Solem GmbH, while wollastonite (Ca-silicate) was a non-treated grade of Quarzwerke GmbH. Table 6. a shows only the resin and the additive components, the crosslinker was the stoichiometric quantity calculated from the epoxy equivalents of the components. 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. As shown by Table 6b, the replacement of silica by softer fillers, such as ATH, reduces the impact and the tensile strength values, although later we demonstrated that by using epoxy-silane treated ATH and wollastonite grades it is
possible to formulate resins with properties similar to the silica filled grade at equal filler content. The addition of mobile or immobile silicone oil to the system somewhat reduces the heat resistance, but the electric breakdown strength remains intact. Formulation 17 did not pass the IEC 587 inclined plane test at 3.5 kV, which is a usual requirement for outdoor insulating materials. All other formulations, containing ATH passed the test. The advantage of the epoxidized silicone additive is shown by the reduced number of overcurrent events during the test.
Table 6a Weight ratios of the components
-19.
Table 6b Physical properties of the compounds shown in the previous table
Claims
1. 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, characterized by the presence of 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.
2. Epoxy resin based composition according to claim 1, characterized by that the silicone additive containing epoxy groups is a poly-siloxane (wherein R may be methyl or phenyl) with the glycidyl group attached in the following way:
CH2-CH-CH2-0-R'-[SiR20-]n-SiMe2-R'-0-CH2-CH-CH2
\ / \ / o o
where 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.
3. Epoxy resin based composition according to claim 1, characterized by that the silicone additive containing epoxy groups is a poly-siloxane described by the following general structure: Q'-0-[SiR2-0]n-[SiR-0]m-Q"
R'-X
where 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 (-SiMe3) 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-CH2-CH-CH2
\ / O
4. Epoxy resin based composition according to claim 2 or 3 characterized by that the mass ratio of the cycloaliphatic epoxy component and of the epoxy group containing silicone additive is between 100:1 and 100:30, preferably between 100:5 and 100:20 and the amount of the crosslinker depends on the concentration of the epoxy groups, and it is added in stoichiometric amount).
5. Epoxy resin based composition according to claim 4 characterized by that the mass ratio of the total amount of the (epoxy resin + epoxy group containing silicone additive + polymeric active diluent) and the total amount of fillers is between 5:1 to 1 :5, preferably between 1 :1 and 1 :3.
6. Epoxy resin based composition according to claim 5 characterized by that, if the total amount of fillers is 100%, the ATH content is between 20 and 60%, preferably between 40 and 50%.
7. Epoxy resin based composition according to claims 5 or 6 characterized by that, if the total amount of fillers is 100%, the content of reinforcing fillers (wollastonite and/or chopped glassfiber) is between 10 and 60%, preferably between 30 and 50%.
8. Epoxy resin based composition according to claims 5 to 7 characterized by that, if the total amount of organic components is 100%), it contains 0.5-10%, preferably 1-3% mobile silicone oil (not bound to the network).
9. Epoxy resin based composition according to claim 2 or 3 characterized by that if the total mass of the (epoxy resin + polymeric active diluent + epoxy group containing siliocne additive) is 100%, then the amount of the polymeric active diluent is 10-50%, preferably 20- 40%), the amount of the epoxy group containing silicone additive is 5- 50%, preferably 10-30%.
10. Epoxy resin based composition according to claim 9 characterized by that the mass ratio of the total amount of the (epoxy resin +epoxy group containing silicone additive + polymeric active diluent) and the total amount of fillers is between 5:1 to 1 :5, preferably between 1 :1 and 1 :3.
11. Epoxy resin based composition according to claim 10 characterized by that, if the total amount of fillers is 100%, the ATH content is between 20 and 60%, preferably between 40 and 50%.
12. Epoxy resin based composition according to claims 10 or 11 characterized by that, if the total amount of fillers is 100%, the content of reinforcing filler (Aerosil) is between 1 and 10%, preferably between 2 and 5%.
13. Epoxy resin based composition according to claims 10 to 12 characterized by that, if the total amount of organic components is 100%), it contains 0.5-10%), preferably 1-3% mobile silicone oil (not bound to the network).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU9700191 | 1997-01-21 | ||
| HU9700191A HU217112B (en) | 1997-01-21 | 1997-01-21 | Electric-insulating compositions based on epoxy-silicon hybridresins |
| PCT/HU1998/000007 WO1998032138A1 (en) | 1997-01-21 | 1998-01-21 | Electric insulation compositions based on epoxy-silicone hybrid resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0896723A1 true EP0896723A1 (en) | 1999-02-17 |
Family
ID=89994659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98902143A Withdrawn EP0896723A1 (en) | 1997-01-21 | 1998-01-21 | Electric insulation compositions based on epoxy-silicone hybrid resins |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0896723A1 (en) |
| JP (1) | JP2001502470A (en) |
| HU (1) | HU217112B (en) |
| WO (1) | WO1998032138A1 (en) |
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| 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 |
| WO2001059791A1 (en) | 2000-02-10 | 2001-08-16 | The Furukawa Electric Co., Ltd. | Insulated wire |
| EP1172408A1 (en) † | 2000-07-14 | 2002-01-16 | Abb Research Ltd. | Volume modified casting masses based on polymer matrix resins |
| EP1176611B1 (en) * | 2001-02-13 | 2006-05-03 | The Furukawa Electric Co., Ltd. | Insulated wire |
| KR20090033226A (en) * | 2006-07-20 | 2009-04-01 | 에이비비 리써치 리미티드 | Hardenable epoxy resin composition |
| ES2411462T3 (en) | 2009-04-02 | 2013-07-05 | Huntsman Advanced Materials (Switzerland) Gmbh | Direct overmolding |
| CN102421835A (en) * | 2009-05-05 | 2012-04-18 | Abb研究有限公司 | Curable sol-gel composition |
| CN103319925A (en) * | 2013-06-04 | 2013-09-25 | 常熟市九洲电器设备有限公司 | High toughness and high-low temperature resistance insulating varnish for motors |
| DE102018202061A1 (en) * | 2018-02-09 | 2019-08-14 | Siemens Aktiengesellschaft | Isolation, electrical machine and method of making the insulation |
| DE102018202058A1 (en) * | 2018-02-09 | 2019-08-14 | Siemens Aktiengesellschaft | Formulation for the preparation of an insulation system, electrical machine and method for producing an insulation system |
| FR3091406B1 (en) * | 2018-12-31 | 2021-01-15 | Centre National De Recherche Scient Cnrs | Material for electrical insulation and manufacturing process |
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| KR930001988B1 (en) * | 1988-04-05 | 1993-03-20 | 미쓰비시뎅끼 가부시끼가이샤 | Epoxy resin composition for semiconductor sealing |
| KR0158868B1 (en) * | 1988-09-20 | 1998-12-01 | 미다 가쓰시게 | Semiconductor device |
| JP3359410B2 (en) * | 1994-03-04 | 2002-12-24 | 三菱電機株式会社 | Epoxy resin composition for molding, molded product for high voltage equipment using the same, and method for producing the same |
-
1997
- 1997-01-21 HU HU9700191A patent/HU217112B/en not_active IP Right Cessation
-
1998
- 1998-01-21 EP EP98902143A patent/EP0896723A1/en not_active Withdrawn
- 1998-01-21 WO PCT/HU1998/000007 patent/WO1998032138A1/en not_active Application Discontinuation
- 1998-01-21 JP JP10534022A patent/JP2001502470A/en active Pending
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| Publication number | Publication date |
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| HU9700191D0 (en) | 1997-03-28 |
| HU217112B (en) | 1999-11-29 |
| HUP9700191A2 (en) | 1998-08-28 |
| JP2001502470A (en) | 2001-02-20 |
| WO1998032138A1 (en) | 1998-07-23 |
| HUP9700191A3 (en) | 1999-04-28 |
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