WO2009109225A1 - Electrical insulation system based on silicone rubber - Google Patents
Electrical insulation system based on silicone rubber Download PDFInfo
- Publication number
- WO2009109225A1 WO2009109225A1 PCT/EP2008/052652 EP2008052652W WO2009109225A1 WO 2009109225 A1 WO2009109225 A1 WO 2009109225A1 EP 2008052652 W EP2008052652 W EP 2008052652W WO 2009109225 A1 WO2009109225 A1 WO 2009109225A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- parts
- range
- silicone rubber
- silicone
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
Definitions
- the present invention refers to an electrical insulation system having an improved tracking and erosion resistance, wherein said electrical insulation system is based on a silicone rubber composition comprising a fluorinated hydrocarbon.
- Silicone rubbers are widely used in the electrical engineering industry, especially for outdoor insulation, due to their good surface properties and the capability to recover hydrophobicity .
- erosion patterns are observed on the rubber surface, whereby the electrical conductivity within said pattern is considerably increased due to discharge degradation.
- Said electrically conductive path is generally called track. Tracks reduce the insulation strength and may lead to flashover or dielectric breakdown.
- a preferred example is high temperature vulcanized polydimethylsiloxane filled with aluminium tri- hydrate [(ATH), (Al 2 O 3 .3H 2 O) ] containing generally about 30 to 70% by weight of ATH, calculated to the total weight of the insulation material [or 43 parts (phr) to 230 parts (phr) of ATH per 100 part of silicone rubber] .
- ATH aluminium tri- hydrate
- Such a material is often used to produce outdoor high-voltage insulation systems.
- Aluminium hydroxide [Al(OH) 3 ] is often referred to as aluminium trihydrate (ATH) because chemically (Al 2 O 3 .3H 2 O) corresponds to 2[Al(OH) 3 ], but the term "ATH” is generally used in the field of polymeric outdoor insulation.
- silicone rubber compositions and especially high temperature vulcanized silicone rubber compositions show an improved tracking and erosion resistance without loss of mechanical properties when said silicone rubber composition is based on a silicone rubber as a silicone base material, and comprises at least one fluorinated hydrocarbon material and at least one filler material, whereby said composition may optionally contain further filler materials and additives .
- the present invention refers to a silicone rubber composition with improved tracking and erosion resistance, wherein said silicone rubber composition is based on a silicone rubber as a base material, and comprises at least one fluorinated hydrocarbon material and at least one inorganic filler material, and optionally further additives, characterized in that: (i) the at least one fluorinated hydrocarbon material is a solid fluorinated hydrocarbon polymer which is present within the range of 1 part (by weight) to 30 parts (by weight) per 100 parts (by weight) of silicone base; and
- the at least one inorganic filler is selected from inorganic fillers known to be used in the field of electrical insulations, wherein
- the total filler content is within the range of 40 parts (by weight) to 230 parts (by weight) per 100 parts (by weight) of silicone base.
- the present invention refers to the hardened resp. cured silicone rubber composition, which preferably is a high temperature vulcanized silicone rubber composition.
- the present invention refers also to the hardenable resp. uncured silicone rubber composition wherein the silicone resin starting materials are present in an non-hardened resp. uncured form and upon hardening yield the final hardened resp. cured silicone rubber composition.
- the present invention further refers to a method of producing said silicone rubber composition.
- the present invention further refers to the use of said silicone rubber composition as an insulation system in electrical articles .
- the present invention further refers to the electrical articles comprising said silicone rubber composition with improved tracking and erosion resistance.
- the fluorinated hydrocarbon material as a solid fluorinated hydrocarbon polymer is preferably present within the range of 2 parts (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base, preferably within the range of 3 parts (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base, preferably within the range of 4 parts (by weight) to 15 parts (by weight) per 100 parts (by weight) of silicone base, preferably within the range of 5 parts (by weight) to 12 parts (by weight) per 100 parts (by weight) of silicone base.
- Solid fluorinated hydrocarbon polymers are known per se and commercially available. Solid fluorinated hydrocarbon polymers for example are polytetrafluoroethylene (PTFE) , tetrafluoroethylene/hexafluoropropy- lene-copolymer (FEP) , tetrafluoroethylene/ethylene-copolymer (ETFE) , tetrafluoroethylene/hexafluoropropylene/vinylidenefluoride-terpolymer, polytrifluorochlorethylene (PCTFE) , trifluorochlorethylene/ethylene- copolymer (ECTFE) , polyvinylfluoride (PVF) , polyvinylidenfluoride (PVDF or PVF 3 ) . Further solid fluorinated hydrocarbon polymers are known and can be used within the scope of the present invention.
- PTFE polytetrafluoroethylene
- FEP tetrafluoroethylene/hexafluoropropy-
- the solid fluorinated hydrocarbon polymer is preferably selected from a fluorinated polymer such as polytetrafluoroethylene (PTFE) , tetra- fluoroethylene/hexafluoropropylene-copolymer (FEP) , tetrafluoro- ethylene/ethylene-copolymer (ETFE) , tetrafluoroethylene/hexafluoro- propylene/vinylidenefluoride-terpolymer, polyvinylfluoride (PVF) , polyvinylidenfluoride (PVDF or PVF 3 ) , preferably from polytetrafluoroethylene (PTFE) , tetrafluoroethylene/hexafluoropropylene-copolymer (FEP) , tetrafluoroethylene/ethylene-copolymer (ETFE) and polyvinyliden- fluoride (PVDF or PVF 3 ) , preferably from polytetraflu
- the fluorinated hydrocarbon polymer may be added to the polymerizable starting mixture in powder form as obtained for example by suspension polymerization or emulsion polymerization, preferably as a free flowing powder, preferably as obtained from emulsion polymerization.
- the fluorinated hydrocarbon polymer may also be prepared by other known methods to a free flowing powder, preferably having an average particle size distribution within the range of 10 nanometer (nm) to 100 micron ( ⁇ m) , preferably within the range of 100 nanometer to 50 micron, preferably within the range of 1 micron to 40 micron, preferably within the range of 2 micron to 10 micron ( ⁇ m) .
- the fluorinated hydrocarbon polymer may also contain a filler material itself or may be coated onto a filler material such as coated onto glass fibers or a filler material as described herein, and subsequently used according to the present invention.
- the silicone rubber composition is based on a silicone rubber as a base material .
- This silicone rubber composition may be made from a room temperature vulcanized/cross-linking silicone rubber composition and preferably is a high temperature vulcanized silicone rubber (HTV-SR) and preferably a high temperature vulcanized polydimethylsiloxane (HTV- PDMS) .
- Such silicone rubbers are generally composed of cross-linked groups of [- (R1R2) Si-O-] , [- (Rl) Si (-0-) 2 ] with terminating groups [ (R1R2R3) Si-O-] , wherein Rl, R2 and R3 are optionally substituted methyl or phenyl, preferably methyl or phenyl, preferably methyl.
- the bridging [ ⁇ Si-O-Si ⁇ ] -group may be replaced by a group of the formula [ ⁇ Si-CH 2 -CH 2 -Si ⁇ ] or [ ⁇ Si-CH 2 -CH 2 -CH 2 -Si ⁇ ] , depending on the cross- linking mechanism and/or the starting materials chosen.
- Such silicone rubbers preferably high temperature vulcanized silicone rubbers and high temperature vulcanized polydimethylsiloxanes as used in the production of electrical isolation systems are known to the expert in the art and need no further detailed description.
- the at least one inorganic filler is selected from inorganic fillers known to be used in the field of electrical insulations and is preferably selected from the group comprising aluminium trihydrate (ATH) ; silica; glass powder; metal oxides such magnesium oxide, titanium oxide; metal nitrides, such as silicon nitride, boron nitride and aluminium nitride; metal carbides, such as silicon carbide; ground natural and synthetic minerals mainly silicates, such as talcum, glimmer, kaolin, wollastonite, bentonite; calcium silicates such as xonolit [Ca 2 Si 6 Oi 7 (OH) 2 ]; aluminium silicates such as andalusite [AI 2 O 3 . SiO 2 ] or zeolithe; and known calcium/magnesium silicates, in different powder sizes.
- ATH aluminium trihydrate
- silica glass powder
- metal oxides such magnesium oxide, titanium oxide
- metal nitrides such as silicon
- the at least one inorganic filler is preferably selected from the group comprising aluminium trihydrate (ATH) and silica.
- ATH aluminium trihydrate
- silica silica
- Each of said filler may be used alone or as a mixture with each other or together with another inorganic filler. If ATH and silica are used together as a mixture, then the ratio of ATH : silica is preferably 5:95 to 25:75, and preferably 15:85 to 25:75.
- the total filler content is preferably within the range of 65 parts (by weight) to 150 parts (by weight) per 100 parts (by weight) of silicone base.
- Average grain sizes and specific surface areas (BET) of the filler material as used in the present invention are known in the art .
- Such filler material is commercially available.
- the filler material may be surface treated resp. surface modified in a manner known per se, for example with silazanes, such as hexamethylsilazane or divinyltetra- methyldisilazane or with vinylalkoxysilanes, such as vinyltrimethoxy- silan, or for example with alkoxysilanes or siloxandiols .
- additives are known per se and are for example inhibitors resp. stabilizers, flame retardants, or colors and pigments.
- the high temperature vulcanized silicone rubber according to the present invention is made from a hardenable liquid or pasteous silicone resin composition.
- said hardenable liquid or pasteous silicone resin composition is a mixture of organopolysiloxanes, preferably a mixture of compounds of the general formula (I) :
- R independent of each other is (Ci_ 4 ) -alkyl which optionally is substituted by chlorine and/or bromine or phenyl; preferably methyl, ethyl, propyl, 3, 3, 3-trifluoropropyl, monofluoromethyl, or difluoromethyl; preferably methyl;
- Ri independent of each other has one of the meanings of R or R 2 , or is -O-Alkyl (Ci-C 4 ) or hydroxyl;
- A is a residue -C 3 H 2s - , preferably - (CH 2 ) s - , wherein s is a whole number from 1 to 3, preferably 1; r is zero or one; m is a number within the range of 500 to 20'000, preferably within the range of 1000 to 15 1 OOO, preferably within the range of 4'00O to 10 1 OOO; and n is a number within the range of zero to 500, preferably zero, or within the range of 2 to 100, preferably a number within the range of 2 to 20; and wherein the groups -[Si(R) (R)O]- und -[Si(Ri) (R 2 )O]- are ordered in an arbitrary sequence.
- R 2 has one of the meanings given for R, wherein R preferably is methyl or phenyl, wherein the molecule contains methyl as well as phenyl residues.
- the ratio of methyl to phenyl is given by the required flowability of the mixture and the properties required in the hardened product.
- R is methyl.
- the compound of formula (I) generally is a mixture of homologous compounds of formula (I) which is known to the expert.
- the mixture of the silicone compounds may be hardened by adding a tri- alkoxysilane of the formula [ (Ci_ 4 ) Alkyl] 4 _ x Si [O-Alkyl (Ci_ 4 ) ] x , wherein x is 1 to 4, preferably 1, 2 or 3, preferably 3; for example methyltri- methoxysilane, methyltriethoxysilane and similar compounds; compounds of the formula [ (C 2 -C 4 ) Alkenyl ] 4 _ x Si [O-Alkyl (Ci-C 4 ) ] x , wherein x is 1 to 4, preferably 1, 2 or 3, preferably 3, such as vinyltrimethoysilane or allyltrimethoysilane, (phenyl) Si [O-alkyl (Ci-C 4 ) ]; or a silane of the formula [ (Ci-C 4 ) Alkyl] SiH 3 or similar low molecular hydrogensiloxanes
- peroxide compounds such as diacylperoxide, dialkylperoxide and other peroxides known per se to harden the siloxane mixture.
- elevated temperatures are used for the hardening process, which yield a high temperature vulcanized silicone rubber as preferred in the present invention.
- a catalyst is preferably used, preferably a complex made from a metal selected from rhodium, nickel, palladium and/or platin, in an amount of preferably 1 to 100 ppm calculated to the metal bound in the complex.
- a metal selected from rhodium, nickel, palladium and/or platin
- Such catalytically active compounds and the silicon compounds of formula (I) to be used are known per se and have been described in the literature.
- the present invention refers also to the hardenable resp. uncured silicone rubber composition wherein the silicone resin starting materials are present in an non-hardened resp. uncured form and upon hardening yield the final hardened resp. cured silicone rubber composition.
- the present invention also refers to a method of producing the silicone rubber composition with improved tracking and erosion resistance according to the present invention, preferably a high temperature vulcanized silicone rubber composition, characterized in that the starting components of the hardenable mixture, i.e. the hardenable mixture of silicone compounds, preferably a mixture of compounds of formula (I), the at least one fluorinated hydrocarbon material as defined above, the at least one filler material as defined above, the catalyst as defined above, and any optional additives, are mixed in any desired sequence and are heated to a temperature within the range of 100 0 C to 15O 0 C, preferably within the range of 12O 0 C to 14O 0 C, for a time long enough to cause complete vulcanization of the composition.
- the starting components of the hardenable mixture i.e. the hardenable mixture of silicone compounds, preferably a mixture of compounds of formula (I)
- the at least one fluorinated hydrocarbon material as defined above the at least one filler material as defined above
- the catalyst as defined above the
- the present invention also refers to the use of the hardenable silicone rubber resin, as defined above, for the production of shaped articles in the field of electrical isolators, specifically in the field of high voltage isolators, especially for outdoor use.
- the high temperature vulcanized silicone rubber composition according to the present invention is useful for the production of electrical insulations and in the production of electrical components especially in the field of cylindrical insulators, preferably metal enclosed applications, especially metal enclosed switchgear applications, such as in the production of pressurized gas-insulated switchgear stations (GIS) or in the production of generator circuit breakers (GCB) , life- tank breakers, dead-tank breaker and related applications.
- Further electrical components to be made with the insulation system according to the present invention comprise the impregnation of electrical coils and the production of spacer insulators and related applications.
- Preferred uses also are in the production of electrical components such as transformers, bushings, insulators, switches, sensors, converters and cable end seals, high-voltage insulations for indoor and outdoor use, especially for outdoor insulators associated with high-voltage lines, as long-rod, composite and cap-type insulators, and also for base insulators in the medium-voltage sector, in the production of insulators associated with outdoor power switches, measuring transducers, lead-throughs, and overvoltage protectors, in switchgear construction, in power switches .
- the present invention also refers to the shaped articles in the field of electrical isolators, specifically in the field of high voltage isolators, especially for outdoor use, as made according to the present invention.
- the following examples illustrate the invention without restricting the scope of the description and claims.
- the components as give in Table 1 are dispersed in the silicone base by either using a duplex kneader, a two-roll mill or a combination of both.
- the homogeneous formulation is then molded and cured at an elevated temperature, chosen on the basis of the peroxide or platinum compound. After remolding, a post-curing step is possible, but not necessary. For the described examples curing was carried out for 30 minutes at 13O 0 C and post-curing for 4 hours at 15O 0 C.
- the proposed formulations contain the following raw materials. For each raw material one commercially available product is given:
- Teflon Powder e.g. Zonyl® MP 1200, DuPont Fluoroproducts, US
- Peroxide e.g. DCLBP-50-PSI : Di (2 , 4-dichlorobenzoyl) peroxide 50% in silicone oil, Degussa Initiators GmbH & Co. KG, Germany
- Table 1 shows an exemplary formulations (Formulation A and Formulation B) and compares these Formulations with a commercial Reference.
- Table 2 lists their properties.
- the composition of proposed formulations i.e. fluorinated compound (Teflon powder), filler, additive and curing agent content, is given in phr (parts per hundred) with respect to the silicone base.
Landscapes
- 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)
Abstract
Silicone rubber composition with improved tracking and erosion resistance, wherein said silicone rubber composition is based on a silicone rubber as a base material, and comprises at least one fluorinated hydrocarbon material and at least one inorganic filler material, and optionally further additives, characterized in that (i) the at least one fluorinated hydrocarbon material is a solid fluorinated hydrocarbon polymer which is present within the range of 1 part (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base; and (ii) the at least one inorganic filler is selected from inorganic fillers known to be used in the field of electrical insulations, wherein (iii) the total filler content is within the range of 40 parts (by weight) to 230 parts (by weight) per 100 parts (by weight) of silicone base; method of producing the composition; and use of composition as an insulation system in electrical articles.
Description
Electrical insulation system based on silicone rubber
The present invention refers to an electrical insulation system having an improved tracking and erosion resistance, wherein said electrical insulation system is based on a silicone rubber composition comprising a fluorinated hydrocarbon.
Silicone rubbers are widely used in the electrical engineering industry, especially for outdoor insulation, due to their good surface properties and the capability to recover hydrophobicity . However, particularly in outdoor and wet environment often erosion patterns are observed on the rubber surface, whereby the electrical conductivity within said pattern is considerably increased due to discharge degradation. Said electrically conductive path is generally called track. Tracks reduce the insulation strength and may lead to flashover or dielectric breakdown.
As a result tracking-resistant polymer systems have been developed for the use as outdoor high-voltage insulation. A preferred example is high temperature vulcanized polydimethylsiloxane filled with aluminium tri- hydrate [(ATH), (Al2O3.3H2O) ] containing generally about 30 to 70% by weight of ATH, calculated to the total weight of the insulation material [or 43 parts (phr) to 230 parts (phr) of ATH per 100 part of silicone rubber] . Such a material is often used to produce outdoor high-voltage insulation systems. Aluminium hydroxide [Al(OH)3] is often referred to as aluminium trihydrate (ATH) because chemically (Al2O3.3H2O) corresponds to 2[Al(OH)3], but the term "ATH" is generally used in the field of polymeric outdoor insulation.
Testing the tracking resistance of various commercial high temperature vulcanized silicone rubber compositions and various commercial high temperature vulcanized polydimethylsiloxane compositions according to IEC (International Electrotechnical Commission) standard 60587 at 4.5 kV revealed that these materials often failed during testing, showing deep erosion and a layer-wise degradation, resulting in a dielectric breakdown in the IEC 60587 tracking test. The degradation mechanism was found to be complicated, as temperatures of above 12000C and even higher than 16000C may arise during surface discharge. Therefore, there
is a need to improve the tracking and erosion resistance of filler containing silicone rubber compositions .
It has now been found that silicone rubber compositions and especially high temperature vulcanized silicone rubber compositions, preferably compositions based on high temperature vulcanized polydimethyl- siloxanes, show an improved tracking and erosion resistance without loss of mechanical properties when said silicone rubber composition is based on a silicone rubber as a silicone base material, and comprises at least one fluorinated hydrocarbon material and at least one filler material, whereby said composition may optionally contain further filler materials and additives .
The present invention is defined in the claims . The present invention refers to a silicone rubber composition with improved tracking and erosion resistance, wherein said silicone rubber composition is based on a silicone rubber as a base material, and comprises at least one fluorinated hydrocarbon material and at least one inorganic filler material, and optionally further additives, characterized in that: (i) the at least one fluorinated hydrocarbon material is a solid fluorinated hydrocarbon polymer which is present within the range of 1 part (by weight) to 30 parts (by weight) per 100 parts (by weight) of silicone base; and
(ii) the at least one inorganic filler is selected from inorganic fillers known to be used in the field of electrical insulations, wherein
(iii) the total filler content is within the range of 40 parts (by weight) to 230 parts (by weight) per 100 parts (by weight) of silicone base.
The present invention refers to the hardened resp. cured silicone rubber composition, which preferably is a high temperature vulcanized silicone rubber composition. The present invention refers also to the hardenable resp. uncured silicone rubber composition wherein the silicone resin starting materials are present in an non-hardened resp. uncured form and upon hardening yield the final hardened resp. cured silicone rubber composition.
The present invention further refers to a method of producing said silicone rubber composition. The present invention further refers to the use of said silicone rubber composition as an insulation system in electrical articles . The present invention further refers to the electrical articles comprising said silicone rubber composition with improved tracking and erosion resistance.
The fluorinated hydrocarbon material as a solid fluorinated hydrocarbon polymer is preferably present within the range of 2 parts (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base, preferably within the range of 3 parts (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base, preferably within the range of 4 parts (by weight) to 15 parts (by weight) per 100 parts (by weight) of silicone base, preferably within the range of 5 parts (by weight) to 12 parts (by weight) per 100 parts (by weight) of silicone base.
Solid fluorinated hydrocarbon polymers are known per se and commercially available. Solid fluorinated hydrocarbon polymers for example are polytetrafluoroethylene (PTFE) , tetrafluoroethylene/hexafluoropropy- lene-copolymer (FEP) , tetrafluoroethylene/ethylene-copolymer (ETFE) , tetrafluoroethylene/hexafluoropropylene/vinylidenefluoride-terpolymer, polytrifluorochlorethylene (PCTFE) , trifluorochlorethylene/ethylene- copolymer (ECTFE) , polyvinylfluoride (PVF) , polyvinylidenfluoride (PVDF or PVF3) . Further solid fluorinated hydrocarbon polymers are known and can be used within the scope of the present invention.
The solid fluorinated hydrocarbon polymer is preferably selected from a fluorinated polymer such as polytetrafluoroethylene (PTFE) , tetra- fluoroethylene/hexafluoropropylene-copolymer (FEP) , tetrafluoro- ethylene/ethylene-copolymer (ETFE) , tetrafluoroethylene/hexafluoro- propylene/vinylidenefluoride-terpolymer, polyvinylfluoride (PVF) , polyvinylidenfluoride (PVDF or PVF3) , preferably from polytetrafluoroethylene (PTFE) , tetrafluoroethylene/hexafluoropropylene-copolymer (FEP) , tetrafluoroethylene/ethylene-copolymer (ETFE) and polyvinyliden- fluoride (PVDF or PVF3) , preferably from polytetrafluoroethylene (PTFE), tetrafluoroethylene/hexafluoropropylene-copolymer (FEP) and tetrafluoroethylene/ethylene-copolymer (ETFE) , preferably from poly-
tetrafluoroethylene (PTFE) and tetrafluoroethylene/ethylene-copolymer (ETFE) , preferably polytetrafluoroethylene (PTFE) .
The fluorinated hydrocarbon polymer may be added to the polymerizable starting mixture in powder form as obtained for example by suspension polymerization or emulsion polymerization, preferably as a free flowing powder, preferably as obtained from emulsion polymerization. The fluorinated hydrocarbon polymer may also be prepared by other known methods to a free flowing powder, preferably having an average particle size distribution within the range of 10 nanometer (nm) to 100 micron (μm) , preferably within the range of 100 nanometer to 50 micron, preferably within the range of 1 micron to 40 micron, preferably within the range of 2 micron to 10 micron (μm) .
The fluorinated hydrocarbon polymer may also contain a filler material itself or may be coated onto a filler material such as coated onto glass fibers or a filler material as described herein, and subsequently used according to the present invention.
The chemical formula of some of the fluorinated hydrocarbon polymers are illustrated as follows:
F F H H F F H H
F F H H - ]- H H - ]-
F C I
ETFE ECTFE
H H H F H F H F PVF PVDF
The silicone rubber composition is based on a silicone rubber as a base material . This silicone rubber composition may be made from a room temperature vulcanized/cross-linking silicone rubber composition and
preferably is a high temperature vulcanized silicone rubber (HTV-SR) and preferably a high temperature vulcanized polydimethylsiloxane (HTV- PDMS) . Such silicone rubbers are generally composed of cross-linked groups of [- (R1R2) Si-O-] , [- (Rl) Si (-0-) 2 ] with terminating groups [ (R1R2R3) Si-O-] , wherein Rl, R2 and R3 are optionally substituted methyl or phenyl, preferably methyl or phenyl, preferably methyl. The bridging [≡Si-O-Si≡] -group may be replaced by a group of the formula [≡Si-CH2-CH2-Si≡] or [≡Si-CH2-CH2-CH2-Si≡] , depending on the cross- linking mechanism and/or the starting materials chosen. Such silicone rubbers, preferably high temperature vulcanized silicone rubbers and high temperature vulcanized polydimethylsiloxanes as used in the production of electrical isolation systems are known to the expert in the art and need no further detailed description.
The at least one inorganic filler is selected from inorganic fillers known to be used in the field of electrical insulations and is preferably selected from the group comprising aluminium trihydrate (ATH) ; silica; glass powder; metal oxides such magnesium oxide, titanium oxide; metal nitrides, such as silicon nitride, boron nitride and aluminium nitride; metal carbides, such as silicon carbide; ground natural and synthetic minerals mainly silicates, such as talcum, glimmer, kaolin, wollastonite, bentonite; calcium silicates such as xonolit [Ca2Si6Oi7(OH)2]; aluminium silicates such as andalusite [AI2O3. SiO2] or zeolithe; and known calcium/magnesium silicates, in different powder sizes.
The at least one inorganic filler is preferably selected from the group comprising aluminium trihydrate (ATH) and silica. Each of said filler may be used alone or as a mixture with each other or together with another inorganic filler. If ATH and silica are used together as a mixture, then the ratio of ATH : silica is preferably 5:95 to 25:75, and preferably 15:85 to 25:75. The total filler content is preferably within the range of 65 parts (by weight) to 150 parts (by weight) per 100 parts (by weight) of silicone base.
Average grain sizes and specific surface areas (BET) of the filler material as used in the present invention are known in the art . Such filler material is commercially available. The filler material may be surface treated resp. surface modified in a manner known per se, for
example with silazanes, such as hexamethylsilazane or divinyltetra- methyldisilazane or with vinylalkoxysilanes, such as vinyltrimethoxy- silan, or for example with alkoxysilanes or siloxandiols .
Further optional additives are known per se and are for example inhibitors resp. stabilizers, flame retardants, or colors and pigments.
The high temperature vulcanized silicone rubber according to the present invention is made from a hardenable liquid or pasteous silicone resin composition. Preferably said hardenable liquid or pasteous silicone resin composition is a mixture of organopolysiloxanes, preferably a mixture of compounds of the general formula (I) :
R independent of each other is (Ci_4) -alkyl which optionally is substituted by chlorine and/or bromine or phenyl; preferably methyl, ethyl, propyl, 3, 3, 3-trifluoropropyl, monofluoromethyl, or difluoromethyl; preferably methyl;
Ri independent of each other has one of the meanings of R or R2, or is -O-Alkyl (Ci-C4) or hydroxyl;
R2 independent of each other has one of the meaning of R, or is hydrogen, or a residue of the formula: -(A)1-CH=CH2;
A is a residue -C3H2s- , preferably - (CH2) s- , wherein s is a whole number from 1 to 3, preferably 1; r is zero or one; m is a number within the range of 500 to 20'000, preferably within the range of 1000 to 151OOO, preferably within the range of 4'00O to 101OOO; and n is a number within the range of zero to 500, preferably zero, or within the range of 2 to 100, preferably a number within the range of 2 to 20; and wherein the groups -[Si(R) (R)O]- und -[Si(Ri) (R2)O]- are ordered in an arbitrary sequence.
Preferably R2 has one of the meanings given for R, wherein R preferably is methyl or phenyl, wherein the molecule contains methyl as well as
phenyl residues. The ratio of methyl to phenyl is given by the required flowability of the mixture and the properties required in the hardened product. Preferably R is methyl. The compound of formula (I) generally is a mixture of homologous compounds of formula (I) which is known to the expert. Preferably at least a part of the substituents Ri has the meaning of -O-Alkyl (Ci-C4) or hydroxyl or of -(A)1-CH=CH2.
The mixture of the silicone compounds may be hardened by adding a tri- alkoxysilane of the formula [ (Ci_4) Alkyl] 4_xSi [O-Alkyl (Ci_4) ] x, wherein x is 1 to 4, preferably 1, 2 or 3, preferably 3; for example methyltri- methoxysilane, methyltriethoxysilane and similar compounds; compounds of the formula [ (C2-C4) Alkenyl ] 4_xSi [O-Alkyl (Ci-C4) ] x, wherein x is 1 to 4, preferably 1, 2 or 3, preferably 3, such as vinyltrimethoysilane or allyltrimethoysilane, (phenyl) Si [O-alkyl (Ci-C4) ]; or a silane of the formula [ (Ci-C4) Alkyl] SiH3 or similar low molecular hydrogensiloxanes . It is also possible to use peroxide compounds, such as diacylperoxide, dialkylperoxide and other peroxides known per se to harden the siloxane mixture. Generally elevated temperatures are used for the hardening process, which yield a high temperature vulcanized silicone rubber as preferred in the present invention.
In an embodiment of the present invention R2 is hydrogen as well as -A-CH=CH2, wherein R2 per molecule either stands for hydrogen only or for -A-CH=CH2 only. The compound wherein R2 is hydrogen and the compound wherein R2 is -A-CH=CH2, are stored separately to avoid any interaction. The compounds are mixed shortly before hardening the mixture. Both compounds are mixed in equimolar amounts and are then hardened resp. vulcanized. Preferably a molar excess of about 2 to 5% of the Si-H- groups is used with respect to the component containing the -A-CH=CH2 substituent. Further a catalyst is preferably used, preferably a complex made from a metal selected from rhodium, nickel, palladium and/or platin, in an amount of preferably 1 to 100 ppm calculated to the metal bound in the complex. Such catalytically active compounds and the silicon compounds of formula (I) to be used are known per se and have been described in the literature.
The present invention refers also to the hardenable resp. uncured silicone rubber composition wherein the silicone resin starting materials are present in an non-hardened resp. uncured form and upon
hardening yield the final hardened resp. cured silicone rubber composition. In this sense the present invention also refers to a hardenable silicone rubber resin, containing a mixture of compounds of formula (I) in the form of a two-component system, wherein one component contains a mixture of compounds of formula (I) wherein R2 is hydrogen and the other component contains a mixture of compounds of formula (I) wherein R2 is -A-CH=CH2; as defined above; said resin being hardenable after mixing of the two components and after addition of a catalyst as defined above.
The present invention also refers to a method of producing the silicone rubber composition with improved tracking and erosion resistance according to the present invention, preferably a high temperature vulcanized silicone rubber composition, characterized in that the starting components of the hardenable mixture, i.e. the hardenable mixture of silicone compounds, preferably a mixture of compounds of formula (I), the at least one fluorinated hydrocarbon material as defined above, the at least one filler material as defined above, the catalyst as defined above, and any optional additives, are mixed in any desired sequence and are heated to a temperature within the range of 1000C to 15O0C, preferably within the range of 12O0C to 14O0C, for a time long enough to cause complete vulcanization of the composition.
The present invention also refers to the use of the hardenable silicone rubber resin, as defined above, for the production of shaped articles in the field of electrical isolators, specifically in the field of high voltage isolators, especially for outdoor use.
The high temperature vulcanized silicone rubber composition according to the present invention is useful for the production of electrical insulations and in the production of electrical components especially in the field of cylindrical insulators, preferably metal enclosed applications, especially metal enclosed switchgear applications, such as in the production of pressurized gas-insulated switchgear stations (GIS) or in the production of generator circuit breakers (GCB) , life- tank breakers, dead-tank breaker and related applications. Further electrical components to be made with the insulation system according to the present invention comprise the impregnation of electrical coils and the production of spacer insulators and related applications.
Preferred uses also are in the production of electrical components such as transformers, bushings, insulators, switches, sensors, converters and cable end seals, high-voltage insulations for indoor and outdoor use, especially for outdoor insulators associated with high-voltage lines, as long-rod, composite and cap-type insulators, and also for base insulators in the medium-voltage sector, in the production of insulators associated with outdoor power switches, measuring transducers, lead-throughs, and overvoltage protectors, in switchgear construction, in power switches .
The present invention also refers to the shaped articles in the field of electrical isolators, specifically in the field of high voltage isolators, especially for outdoor use, as made according to the present invention. The following examples illustrate the invention without restricting the scope of the description and claims.
Example 1
The components as give in Table 1 are dispersed in the silicone base by either using a duplex kneader, a two-roll mill or a combination of both. The homogeneous formulation is then molded and cured at an elevated temperature, chosen on the basis of the peroxide or platinum compound. After remolding, a post-curing step is possible, but not necessary. For the described examples curing was carried out for 30 minutes at 13O0C and post-curing for 4 hours at 15O0C.
The proposed formulations contain the following raw materials. For each raw material one commercially available product is given:
• Silicone rubber base stabilized with fumed silica
(e.g. Elastosil® R 401/70 OH, Wacker Chemie GmbH, Germany) • ATH (aluminiumtrihydrate, e.g. Martinal® OL-104/S, Martinswerk GmbH, Germany)
• Teflon Powder (e.g. Zonyl® MP 1200, DuPont Fluoroproducts, US)
• Peroxide (e.g. DCLBP-50-PSI : Di (2 , 4-dichlorobenzoyl) peroxide 50% in silicone oil, Degussa Initiators GmbH & Co. KG, Germany)
Table 1 shows an exemplary formulations (Formulation A and Formulation B) and compares these Formulations with a commercial Reference.
Table 2 lists their properties. The composition of proposed formulations, i.e. fluorinated compound (Teflon powder), filler, additive and curing agent content, is given in phr (parts per hundred) with respect to the silicone base.
Table 1 (Composition)
Table 2 (Properties)
Comparison between Reference and Formulations A and B
The addition of 5 phr or 10 phr of Teflon powder leads to a distinct improvement of tracking resistance without significant deterioration of mechanical properties .
Claims
1. Silicone rubber composition with improved tracking and erosion resistance, wherein said silicone rubber composition is based on a silicone rubber as a base material, and comprises at least one fluori- nated hydrocarbon material and at least one inorganic filler material, and optionally further additives, characterized in that: (i) the at least one fluorinated hydrocarbon material is a solid fluorinated hydrocarbon polymer which is present within the range of 1 part (by weight) to 30 parts (by weight) per 100 parts (by weight) of silicone base; and (ii) the at least one inorganic filler is selected from inorganic fillers known to be used in the field of electrical insulations, wherein (iii) the total filler content is within the range of 40 parts (by weight) to 230 parts (by weight) per 100 parts (by weight) of silicone base.
2. Composition according to claim 1, characterized in that said composition is a hardened silicone rubber composition, and preferably is a high temperature vulcanized silicone rubber composition.
3. Composition according to claim 1 or 2, characterized in that the fluorinated hydrocarbon material is present within the range of 2 parts (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base; preferably within the range of 3 parts (by weight) to 20 parts (by weight) per 100 parts (by weight) of silicone base; preferably within the range of 4 parts (by weight) to 15 parts (by weight) per 100 parts (by weight) of silicone base; preferably within the range of 5 parts (by weight) to 12 parts (by weight) per 100 parts (by weight) of silicone base.
4. Composition according to any one of the claims 1-3, characterized in that the fluorinated hydrocarbon material is selected from poly- tetrafluoroethylene (PTFE) , tetrafluoroethylene/hexafluoropropylene- copolymer (FEP) , tetrafluoroethylene/ethylene-copolymer (ETFE) , tetrafluoroethylene/hexafluoropropylene/vinylidenefluoride-terpolymer, polytrifluorochlorethylene (PCTFE) , trifluorochlorethylene/ethylene- copolymer (ECTFE) , polyvinylfluoride (PVF) , polyvinylidenfluoride (PVDF or PVF3) .
5. Composition according to claim 4, characterized in that the fluorinated hydrocarbon material is selected from polytetrafluoro- ethylene (PTFE) , tetrafluoroethylene/hexafluoropropylene-copolymer (FEP) and tetrafluoroethylene/ethylene-copolymer (ETFE) , preferably from polytetrafluoroethylene (PTFE) and tetrafluoroethylene/ethylene- copolymer (ETFE) , and preferably is polytetrafluoroethylene (PTFE) .
6. Composition according to any one of the claims 1-5, characterized in that the fluorinated hydrocarbon material has an average particle size distribution within the range of 10 nanometer (nm) to 100 micron (μm) , preferably within the range of 100 nanometer to 50 micron, prefe- rably within the range of 1 micron to 40 micron, preferably within the range of 2 micron to 10 micron (μm) .
7. Composition according to any one of the claims 1-6, characterized in that the inorganic filler is selected from the group comprising aluminium trihydrate; silica; glass powder; metal oxides, preferably magnesium oxide, titanium oxide; metal nitrides, preferably silicon nitride, boron nitride and aluminium nitride; metal carbides, preferably silicon carbide; ground natural and synthetic minerals, preferably talcum, glimmer, kaolin, wollastonite, bentonite; calcium silicates, preferably xonolit [Ca2Si6Oi7(OH)2]; aluminium silicates, preferably andalusite [Al2O3-SiO2] or zeolithe; and known calcium/magnesium silicates, in different powder sizes.
8. Composition according to claim 7, characterized in that the inorganic filler is selected from aluminium trihydrate (ATH) and silica, optionally as a mixture, wherein the ratio of ATH : silica is within the range of 5:95 to 25:75, preferably within the range of 15:85 to 25:75, and the total filler content is within the range of 65 parts (by weight) to 150 parts (by weight) per 100 parts (by weight) of silicone base.
9. Composition according to any one of the claims 1-8, characterized in that the filler material has been surface treated with silazanes, or with vinylalkoxysilanes .
10. Composition according to any one of the claims 1-9, characterized in that said composition further contains additives, preferably inhibitors, stabilizers, flame retardants and/or colors and pigments.
11. Composition according to any one of the claims 1-10, characterized in that the high temperature vulcanized silicone rubber is made from a hardenable liquid or pasteous silicone resin composition being a mixture of organopolysiloxanes of the general formula (I) :
Ri independent of each other has one of the meanings of R or R2, or is -O-Alkyl (Ci-C4) or hydroxyl;
R2 independent of each other has one of the meaning of R, or is hydrogen, or a residue of the formula: -(A)1-CH=CH2;
A is a residue -C3H2s- , preferably - (CH2) s- , wherein s is a whole number from 1 to 3, preferably 1; r is zero or one; m is a number within the range of 500 to 20'000, preferably within the range of 1000 to 151OOO, preferably within the range of 4'00O to 101OOO; and n is a number within the range of zero to 500, preferably zero, or within the range of 2 to 100, preferably a number within the range of 2 to 20; and wherein the groups -[Si(R) (R)O]- und -[Si(Ri) (R2)O]- are ordered in an arbitrary sequence.
12. Hardenable silicone rubber composition containing the components as defined in any one of the claims 1-11, characterized in that the silicone resin starting materials are present in an non-hardened form and upon hardening yield the final hardened silicone rubber composition as defined in any one of the claims 1-11.
13. Composition according to claim 12, characterized in that the fluorinated hydrocarbon material is present as a free flowing powder, optionally containing a filler material or coated onto a filler material, preferably coated onto glass fibers or a filler material as defined in claim 7.
14. Method of producing the silicone rubber composition according to any one of the claims 1-11, characterized in that the starting compo- nents of the hardenable mixture, i.e. the hardenable mixture of silicone compounds, preferably a mixture of compounds of formula (I), the at least one fluorinated hydrocarbon material, the at least one filler material, the catalyst, and any optional additives, are mixed in any desired sequence and are heated to a temperature within the range of 1000C to 2000C, preferably within the range of 12O0C to 15O0C, for a time long enough to cause complete hardening resp. vulcanization of the composition .
15. The use of the hardenable silicone rubber resin according to the claims 12 and 13, as an insulation system in electrical articles, preferably in the field of electrical isolators, preferably in the field of high voltage isolators, especially for outdoor use.
16. The use according to claim 15 for the production of electrical insulations and for the production of electrical components especially in the field of cylindrical insulators, preferably metal enclosed applications, especially metal enclosed switchgear applications, such as in the production of pressurized gas-insulated switchgear stations (GIS) or in the production of generator circuit breakers (GCB) , life- tank breakers, dead-tank breaker and related applications. Further electrical components to be made with the insulation system according to the present invention comprise the impregnation of electrical coils and the production of spacer insulators and related applications.
17. The use according to claim 15 in the production of transformers, bushings, insulators, switches, sensors, converters and cable end seals, high-voltage insulations for indoor and outdoor use, especially for outdoor insulators associated with high-voltage lines, as long-rod, composite and cap-type insulators, and also for base insulators in the medium-voltage sector, in the production of insulators associated with outdoor power switches, measuring transducers, lead-throughs, and overvoltage protectors, in switchgear construction, in power switches.
18. Shaped articles made according to any one of the claims 15-17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2008/052652 WO2009109225A1 (en) | 2008-03-05 | 2008-03-05 | Electrical insulation system based on silicone rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2008/052652 WO2009109225A1 (en) | 2008-03-05 | 2008-03-05 | Electrical insulation system based on silicone rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009109225A1 true WO2009109225A1 (en) | 2009-09-11 |
Family
ID=40010842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2008/052652 WO2009109225A1 (en) | 2008-03-05 | 2008-03-05 | Electrical insulation system based on silicone rubber |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2009109225A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268234A (en) * | 2011-06-30 | 2011-12-07 | 郑州中原应用技术研究开发有限公司 | Double-component silicone seal glue for solar battery pack and glue-injecting process thereof |
| CN103613885A (en) * | 2013-10-28 | 2014-03-05 | 安徽东方金河精密机械制造有限公司 | Special mixed rubber sealing ring for capacitors, and making method thereof |
| CN103613891A (en) * | 2013-10-28 | 2014-03-05 | 安徽东方金河精密机械制造有限公司 | Special rubber sealing ring for capacitor, and making method thereof |
| US8717732B2 (en) | 2009-12-04 | 2014-05-06 | Abb Research Ltd. | High voltage surge arrester |
| CN105505293A (en) * | 2016-01-15 | 2016-04-20 | 杨帆 | Antimicrobial and flame-retardant silicone sealant and preparation method thereof |
| CN108546412A (en) * | 2018-04-24 | 2018-09-18 | 常州达奥新材料科技有限公司 | A kind of preparation method of rubber packing material |
| CN111681811A (en) * | 2020-05-15 | 2020-09-18 | 河南胜华电缆集团有限公司 | Flexible fireproof cable and preparation method of heat insulation layer thereof |
| CN114874632A (en) * | 2022-06-13 | 2022-08-09 | 温州益坤电气股份有限公司 | Anti-fouling wear-resistant silicon rubber material for high-speed motor train unit and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969308A (en) * | 1968-08-01 | 1976-07-13 | Raychem Limited | Polymer compositions |
| US5641827A (en) * | 1996-03-20 | 1997-06-24 | Raychem Corporation | Tracking and erosion resistant composition |
| EP0928008A2 (en) * | 1997-12-30 | 1999-07-07 | General Electric Company | Silicone compositions for high voltage insulator applications |
-
2008
- 2008-03-05 WO PCT/EP2008/052652 patent/WO2009109225A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969308A (en) * | 1968-08-01 | 1976-07-13 | Raychem Limited | Polymer compositions |
| US5641827A (en) * | 1996-03-20 | 1997-06-24 | Raychem Corporation | Tracking and erosion resistant composition |
| EP0928008A2 (en) * | 1997-12-30 | 1999-07-07 | General Electric Company | Silicone compositions for high voltage insulator applications |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8717732B2 (en) | 2009-12-04 | 2014-05-06 | Abb Research Ltd. | High voltage surge arrester |
| CN102268234A (en) * | 2011-06-30 | 2011-12-07 | 郑州中原应用技术研究开发有限公司 | Double-component silicone seal glue for solar battery pack and glue-injecting process thereof |
| CN103613891B (en) * | 2013-10-28 | 2016-05-25 | 安徽东方金河精密机械制造有限公司 | A kind of capacitor special (purpose) rubber sealing ring and preparation method thereof |
| CN103613891A (en) * | 2013-10-28 | 2014-03-05 | 安徽东方金河精密机械制造有限公司 | Special rubber sealing ring for capacitor, and making method thereof |
| CN103613885B (en) * | 2013-10-28 | 2016-05-25 | 安徽东方金河精密机械制造有限公司 | A kind of mixing of rubber capacitor special sealing ring and preparation method thereof |
| CN103613885A (en) * | 2013-10-28 | 2014-03-05 | 安徽东方金河精密机械制造有限公司 | Special mixed rubber sealing ring for capacitors, and making method thereof |
| CN105505293A (en) * | 2016-01-15 | 2016-04-20 | 杨帆 | Antimicrobial and flame-retardant silicone sealant and preparation method thereof |
| CN105505293B (en) * | 2016-01-15 | 2017-12-12 | 河南理工大学 | Antibacterial flame-retardant silicone sealant and preparation method thereof |
| CN108546412A (en) * | 2018-04-24 | 2018-09-18 | 常州达奥新材料科技有限公司 | A kind of preparation method of rubber packing material |
| CN111681811A (en) * | 2020-05-15 | 2020-09-18 | 河南胜华电缆集团有限公司 | Flexible fireproof cable and preparation method of heat insulation layer thereof |
| CN111681811B (en) * | 2020-05-15 | 2022-05-03 | 河南胜华电缆集团有限公司 | Flexible fireproof cable and preparation method of heat insulation layer thereof |
| CN114874632A (en) * | 2022-06-13 | 2022-08-09 | 温州益坤电气股份有限公司 | Anti-fouling wear-resistant silicon rubber material for high-speed motor train unit and preparation method thereof |
| CN114874632B (en) * | 2022-06-13 | 2023-07-25 | 温州益坤电气股份有限公司 | Anti-fouling and wear-resistant silicone rubber material for high-speed motor train unit and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2009109225A1 (en) | Electrical insulation system based on silicone rubber | |
| WO2010112081A1 (en) | Silicone rubber composition | |
| JP4917164B2 (en) | Power cable member | |
| KR100999332B1 (en) | Hot-vulcanizable polyorganosiloxane compositions useful particularly for manufacturing electrical cables or wires | |
| KR102033211B1 (en) | Hot-vulcanisable polyorganosiloxane compositions for use in particular for the production of electrical wires or cables | |
| US8153718B2 (en) | Heat-vulcanizable polyorganosiloxane compositions and electric wires/cables produced therefrom | |
| US7851525B2 (en) | High temperature vulcanized silicone rubber | |
| JP3859791B2 (en) | Liquid silicone rubber composition for high voltage electrical insulation parts and method for producing the same | |
| KR20110018874A (en) | Silicone rubber compositions | |
| JP7476901B2 (en) | Millable silicone rubber composition, silicone rubber cured product, and electrical insulating member for connecting power cables | |
| JPH1077413A (en) | Heat-curable silicone rubber composition | |
| JP2006182823A (en) | Composition for high voltage electrically insulating silicone rubber, high voltage electrically insulating silicone rubber composition and high voltage electrical insulator | |
| WO2010127693A1 (en) | Curable sol-gel composition | |
| JP4956033B2 (en) | Heat-curable silicone rubber composition and silicone rubber molded article. | |
| EP3473661B1 (en) | Silicone composition, a cured silicone rubber product and a power cable | |
| JP6888593B2 (en) | Mirable type silicone rubber composition and electric field relaxation layer | |
| US6264865B1 (en) | Silicone rubber base compound for electrical wire coating, silicone composition for electrical wire coating, and process for the production of silicone rubber coated electrical wire | |
| KR100510343B1 (en) | Heat curable silicone rubber compositions having electrical insulation and high strength | |
| WO2016074172A1 (en) | Electrical insulating material and method for preparing insulating material element | |
| EP1052655B1 (en) | Silicone rubber compositions for high-voltage electrical insulators | |
| US6232387B1 (en) | Silicone rubber compositions for high-voltage electrical insulators | |
| JPH08325459A (en) | Silicone rubber composition for high-voltage electrical insulator | |
| MXPA01000118A (en) | Hydrophobicity imparting particulate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08717403 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 08717403 Country of ref document: EP Kind code of ref document: A1 |