CN102834875A - Composite insulation material for electrical insulation, method for producing and using the same - Google Patents
Composite insulation material for electrical insulation, method for producing and using the same Download PDFInfo
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- CN102834875A CN102834875A CN2011800199274A CN201180019927A CN102834875A CN 102834875 A CN102834875 A CN 102834875A CN 2011800199274 A CN2011800199274 A CN 2011800199274A CN 201180019927 A CN201180019927 A CN 201180019927A CN 102834875 A CN102834875 A CN 102834875A
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- composite material
- insulating composite
- filler powder
- nano particle
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—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
Abstract
A composite insulation material for electrical insulation has a resin component, a hardener component and a filler powder mixture which is distributed in the composite insulation material and which has a first fraction of filler powder comprising microparticles and a second fraction of filler powder comprising nanoparticles, wherein the particle distribution of the filler powder mixture is bimodal and has a proportion of 60 to 80% by weight in the composite insulation material and the second fraction of filler powder has a proportion of 0.1 to 6% by weight in the composite insulation material.
Description
At electrotechnics, particularly in the switchgear technology, the epoxy resin formulation that is filled with mineral matter of own knowledge hot curing and cold curing expects to be used to prepare to have high chemical resistance and high-resistance insulating composite material as perfusion.This epoxy resin formulation as bi-component batch of material (" 2K ") processing, wherein is used in the mixture with phthalic anhydride based on the reaction resin of bisphenol-A-diglycidyl ether or bisphenol-f-diglycidyl ether.For improve middle pressure-with the high-tension electricity load under insulating effect; For example be improvement part flash-over characteristic or raising breakdown strength; The inorganic filler of micron order size is added in the reaction resin mixture with the ratio of the highest 70 weight %, and said inorganic filler for example is silica derivatives such as alpha-quartz or amorphous quartzy material, aluminium oxide, mica, boron nitride.Use azepine derivatives ring-type and/or aliphatic nature for quickening hot gelatine/curing.
The inorganic filler that in reaction resin, adds the sphere/dihedral of big volume ratio particularly when proportion of filler surpasses 40 volume %, causes the disadvantageous high processing viscosity of this prepolymerization material.Produce the still upper maximum of exercisable proportion of filler thus, should have enough flowables for metering process and pumping process fast because this reactivity is sealed material.Hope in addition to coagulate the bubble of overflowing and in shaping jig, to be sealed through come-up in the Cheng Qian at the beginning hot glue because in the hole in the moulding material that solidifies with shrinkage hole can cause rejected region with cause thus mechanical and electric aspect the weaken fragile position of this moulding material.On the other hand, high filer content advantageously causes big resistance to cracking and anti-breaking property in epoxy resin composite material just, because the process of initiation crackle and crack propagation process slow down owing to said particle or stop.
In epoxy resin/filler powder-composite material commonly used, be about in average processing temperature under 50 ℃ the situation, the maximum of quartz powder filler ratio can be operated the upper limit and is about 66 weight %.Higher compactedness only can be followed consequent viscosity to reduce through the rising processing temperature to realize under exercisable processing fluidity still.But because the preparation cost that increases and the technology boundary condition of deterioration, so this is undesirable or impossible, because the rising processing temperature will shorten time pot life (Topfzeitfenster) up to the beginning gelatine.
The hard ceramic particles that the sphere of known use micron order size or dihedral filler, particularly low price are easy to obtain is used to improve the fracture toughness and the energy to failure of disconnected plastic molded material.But the medium loading of this type and the high epoxy resin composite that loads demonstrate under cyclical heat load and/or mechanical load (as through summer/winter-circulation, the vibration that caused by operation etc.) and have formed the crackle that can cause component failure.Be used to improve crackle stop the micron order size, soft of ability and organically particle (synthetic rubber) given to remedy because cause the raising of acquisition maximum permissible load limit value through the plastically deformable property (ductility) of this particle.But the shortcoming here is, said rubber grain since synthesis condition be easy to assemble, and be easy to thus form cause that viscosity increases bunch.
In DE 10345139 A1, described in the epoxy reaction reactive resin system combination and loaded inorganic micron order and nano level quartz particles and add the i.e. three peak filler level branches of silicon elasticity particulate simultaneously, can cause being used for diode, ignition coil and through the linear attenuation of sealing material, thermal expansion and the maximum favourable variation that allows tear stress and tear elongation of the electric winding of dipping.But the shortcoming here is, this used powder of nanometric particles can form inseparable primary nanoparticle aggregate and the primary nanoparticle aggregation that diameter is hundreds of nanometers and since the fractals of primary nanoparticle aggregate its impair processing viscosity.
The objective of the invention is to; Be provided for the insulating composite material of electric insulation, the preparation method of this insulating composite material and the application of this insulating composite material, this insulating composite material has low viscosity and however still good fracture mechanics overall performance when casting.
The insulating composite material that is used for electric insulation according to the present invention has resinous principle, curing agent component and is distributed in the filler powder mixture of this insulating composite material; This mixture has the first filler powder level branch of micron particles (Mikropartikel) and the second filler powder level branch of nano particle; Wherein the distribution of particles of this filler powder mixture is a bimodal distribution; And the ratio in insulating composite material is 60-80 weight %, and the content that the second filler powder level in insulating composite material is divided is 0.1-6 weight %.
The distribution of particles of this filler powder mixture preferably has the particle size distribution that does not have overlapping nano particle and micron particles.In addition, the nano particle that this second filler powder level is divided particularly prepares based on polybutadiene and/or polybutadiene-polystyrene-common-polymer preferably by polymer.In addition, resinous principle preferably epoxy resin or higher official can epoxy resin, it is based on bisphenol-A-diglycidyl ether, bisphenol-f-diglycidyl ether, or alicyclic resin or by its mixture of forming.Curing agent component is preferably based on anhydride curing agent class, particularly phthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride or other anhydride ester derivs.
It is 0.3-300 μ m that the micron particles that this first filler powder level is divided preferably has granularity.Here preferably; The micron particles that this first filler powder level is divided is selected from sphere and angled metal oxide, half-metal oxide, metal carbides, semimetal carbide, metal hydroxides or semimetal hydroxide, particularly is selected from silica flour, quartzy material, aluminium oxide, carborundum, aluminium hydroxide and magnesium hydroxide.In addition preferably, the surface of the micron particles of this first filler powder level branch is the matrix compatibilized.
The nano particle that this second filler powder level is divided preferably has spherical form, and particularly prepares as polybutadiene-polystyrene-altogether-mixture of polymers based on polybutadiene, polystyrene or its.Here preferably, the granularity of the nano particle that this second filler powder level is divided is 50-120 nm, and is substantially free of aggregate and/or does not contain aggregation.In addition, the preferred surperficial compatibilized of the nano particle that divides of this second filler powder level through the methyl methacrylate derivatization of polymerization.
The method that is used for preparing insulating composite material according to the present invention has the following step: nano particle is sneaked into resinous principle; Produce the reaction resin system.According to the present invention; This insulating composite material is used for cast when the preparation insulating component; Said insulating component is used for medium and high pressure to be used, especially for male part and the transformer and the current transformer of plug ferrule and cable sleeve, cable fitting, support insulator, fuse box, bus (Sammelschienen).
Advantageously has improved fracture mechanical property and low perfusion material viscosity according to insulating composite material of the present invention.In detail; Promptly the perfusion material of this insulating composite material has high flowability, has wherein realized the thermal expansion of the energy to failure (critical energy to failure) of the fracture toughness (critical stress intensity coefficient) of high molding compounds, high molding compounds, low molding compounds, high molding compounds-gamma transition scope and low perfusion material processing viscosity.
Compare with the particle size distribution that independent filler powder level is divided; According to the present invention; This filler powder mixture reaches higher packing density in insulating composite material; Thus, have dynamic viscosity by the reaction resin system of this insulating composite material preparation, said viscosity for example under typical processing temperature in 0.01-500 s
-1Rate of shear rate scope advantageously be 2-30 Pas.The viscosity of the insulating composite material that is obtained according to the present invention reduce with and the increase of fracture mechanics characteristic value obtain through the nano particle masterbatch is provided.Obtained the dispersion with the nano particle loading, this dispersion has the base matrix (Grundmatrix) identical with the original principle of treating improved epoxy resin ingredients.Nano particle advantageously goes to be present in the insulating composite material with assembling, and forms low viscous dispersion.Unexpectedly, this in insulating composite material is the reduction that providing of combination demonstrates processing viscosity with nano particle and micron particles, though the packing volume content of the mixture that does not contain nano particle of benchmark increases.
Reached the grain packing coefficient optimization that produces on the spot through mix the processing viscosity that nano particle reduces the perfusion material of insulating composite material according to the present invention.In this case, nano particle has occupied the wedge shape space between gap and the micron particles, and the dynamic viscosity of this insulating composite material reduces under typical processing temperature thus.
Through there is not overlapping micron filler (Mikrof ü llstoff)/Nano filling-mixed level branch that contains that the nano particle that goes gathering masterbatch is provided according to preferably basic particle size distribution provided by the invention; Make with this masterbatch and to reduce to the processing viscosity of the epoxy resin formulation of high filling in commonly used, and improved fracture mechanical characteristics value owing to the existence of nano particle in the hot curing moulding material simultaneously.Show in addition, compare, adopt organic nanometer granule significantly to improve the stability of the fracture mechanics of moulding material with the inorganic counterparts of pottery, but the three peak property that needn't use the required filler level in there to divide.Particularly compare with using the common combination by the quartzy material of pottery nano particle and polysiloxane particle, the organic nanometer granule of polybutadiene that use has an acryloyl basic unit of grafting improves matrix-compatibility, and it be excellent for oneself to show.Advantageously, be somebody's turn to do the single bimodal mixture of being made up of micron order silica flour can reduce viscosity and improve moulding material simultaneously under the situation of low ratio polybutadiene-nano particle fracture mechanics.In addition, the perfusion material viscosity that reduces according to the present invention has also been opened the possibility of further raising proportion of filler, to reach the mobile level of master reference.Can in the epoxy resin preparation, realize the proportion of filler that improves with the method, otherwise the raising of proportion of filler only can realize just under elevated temperature or additional flow promortor.Ratio through increasing filler particles further helps fracture toughness and has improved required at least energy to failure in addition.
By means of a plurality of embodiment the present invention is detailed below.
In order to explain, with constant total filler content but increase continuously the nano particle ratio and come example Journal of Sex Research embodiment (comparison sheet 1 and 2).Here resinous principle A has bisphenol-A-diglycidyl ether and curing agent component B has methyl tetrahydrophthalic anhydride.This mixing ratio is 100: 82 (m/m).Adopt average diameter D as the micron filler
50The silica flour of the surface silicon alkanisation of=20 μ m; Organic (embodiment P1-P4) nano particle of inorganic (embodiment A 1-A4) and polymerization adds as the batch of material of resinous principle A.The benchmark system (reference) that does not contain nano particle is system as a comparison.
Table 1: filler is formed and rheological property
aPress the Searle-Geometrie of DIN 53019, T=50 ℃.
Table 2: moulding material performance
A, bAccording to ASTM E 399, two reversing-check, T=25 ℃
cγ=3 α (linear hot longitudinal dilatation coefficient), ISO 11359-2
dDynamically-mechanics heat analysis (DMTA).
Consider that possible filler increases, keeping under the mobile condition of benchmark, exemplarily studied utilization that viscosity is reduced (referring to table 3 and 4 with the embodiment of total filler content with raising; Inorganic nano particle embodiment A 5-A8, organic nanometer granule embodiment P5-P8).Here, the resin material (A+B) that does not contain filler keeps the composition of its component ratio constant.Depend on nano-particle content, this filler level is divided in proportion so to be increased, with maximum and the mobile limit value η of the characteristic of benchmark mixture that must be in flow curve
Max, RefConsistent.Thus, compare with the perfusion material that does not contain nano particle, the embodiment of all descriptions all shows identical flow behavior.
Table 3: filler is formed and rheological behavior
Table 4: moulding material performance
According to micron order filler of the present invention with go the combination of the nano particle of gathering to make in power technology fully; Particularly in switchgear components, use epoxy molding material to become possibility; It has seen improvement from the fracture mechanics angle, but wherein simultaneously the flowability of the perfusion material on basis is had no adverse effect.This base matrix can comprise the aromatic resin or the cycloaliphatic epoxy resin of bisphenol-A-diglycidyl ether or bisphenol-f-diglycidyl ether type.As the solidification material, (alkylating) phthalic anhydride such as methyl tetrahydrophthalic anhydride or methylhexahydrophthalic anhydride prove suitable.As promoter, tertiary amine for example dimethylaniline or imdazole derivatives is favourable.Also can add additive on a small quantity as removing antifoaming agent, dispersing aid, colorant and flexibilizer.
As micron-sized filler, granularity is that the silica flour or the quartzy material of the surface silicon alkanisation of 0.3-300 μ m proves suitable.Here, this nano-scale particle is inorganic in nature (particle diameter D
50The amorphous quartzy of=20-40 nm expected), but preferred organic character.Use that polybutadiene-nano particle or polybutadiene-polystyrene-altogether-polymer-nano particle is specially suitable, for particle surface on resinous substrates compatible better, can be with it with polymethyl methacrylate layers derivatization (so-called core-shell-particle).Preferred particle diameter is D to organic nanometer granule
50=80-100 nm.This particle has the form of going gathering fully, can't assemble cluster.The content of nano particle is 0.1-6 weight %.
Preparation according to the present invention is particularly useful for electrotechniical switching device technical elements, for example in preparation during based on the male part of the plug ferrule of thermoset plastics and cable sleeve, cable fitting, support insulator, fuse box, bus and transformer and current transformer.
Claims (13)
1. the insulating composite material that is used for electric insulation; Its resinous composition, curing agent component and be distributed in the filler powder mixture in this insulating composite material; This mixture has the first filler powder level branch of micron particles and the second filler powder level branch of nano particle; Wherein the distribution of particles of this filler powder mixture is a bimodal distribution; And the ratio that in insulating composite material, has 60-80 weight, and said second filler powder level branch has the ratio of 0.1-6 weight % in insulating composite material.
2. according to the insulating composite material of claim 1, wherein the distribution of particles of this filler powder mixture does not have particle size distribution overlapping of nano particle and micron particles.
3. according to the insulating composite material of claim 1 or 2, the nano particle that the wherein said second filler powder level is divided derives from polymer, and especially based on polybutadiene and/or polybutadiene-polystyrene-common-polymer manufacture.
4. according to the insulating composite material of one of claim 1-3; Wherein said resinous principle is the epoxy resin of epoxy resin or higher official ability; It is based on bisphenol-A-diglycidyl ether, bisphenol-f-diglycidyl ether, or alicyclic resin or by its mixture of forming.
5. according to the insulating composite material of one of claim 1-4, wherein said curing agent component acid anhydride-based curing agent class, particularly phthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride or other anhydride ester derivs.
6. according to the insulating composite material of one of claim 1-5, the micron particles of the wherein said first filler powder level branch (C) has the granularity of 0.3-300 μ m.
7. according to the insulating composite material of claim 6; The micron particles that the wherein said first filler powder level is divided is selected from sphere and angled metal oxide, half-metal oxide, metal carbides, semimetal carbide, metal hydroxides or semimetal hydroxide, particularly is selected from silica flour, quartzy material, aluminium oxide, carborundum, aluminium hydroxide and magnesium hydroxide.
8. according to the insulating composite material of claim 7, the surface of the micron particles that the wherein said first filler powder level is divided is through the matrix compatibilized.
9. according to the insulating composite material of one of claim 1-8; The nano particle that the wherein said second filler powder level is divided has spherical form, and particularly based on polybutadiene, polystyrene or its as polybutadiene-polystyrene-altogether-mixture of polymers preparation.
10. according to the insulating composite material of claim 9, the nano particle that the wherein said second filler powder level is divided has the granularity of 50-120 nm, and is substantially free of aggregate and/or does not contain aggregation.
11. according to the insulating composite material of claim 10, wherein make nano particle that the said second filler powder level divides through the methyl methacrylate derivatization of polymerization surperficial compatibilized.
12. be used to prepare the method for the insulating composite material of claim 1-11, it has the following step: nano particle is sneaked in the resinous principle; Produce the reaction resin system.
13. the application that is used to pour into a mould when the preparation insulating component according to the insulating composite material of claim 1-12; Said insulating component is used for medium and high pressure to be used, especially for male part and the transformer and the current transformer of plug ferrule and cable sleeve, cable fitting, support insulator, fuse box, bus.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010015398.2 | 2010-04-19 | ||
| DE102010015398A DE102010015398A1 (en) | 2010-04-19 | 2010-04-19 | Insulating composite material for electrical insulation, method of making and using same |
| PCT/EP2011/055816 WO2011131537A2 (en) | 2010-04-19 | 2011-04-13 | Composite insulation material for electrical insulation, method for producing and using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102834875A true CN102834875A (en) | 2012-12-19 |
Family
ID=44280646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800199274A Pending CN102834875A (en) | 2010-04-19 | 2011-04-13 | Composite insulation material for electrical insulation, method for producing and using the same |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2529377A2 (en) |
| CN (1) | CN102834875A (en) |
| DE (1) | DE102010015398A1 (en) |
| WO (1) | WO2011131537A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694636A (en) * | 2013-12-10 | 2014-04-02 | 中国科学院过程工程研究所 | Electric insulating epoxy resin composition, preparation method and use of composition |
| CN104177780A (en) * | 2014-08-20 | 2014-12-03 | 国家电网公司 | Outdoor electric-insulation modified epoxy resin composition |
| CN104882233A (en) * | 2015-05-11 | 2015-09-02 | 江苏江城电气有限公司 | Manufacturing technique of insulated film dedicated to wind-power tubular bus |
| CN105801001A (en) * | 2016-03-01 | 2016-07-27 | 昆山东大智汇技术咨询有限公司 | Mineral casting raw material formula and process for fire-resistant cast bus |
| CN108305723A (en) * | 2018-02-01 | 2018-07-20 | 清华大学 | Benzvalene form and support insulator based on nonlinear material doping |
| CN113906524A (en) * | 2019-03-27 | 2022-01-07 | 西门子股份公司 | Casting resin, molding material made of the same, use thereof and electrical insulation |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011083409A1 (en) * | 2011-09-26 | 2013-03-28 | Siemens Aktiengesellschaft | Insulating systems with improved partial discharge resistance, process for the preparation thereof |
| EP2623565A1 (en) * | 2012-02-06 | 2013-08-07 | Siemens Aktiengesellschaft | Repair substance |
| DE102012205046A1 (en) * | 2012-03-29 | 2013-10-02 | Siemens Aktiengesellschaft | An electrical insulation body for a high-voltage rotary machine and method for producing the electrical insulation body |
| CN104900299B (en) * | 2015-04-10 | 2017-01-18 | 西北核技术研究所 | Polymer insulator with uniform hole distribution on surface and preparation method thereof |
| US20180171101A1 (en) * | 2015-06-16 | 2018-06-21 | Huntsman International Llc | Epoxy Resin Composition |
| DE102015218839A1 (en) | 2015-09-30 | 2017-03-30 | Siemens Aktiengesellschaft | Potting compound and use |
| DE102019204190A1 (en) * | 2019-03-27 | 2020-10-01 | Siemens Aktiengesellschaft | Cast resin, molded body made therefrom and use of the molded body |
| CN114496429B (en) * | 2022-03-07 | 2022-10-11 | 华北电力大学 | Nonlinear conductive composite material based on nano electrostatic adsorption and preparation method thereof |
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| CN101423651A (en) * | 2007-11-02 | 2009-05-06 | 中国船舶重工集团公司第七二五研究所 | Process for preparing low temperature, high heat conducting and electrical insulation epoxy resin nano composite material |
| CN101481468A (en) * | 2003-07-03 | 2009-07-15 | 德古萨公司 | Silane formulation with high filler content |
| DE102008030904A1 (en) * | 2008-06-30 | 2009-12-31 | Siemens Aktiengesellschaft | Composite with nano-powder and use of the composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2151949T3 (en) * | 1994-12-13 | 2001-01-16 | Ciba Sc Holding Ag | ENDURABLE LIQUID MASSES, BASED ON EPOXY RESIN, CONTAINING A NUCLEUS / WRAPPED TYPE TENACITY PROMOTER. |
| DE10345139A1 (en) | 2003-09-29 | 2005-04-21 | Bosch Gmbh Robert | Thermosetting reaction resin system, useful e.g. for impregnating electrical coils and sealing diodes, comprises resin component (containing dispersed polymer particles) and mineral fillers (containing nanoparticles) |
-
2010
- 2010-04-19 DE DE102010015398A patent/DE102010015398A1/en not_active Ceased
-
2011
- 2011-04-13 WO PCT/EP2011/055816 patent/WO2011131537A2/en active Application Filing
- 2011-04-13 CN CN2011800199274A patent/CN102834875A/en active Pending
- 2011-04-13 EP EP11715216A patent/EP2529377A2/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481468A (en) * | 2003-07-03 | 2009-07-15 | 德古萨公司 | Silane formulation with high filler content |
| CN101423651A (en) * | 2007-11-02 | 2009-05-06 | 中国船舶重工集团公司第七二五研究所 | Process for preparing low temperature, high heat conducting and electrical insulation epoxy resin nano composite material |
| DE102008030904A1 (en) * | 2008-06-30 | 2009-12-31 | Siemens Aktiengesellschaft | Composite with nano-powder and use of the composite material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694636A (en) * | 2013-12-10 | 2014-04-02 | 中国科学院过程工程研究所 | Electric insulating epoxy resin composition, preparation method and use of composition |
| CN104177780A (en) * | 2014-08-20 | 2014-12-03 | 国家电网公司 | Outdoor electric-insulation modified epoxy resin composition |
| CN104882233A (en) * | 2015-05-11 | 2015-09-02 | 江苏江城电气有限公司 | Manufacturing technique of insulated film dedicated to wind-power tubular bus |
| CN105801001A (en) * | 2016-03-01 | 2016-07-27 | 昆山东大智汇技术咨询有限公司 | Mineral casting raw material formula and process for fire-resistant cast bus |
| CN108305723A (en) * | 2018-02-01 | 2018-07-20 | 清华大学 | Benzvalene form and support insulator based on nonlinear material doping |
| CN113906524A (en) * | 2019-03-27 | 2022-01-07 | 西门子股份公司 | Casting resin, molding material made of the same, use thereof and electrical insulation |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2529377A2 (en) | 2012-12-05 |
| DE102010015398A1 (en) | 2011-10-20 |
| WO2011131537A3 (en) | 2012-05-03 |
| WO2011131537A2 (en) | 2011-10-27 |
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Application publication date: 20121219 |