CN102020850B - Corona resistant composition and preparation method thereof - Google Patents
Corona resistant composition and preparation method thereof Download PDFInfo
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- CN102020850B CN102020850B CN2009101901663A CN200910190166A CN102020850B CN 102020850 B CN102020850 B CN 102020850B CN 2009101901663 A CN2009101901663 A CN 2009101901663A CN 200910190166 A CN200910190166 A CN 200910190166A CN 102020850 B CN102020850 B CN 102020850B
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Abstract
The invention provides a corona resistant composition and a preparation method thereof. The corona resistant composition comprises polyimide and nano alumina granules; and based on the total weight of the corona resistant composition, the polyimide accounts for 70 to 95 percent, the nano alumina granules account for 5 to 30 percent, a silane coupling agent accounts for 0.01 to 0.3 percent, and a polyester modified acrylate block copolymer dispersant accounts for 0.005 to 0.3 percent. The prepared corona resistant composition has excellent corona resistance; and under the condition that the thickness of the corona resistant composition is 22 to 28 microns, the corona resistant time of the corona resistant composition is more than one hundred thousand hours.
Description
Technical field
The present invention relates to a kind of composition and method of making the same of anti-the corona, relate in particular to a kind of composition and method of making the same of anti-corona that contains polyimide and nano alumina particles.
Background technology
In recent years, owing to have advantages such as efficient, energy-conservation, easy to use, frequency control motor had obtained rapid popularization, and progressively replaced mechanical speed change and dc speed-regulating motor.But the pulse wave that RHVC provides; Have towering spike crest, the precipitous rise time arranged, variable or high frequency; Sometimes can reach 20KHz; Add pulsed voltage and on winding, divide polarity inhomogeneous, make near the turn-to-turn voltage of the winding of head end exceed tens of times of evenly distribute voltages, the result causes winding inter-turn generation shelf depreciation; The inner insulation layer of frequency conversion electrical equipment receives the influence of multiple factors such as electricity, heat, machinery and causes destroying, and is more remarkable to the destruction of insulation layer with corona especially.Make the very easy in use breakdown between adjacent turns of variable-frequency motor.For guaranteeing the operation life of variable-frequency motor, people also transfer to research emphasis on the corona-resistance property of strengthening motor winding insulation material except on convertible circuit and control techniques, suppressing the spike superpotential on the motor terminal as much as possible.
As just disclosing a kind of compsn of anti-the corona in the existing technology; This compsn of anti-the corona comprises: A. polymeric matrix; The high temperature polymer that contains at least 50,60,70,75,80,85,90,95,96,97,98,99 or 100 weight %, one or more parts that are selected from acid amides, imide, ether, sulfone, epoxy, carbonic ether and ester that this high temperature polymer has; B. its amount (based on the gross weight of the compsn of anti-the corona) of the compounded mix of anti-corona the: i. is in following any two (comprising end points) weight percentage scopes: 2,3,4,5,6,7,8,9,10,12,15,18,20,24,25,28,30,32,34,35,36,38,40,42,44,46,48 and 50 weight %; Ii. average particle size particle size (being scattered in the polymeric materials) is in following any two (comprising end points) size ranges: 5,10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95,100,125,150,175,200,250,300,350,400,450 and 500 nanometers; Wherein, At least 80,85,90,92,94,95,96,98,99 or 100% dispersive compounded mix is in above-mentioned size range; Iii. contain ceramic oxide component and organic constituent, wherein organic-siloxanes or organic-metallic oxygen alkane part are contained in the part interface between two components at least.
Though this prior art is added ceramic oxide in the polymeric matrix to; Improved the corona-resistance property of the compsn of anti-the corona; But because the ceramic oxide particulate specific surface area and the surface energy that add are big, and there is stronger interaction between the ceramic oxide particle, is easy to generate reunion; Though added organic-siloxanes or organic-metallic oxygen alkane therein,, still be difficult to make ceramic oxide in polymkeric substance, to reach abundant dispersion state, thereby limited the corona-resistance property of this compsn of anti-the corona.
Summary of the invention
The technical problem that the present invention solved provides the good compsn of anti-corona of a kind of corona-resistance property.
For this reason; The invention provides a kind of compsn of anti-the corona, comprise polyimide, nano alumina particles, silane coupling agent, polyester modification acrylate block copolymer dispersion agent, is benchmark with anti-corona composition total weight; Polyimide accounts for 70-95%; Nano alumina particles accounts for 5-30%, and silane coupling agent accounts for 0.01-0.3%, and polyester modification acrylate block copolymer dispersion agent accounts for 0.005-0.3%; The described compsn of anti-the corona is that the anti-corona time under the condition of 25 μ m is more than 100,000 hours at mean thickness.
The present invention also provides a kind of anti-corona preparation of compositions method, and this method comprises:
(1) nano alumina particles, silane coupling agent, polyester modification acrylate block copolymer dispersion agent are put into dispersed with stirring in the solvent, make nano oxidized aluminum slurry;
(2) aromatic diamine, tetracarboxylic dianhydride are joined in the nano oxidized aluminum slurry of preparation in the step 1 successively, heating reacts, and makes nano aluminium oxide/polyamic acid composite mortar;
(3) with the heating of nano aluminium oxide/polyamic acid composite mortar, imidization reaction taking place, obtain the compsn of anti-the corona, is under the condition of 25 μ m at the mean thickness of the above-mentioned compsn of anti-the corona, and the anti-corona time of the compsn of anti-the corona is more than 100,000 hours.
Polyimide and nano alumina particles in the compsn of anti-corona the provided by the present invention; Has the good interface intermiscibility; Nano alumina particles is evenly distributed in polyimide, and the prepared compsn of anti-the corona has good corona-resistance property, is under the condition of 25 μ m at mean thickness; The anti-corona time of this compsn of anti-the corona can reach more than 100,000 hours, and this compsn of anti-the corona also has mechanical property preferably simultaneously.
Embodiment
The present invention provides a kind of compsn of anti-the corona; Comprise polyimide, nano alumina particles, silane coupling agent, polyester modification acrylate block copolymer dispersion agent; With anti-corona composition total weight is benchmark, and polyimide accounts for 70-95%, and nano alumina particles accounts for 5-30%; Silane coupling agent accounts for 0.01-0.3%; Polyester modification acrylate block copolymer dispersion agent accounts for 0.005-0.3%, is under the condition of 25 μ m at the mean thickness of the above-mentioned compsn of anti-the corona, and the anti-corona time of the compsn of anti-the corona is more than 100,000 hours.
Polyimide English name Polyimide (be called for short PI) is reacted and is made by aromatic diamine and aromatic series dianhydride, aromatic tetracarboxylic acid or aromatic tetracarboxylic acid's dialkyl.By bibenzene tetracarboxylic dianhydride and Ursol D synthetic polyimide, heat decomposition temperature reaches 600 ℃.Polyimide can be low temperature resistant, as can embrittlement in-269 ℃ liquid helium.Polyimide has excellent dielectric properties simultaneously, and specific inductivity is about 3.4.
The polyimide that is adopted among the present invention is by the generation that reacts of tetracarboxylic dianhydride and aromatic diamine, wherein said tetracarboxylic dianhydride be selected from pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1; 4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6; 7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1, two (trifluoromethyl)-2,3,5 of 4-, 6-benzene tertacarbonic acid dianhydride (P6GDA), 3; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,6-dichloronaphtalene-1,4; 5,8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5,8-tetracarboxylic dianhydride, 2,3; 6,7-Tetrachloronaphthalene-2,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9; 10-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5, a kind of among the 6-tetracarboxylic dianhydride.Under preferable case, be selected from equal benzene tertacarbonic acid's dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-a kind of in the benzophenone tetracarboxylic dianhydride.Aromatic diamine be selected from 4,4,4 '-diaminobenzophenone, 3,3 '-dimethyl--4; 4 '-diaminobenzophenone, 3,3 '-two chloro-4,4 '-diaminobenzophenone, mphenylenediamine, Ursol D, 4 '-methylene-bis (neighbour-chloroaniline), 3,3 '-dichloro diphenylamine, 3; 3 '-alkylsulfonyl pentanoic, 1,5-diaminonaphthalene, 2,2 '-two (4-amino-phenols), 4,4 '-benzidine, 4; 4 '-methylene dianiline (MDA), 4,4 '-sulfenyl pentanoic, 4,4 '-isopropylidene pentanoic, 3,3 '-tolidine, 3; 3 '-dimethoxy benzidine, 3,3 '-dicarboxylate biphenyl amine, 2,4 di amino toluene, 2; 5-diaminotoluene, 2,4-diamino--5-toluene(mono)chloride, 2, a kind of in 4-diamino--6-toluene(mono)chloride.
Adopt nano alumina particles as weighting material in the compsn of anti-corona that provides among the present invention; After nano alumina particles joins in the polyimide resin; Can form one deck inorganic oxide " shell "; Ozone, charged particle and heat etc. to the high-frequency electrical pulses stream shield effectively, the insulating material of protection internal layer.The median size of the nano alumina particles that is adopted among the present invention is 5-500nm; Under the preferable case 50-300nm; The nano particle within this scope have and silane coupling agent, polyester modification acrylate block copolymer between enough contacts area; Can not add simultaneously the generation of reaggregation again because surface energy is too high; This helps the raising of material corona-resistance property, and the uniform distribution of nano alumina particles also has very great help for the raising of the mechanical property of the compsn of anti-the corona simultaneously, and is opposite; If nano alumina particles is skewness in polyimide, its result who causes is that the corona-resistance property that causes the compsn of anti-the corona descends, mechanical properties decrease.
The contriver finds in experiment, though use silane coupling agent or polyester modification acrylate block copolymer dispersion agent can improve the dispersion effect of nano aluminium oxide in polyimide separately; Compare with the composite use of polyester modification acrylate block copolymer dispersion agent with the silane coupling agent that is adopted among the present invention, its effect does not obviously have the dispersion effect of technical scheme provided by the present invention obvious, and the quality of dispersion effect; Influence the anti-corona effects of the compsn of anti-the corona, because, inhomogeneous if aluminum oxide disperses in polyimide; Can in polyimide, reunite, when the generation high-frequency pulse current impacts the compsn of anti-the corona, because the nano aluminium oxide skewness in the polyimide; Can cause in the polyimide; Be distributed with nano oxidized aluminum portions and do not distribute and have the difference on the aging speed between the nano oxidized aluminum portions, and then quickened the aging speed of the compsn of anti-the corona, and adopt silane coupling agent and polyester modification acrylate block copolymer dispersion agent to be used among the present invention; In use produce synergy; Improve the nano aluminium oxide surface polarity, increased the interfacial phase dissolubility of nano aluminium oxide and polyimide resin, made nano aluminium oxide be dispersed in the polyimide more uniformly; Be evenly distributed on the nano alumina particles in the polyimide resin; Make and had the each several part of polyimide resin the corona-resistance property of homogeneous, thereby prolonged the anti-corona time of the compsn of anti-the corona.
The present invention also provides a kind of preparation anti-corona method for compositions, and this method comprises:
(1) nano alumina particles, silane coupling agent, polyester modification acrylate block copolymer dispersion agent are added in the solvent, dispersed with stirring makes nano oxidized aluminum slurry;
(2) aromatic diamine, tetracarboxylic dianhydride are joined in the nano oxidized aluminum slurry for preparing in 1 step successively, heating reacts, and makes nano aluminium oxide/polyamic acid composite mortar;
(3) with nano aluminium oxide/polyamic acid composite mortar, imidization reaction takes place in heating, prepares the compsn of anti-corona the provided by the present invention.
Wherein the weight ratio of nano alumina particles, silane coupling agent, polyester modification acrylate block copolymer dispersion agent, solvent is 1 in the step 1: 0.02-0.1: 0.01-0.1: 10-100.
Used silane coupling agent is a kind of in the common various silane coupling agents in this area such as Racemic glycidol oxygen propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-mercaptan aminopropyl trimethoxysilane, the anilinomethyl Ethoxysilane in the step 1.Above-mentioned silane coupling agent can be through being purchased the KH550 type silane coupling agent that obtains like the production of Dow corning company.
Used polyester modification acrylate block copolymer dispersion agent in the step 1, it has following structure:
Wherein x is the integer of 10-40, and y is the integer of 40-50.
Polyester modification acrylate block copolymer dispersion agent can be through being purchased acquisition, like the modified acroleic acid ester block copolymer of Bi Ke chemical company production.
And the solvent in the step 1 is selected from N, dinethylformamide, DMAC N,N, a kind of in the N-Methyl pyrrolidone.
In step 2, successively aromatic diamine, tetracarboxylic dianhydride are added in the nano oxidized aluminum slurry that makes in the step 1, wherein, the weight ratio of nano oxidized aluminum slurry and aromatic diamine, aromatic series dianhydride is 1: 0.04-0.15: 0.04-0.15.
In step 2, adopt the tetracarboxylic dianhydride joined in the solution of aromatic diamine and react, rather than with tetracarboxylic dianhydride elder generation and stirring solvent, obtain tetracarboxylic dianhydride's solution after; Add aromatic diamine again; This be because, if earlier the tetracarboxylic dianhydride is joined in the solvent, stir for some time after; The tetracarboxylic dianhydride can with solvent generation complex reaction, can reduce the reactive behavior of tetracarboxylic dianhydride and aromatic diamine like this.
Polymerization takes place in aromatic diamine that in step 2, relates to and tetracarboxylic dianhydride under the condition that solvent exists; Generate the reaction of polyamic acid; And the imidization reaction that cyclodehydration takes place in heat-processed related polyamic acid in the step 3 is reaction known in those skilled in the art, repeats no more at this.
React in the process that generates polyimide at aromatic diamine and tetracarboxylic dianhydride; Because nano alumina particles is dispersed in the solution that contains aromatic diamine and tetracarboxylic dianhydride; Therefore when reacting, can original position generate polyamic acid on the nano alumina particles surface, and these are created on the polyamic acid on nano alumina particles surface; Can further improve the intermiscibility of nano alumina particles and polyamic acid, improve the dispersion effect of nano aluminium oxide in polyamic acid.Temperature in the heating described in the step 2 is 10-60 ℃; And the reaction conditions of the imidization in 3 steps comprises, aluminum oxide/polyamic acid composite mortar is passed through following heat treatment process successively: keep down 0.5-1.5 hour, 180-250 ℃ to keep 0.5-1.5 hour, 230-280 ℃ to keep 0.5-1.5 hour, 260-350 ℃ to keep 0.5-1.5 hour down down down at 70-200 ℃.
Following mask body is introduced a kind of concrete, anti-corona preparation of compositions method provided by the present invention:
(1) nano aluminium oxide pulp preparation
The alumina particle of the 50-300nm of 2-30g is dispersed in the N of 500-5000g; In the N-N,N-DIMETHYLACETAMIDE; Ultrasonic auxiliary machinery dispersed with stirring; Add then 0.01-4g coupling agent γ-An Jibingjisanyiyangjiguiwan (Z-6011, Dow corning company) and 0.01-4g the polyester modification acrylate block copolymer, obtain nano oxidized aluminum slurry after stirring 10-150min.
(2) take by weighing the 10-100g aromatic diamine, the aromatic series dianhydride of 10-100g joins the aromatic diamine that weighs up in 1 step in the resultant nano oxidized aluminum slurry earlier, stirs; Add the tetracarboxylic dianhydride then, adopt heating in water bath during this period, keeping temperature is 10-60 ℃; Stirring velocity is 50-3000 rev/min, and churning time is 0.2-15h, during this period; Tetracarboxylic dianhydride and aromatic diamine react, and through this step, obtain nano aluminium oxide/polyamic acid composite mortar;
(3) with the nano aluminium oxide/polyamic acid composite mortar that obtains in the step 2; The degassing; Dry; Make polyamic acid that cyclodehydration reaction at high temperature take place and generate the compsn of anti-the corona that the polymkeric substance that can qualitatively judge in the compsn of anti-corona that method provided by the invention can access according to the ABC of organic synthesis is a polyimide.Certainly, also can carry out qualitative sign according to ir spectra.1720cm in the ir spectra
-1Near strong peak is a C=O stretching vibration absorption peak, 1380cm
-1Strong peak is a C-N stretching vibration absorption peak in neighbouring.If occur above-mentioned peak in the ir spectra, then can explain to have obtained polyimide.Said ir spectra spectrogram can adopt the U.S. NEXUS470 of Nicolet company type fourier transform infrared spectroscopy, Potassium Bromide coating to obtain.The said determination method has been conventionally known to one of skill in the art, repeats no more at this.Owing to adopt very sophisticated method synthesis of polyimides among the present invention, therefore especially the structure of polyimide film is not characterized in an embodiment.
Thereby the quality of polyimide in the compsn of anti-corona that in above-mentioned steps, finally obtains for the quality raising that further improves polyamide acid film; Under the preferable case, the polyamic acid solution described in the method provided by the invention is the polyamic acid solution of process at 15-40 ℃ of following vacuum outgas 1-12 hour preferred 1-2 hour.In other words; Under the preferable case, method provided by the invention also is included in before the polyamic acid solution heating, earlier with nano aluminium oxide/polyamic acid solution at 15-40 ℃ of following vacuum outgas 1-12 hour; Preferred 1-2 hour, to remove the bubble that possibly exist in the solution.The vacuum tightness of said vacuum outgas can guarantee the non-volatile or a small amount of volatilization of nano aluminium oxide/polyamic acid solution, and under the preferable case, said vacuum tightness is the 0.001-0.1 MPa.
The drying of in step 3, being mentioned adopts the progressively mode of imidization of gradient increased temperature, and heating is converted into polyimide with polyamic acid under nitrogen, argon gas or vacuum, obtains the compsn of anti-the corona.The temperature of heating is 70-200 ℃ and keeps down 0.5-1.5 hour, 180-250 ℃ to keep 0.5-1.5 hour, 230-280 ℃ to keep 0.5-1.5 hour, 260-350 ℃ to keep 0.5-1.5 hour down down down.
Specify the composition and method of making the same of anti-corona the provided by the present invention with concrete embodiment below.
Embodiment 1
Present embodiment is used for explaining the composition and method of making the same of anti-corona the provided by the present invention.
Take by weighing the nano alumina particles that the 20g median size is 80nm, the γ-An Jibingjisanyiyangjiguiwan coupling agent of 0.6g, the polyester modification acrylate block copolymer dispersion agent of 0.2g; And 800mL solvent DMAC N,N, put into double-layer glass reaction kettle (RAT; Wuxi City Shen Ke instrument plant) in, is under the condition of 1000r/min, stirs 1h and obtain nano oxidized aluminum slurry at rotating speed; Take by weighing 4,4 of 71.60g '-diamino-diphenyl ether and join in the nano oxidized aluminum slurry, take by weighing the pyromellitic acid anhydride of 78.47g after the stirring and dissolving; Join in the nano oxidized aluminum slurry, at ambient temperature, reaction 4h obtains nano aluminium oxide/polyamic acid composite mortar; With this composite mortar filter, 25 ℃; Vacuum tightness is vacuum outgas 2 hours under 0.01 MPa, keeping 1 hour, 200 ℃ to keep 0.5 hour, 250 ℃ to keep 1 hour, 300 ℃ to keep under 0.5 hour, 350 ℃ the condition heating down 0.5 hour down down under 100 ℃ the temperature, obtains anti-corona composition sample T1 then.
Embodiment 2
Present embodiment is used for explaining the composition and method of making the same of anti-corona the provided by the present invention.
Take by weighing the nano alumina particles that the 20g median size is 100nm, the γ of 0.6g-mercaptan aminopropyl trimethoxysilane coupling agent, the polyester modification acrylate block copolymer dispersion agent of 0.2g; And 800mL solvent N, dinethylformamide is put into double-layer glass reaction kettle (RAT; Wuxi City Shen Ke instrument plant) in, is under the condition of 1400r/min, stirs 1h and obtain nano oxidized aluminum slurry at rotating speed; Take by weighing 4,4 of 78.76g '-diamino-diphenyl ether and join in the slurry, take by weighing 4 of 86.32g after the stirring and dissolving; 4 '-biphenyl tetracarboxylic dianhydride, join in the nano oxidized aluminum slurry, at ambient temperature; Reaction 4h obtains nano aluminium oxide/polyamic acid composite mortar; This composite mortar is filtered, is 0.01 MPa vacuum outgas 3 hours in vacuum tightness under 30 ℃, keeping 1 hour, 200 ℃ to keep 0.5 hour, 250 ℃ to keep 1 hour, 300 ℃ to keep under 0.5 hour, 325 ℃ the condition heating down 1 hour down down under 100 ℃ the temperature, obtain anti-corona composition sample T2 then.
Embodiment 3
Present embodiment is used for explaining the composition and method of making the same of anti-corona the provided by the present invention.
Take by weighing the nano alumina particles that the 15g median size is 50nm, the γ of 0.5g-mercaptan aminopropyl trimethoxysilane coupling agent, the polyester modification acrylate block copolymer dispersion agent of 0.1g; And 600mL solvent N, dinethylformamide is put into double-layer glass reaction kettle (RAT; Wuxi City Shen Ke instrument plant) in, is under the condition of 120r/min, stirs 2h and obtain nano oxidized aluminum slurry at rotating speed; Take by weighing 4,4 of 53.7g '-diamino-diphenyl ether and join in the slurry, take by weighing 3 of 58.85g after the stirring and dissolving; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride; Join in the nano oxidized aluminum slurry, under 40 ℃ of conditions, reaction 4h obtains nano aluminium oxide/polyamic acid composite mortar; With this composite mortar filter, 25 ℃, vacuum tightness is under 0.01 MPa, vacuum outgas 2 hours; Keeping 1 hour, 200 ℃ to keep 0.5 hour, 250 ℃ to keep 1 hour, 300 ℃ to keep down keeping 0.5 hour under 0.5 hour, 325 ℃ the condition down down under 100 ℃ the temperature, obtain anti-corona composition sample T3 then.
Comparative Examples 1
The present invention is used for explaining a kind of composition and method of making the same of anti-corona that provides in the prior art.
This Comparative Examples adopts the method for recording and narrating among the CN1572837A embodiment 1 to make anti-corona composition sample D1.
Embodiment 4-6
Present embodiment is used for each item performance of the prepared sample T1-T3 of test implementation example 1-3, and these performances mainly comprise:
1) corona-resistance property test
It is that the film of 25 μ m is put into the anti-corona tester of insulating material and carried out anti-corona test that the sample T1-T3 of embodiment 1-3 preparation is processed mean thickness.
The anti-corona tester of the Shanghai application for issue detecting instrument JGM-3 of factory type insulating material is adopted in this test, and test condition is voltage 3KV, frequency 20KHz, rise time of a pulse 50ns, pulse waveform is a square wave, polarity is bipolar, experimental electrode is the stainless steel electrode of diameter 6mm.According to test result, calculate MV then, be test result, test result is seen table 1.
2) tensile strength and elongation at break test
It is the method for being recorded and narrated among the GB/T 13022-1991 that n is adopted in this test, and test result is seen table 1.
Comparative Examples 2
This Comparative Examples is used for each item performance of test comparison example 1 prepared sample D1; Before test, earlier the D1 sample is processed the film that mean thickness is 25 μ m; According to each item performance test described in the embodiment 4-6 D1 being carried out performance test, test result is seen table 1 then.
Table 1
| T1 | T2 | T3 | D1 | |
| Tensile strength (Mpa) | 152 | 144 | 140 | 138 |
| Elongation at break (%) | 48 | 45 | 39 | 43 |
| The anti-corona time (h) | 102000 | 101130 | 101980 | 78200 |
Can find out from table 1; The anti-corona time of the compsn of anti-corona T1 that the embodiment of the invention 1 provides is 102000h, and the anti-corona time of the sample D1 for preparing in the Comparative Examples 1 is 78200h, much smaller than the anti-corona time provided by the present invention; And simultaneously; The tensile strength of T1 is 152Mpa, and elongation at break is 48%, and the tensile strength of the sample D1 of preparation is 138Mpa in the Comparative Examples 1; Elongation at break is 33%; This shows that the compsn of anti-corona the provided by the invention has long characteristics of anti-corona time, prove absolutely that product provided by the present invention has good corona-resistance property, sample provided by the present invention also has the good characteristics of mechanical property simultaneously.
Claims (9)
1. compsn of anti-the corona; Comprising polyimide, nano alumina particles, silane coupling agent, dispersion agent, is benchmark with anti-corona composition total weight, and polyimide accounts for 70-95%; Nano alumina particles accounts for 5-30%; Silane coupling agent accounts for 0.01-0.3%, and dispersion agent accounts for 0.005-0.3%, and the said components sum is 100%; The mean thickness of the film that forms at the compsn of anti-the corona is under the condition of 25 μ m, and the anti-corona time of the film that the compsn of anti-the corona forms, wherein said dispersion agent had following structure greater than 100,000 hours:
Wherein x is the integer of 10-40, and y is the integer of 40-50.
2. the compsn of anti-corona the according to claim 1, the median size of wherein said nano alumina particles are 5-500nm.
3. the compsn of anti-corona the according to claim 2, the median size of wherein said nano alumina particles are 50-300nm.
4. anti-corona preparation of compositions method, this method comprises:
(1) with stirring in nano alumina particles, silane coupling agent, the dispersion agent adding solvent, makes nano oxidized aluminum slurry;
(2) aromatic diamine, tetracarboxylic dianhydride are joined in the nano oxidized aluminum slurry of preparation in the step 1 successively, the heating initiated polymerization makes nano aluminium oxide/polyamic acid composite mortar;
(3) with the heating of nano aluminium oxide/polyamic acid composite mortar, imidization reaction taking place, obtain the compsn of anti-the corona, is under the condition of 25 μ m at the mean thickness of the above-mentioned compsn of anti-the corona, and the anti-corona time of the compsn of anti-the corona is more than 100,000 hours,
Wherein said dispersion agent has following structure:
Wherein x is the integer of 10-40, and y is the integer of 40-50,
Wherein the weight ratio of nano alumina particles, silane coupling agent, dispersion agent, solvent described in 1 step is 1: 0.02-0.1: 0.01-0.1: 10-100,
Wherein, the described nano oxidized aluminum slurry of step 2, aromatic diamine and tetracarboxylic dianhydride's weight ratio is 1: 0.04-0.15: 0.04-0.15.
5. according to the said anti-corona preparation of compositions method of claim 4, wherein the temperature of the heating described in the step 2 is 10-60 ℃.
6. according to the said anti-corona preparation of compositions method of claim 4; Wherein the reaction conditions of the imidization reaction in 3 steps comprises, nano aluminium oxide/polyamic acid composite mortar is passed through following heat treatment process successively: under 70-200 ℃ temperature, keep 0.5-1.5 hour, 180-250 ℃ to keep 0.5-1.5 hour, 230-280 ℃ to keep 0.5-1.5 hour, 260-350 ℃ to keep 0.5-1.5 hour down down down.
7. according to the said anti-corona preparation of compositions method of claim 4, wherein the tetracarboxylic dianhydride described in the step 2 be selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1; 4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6; 7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 1, two (trifluoromethyl)-2,3,5 of 4-, 6-benzene tertacarbonic acid dianhydride, 3; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,6-dichloronaphtalene-1,4; 5,8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5,8-tetracarboxylic dianhydride, 2,3; 6,7-Tetrachloronaphthalene-2,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9; 10-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5, a kind of among the 6-tetracarboxylic dianhydride.
8. according to the said anti-corona preparation of compositions method of claim 4, wherein the aromatic diamine described in the step 2 be selected from 4,4,4 '-diaminobenzophenone, 3; 3 '-dimethyl--4,4 '-diaminobenzophenone, 3,3 '-two chloro-4; 4 '-diaminobenzophenone, mphenylenediamine, Ursol D, 4 '-methylene-bis (neighbour-chloroaniline), 3,3 '-alkylsulfonyl pentanoic, 1,5-diaminonaphthalene, 2; 2 '-two (4-amino-phenols), 4,4 '-benzidine, 4,4 '-methylene dianiline (MDA), 4; 4 '-sulfenyl pentanoic, 4,4 '-isopropylidene pentanoic, 3,3 '-tolidine, 3; 3 '-dimethoxy benzidine, 3,3 '-dicarboxylate biphenyl amine, 2,4 di amino toluene, 2; 5-diaminotoluene, 2,4-diamino--5-toluene(mono)chloride, 2, a kind of in 4-diamino--6-toluene(mono)chloride.
9. according to the said anti-corona preparation of compositions method of claim 4, wherein the solvent described in the step 1 is selected from N, dinethylformamide, DMAC N,N, a kind of in N-Methyl pyrrolidone, the DMSO 99.8MIN..
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| DE102011080884A1 (en) * | 2011-08-12 | 2013-02-14 | Siemens Aktiengesellschaft | Coating with high corona resistance, as well as manufacturing method thereto |
| JP5854930B2 (en) * | 2011-08-25 | 2016-02-09 | 日東電工株式会社 | Insulation film |
| TWI521016B (en) * | 2012-07-18 | 2016-02-11 | 財團法人工業技術研究院 | Method for etching a polyimide-containing layer |
| CN102796376A (en) * | 2012-08-31 | 2012-11-28 | 江苏亚宝绝缘材料股份有限公司 | Corona-resistant composition and preparation method thereof |
| CN103029395B (en) * | 2012-12-21 | 2015-05-13 | 深圳瑞华泰薄膜科技有限公司 | Corona-resistant polyimide film material and preparation method thereof |
| DE102014219441A1 (en) | 2014-09-25 | 2016-03-31 | Siemens Aktiengesellschaft | Corona protection system and electrical machine |
| DE102014219439A1 (en) | 2014-09-25 | 2016-03-31 | Siemens Aktiengesellschaft | Corona protection system for an electrical machine |
| DE102014219440A1 (en) * | 2014-09-25 | 2016-03-31 | Siemens Aktiengesellschaft | Corona protection system for an electric machine and electric machine |
| CN105694036A (en) * | 2016-03-18 | 2016-06-22 | 江苏亚宝绝缘材料股份有限公司 | Polyimide resin doped with alumina oxide |
| CN116082682B (en) * | 2023-03-03 | 2024-04-05 | 四川大学 | Polyimide/fluorinated nano Al 2 O 3 Composite film and preparation method thereof |
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| Title |
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| 黄孙息等."耐电晕聚酰亚胺薄膜研究进展".《绝缘材料》.2009,第42卷(第1期),第21-24页. |
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