CN115594978B - High-voltage-resistant insulating rubber plate and preparation method thereof - Google Patents
High-voltage-resistant insulating rubber plate and preparation method thereof Download PDFInfo
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- CN115594978B CN115594978B CN202211339825.7A CN202211339825A CN115594978B CN 115594978 B CN115594978 B CN 115594978B CN 202211339825 A CN202211339825 A CN 202211339825A CN 115594978 B CN115594978 B CN 115594978B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003381 stabilizer Substances 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 10
- 239000004945 silicone rubber Substances 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 239000012188 paraffin wax Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000005516 deep trap Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 12
- 230000003712 anti-aging effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 5
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- -1 methyl siloxane Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010074 rubber mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
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- 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)
- Organic Insulating Materials (AREA)
Abstract
The invention relates to a high-voltage-resistant insulating rubber plate and a preparation method thereof, and belongs to the technical field of special rubber. The rubber plate comprises the following components in percentage by weight: 6.5 to 8.2 weight percent of voltage stabilizer, 0.5 to 0.6 weight percent of vulcanizing agent, 0.37 to 0.45 weight percent of accelerator, 0.3 to 0.5 weight percent of age resister, 15 to 20 weight percent of carbon black, 1 to 3 weight percent of stearic acid, 2 to 5 weight percent of microcrystalline paraffin, 2 to 5 weight percent of paraffin oil and the balance of vinyl silicone rubber raw rubber; one end of the voltage stabilizer is connected with submicron silicon dioxide, a deep trap is introduced to bind carriers, the other end of the voltage stabilizer is grafted with a large pi bond containing a conjugated structure and an ester functional group, a long-path deep trap is obtained by introducing the voltage stabilizer in cooperation with the silicon dioxide, a tortuous network with an electron capturing capability is formed in a matrix, hindered electron migration is realized, and a terminal double bond is crosslinked with rubber raw rubber to fix the voltage stabilizer and perform a stable function.
Description
Technical Field
The invention belongs to the technical field of special rubber, and particularly relates to a high-voltage-resistant insulating rubber plate and a preparation method thereof.
Background
Under the condition of the same transmission power, the higher the voltage is, the smaller the current is, and the lower the heat loss generated by the current is in the electric energy transmission process, so that the loss cost of transmission is reduced, along with the development of modern industry, more and more large-scale equipment with high power and high voltage is continuously developed, and correspondingly, the high-voltage resistant insulating material is required to be used for protection so as to ensure the safe and stable operation of high-voltage ionization facilities.
The electric breakdown resistance is an inherent property of a material, under high voltage, charges are injected into the insulating material or migration of carriers in the insulating material is accelerated, and under the action of a strong enough electric field, the insulating material loses the dielectric property of the insulating material to become a conductor and loses the protection effect; rubber has excellent plasticity and pressure-resistant insulating capability, is widely applied to insulating protective materials, the dielectric strength of common rubber is generally not high, a certain amount of voltage stabilizer is generally added to prevent migration of carriers so as to improve voltage breakdown resistance, such as 2, 4-dihydroxybenzophenone, aminobenzoic acid and the like, and the small molecular voltage stabilizer can play a certain role in strengthening, but is easy to migrate in a matrix and difficult to play a role in stability, and the dielectric strength of the pressure-resistant rubber material with better prior art is about 40 kV/mm.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a high-voltage-resistant insulating rubber plate and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the high-voltage-resistant insulating rubber plate comprises the following components in percentage by weight:
6.5 to 8.2 weight percent of voltage stabilizer, 0.5 to 0.6 weight percent of vulcanizing agent, 0.37 to 0.45 weight percent of accelerator, 0.3 to 0.5 weight percent of age resister, 15 to 20 weight percent of carbon black, 1 to 3 weight percent of stearic acid, 2 to 5 weight percent of microcrystalline paraffin, 2 to 5 weight percent of paraffin oil and the balance of vinyl silicone rubber raw rubber;
the voltage stabilizer is prepared by the following method:
step A1: mixing pentaerythritol and dioxane, heating and stirring to completely dissolve the pentaerythritol, adding a small amount of triethylamine to mix, then keeping the temperature at 75-80 ℃, setting the stirring speed to be 300-400rpm, slowly adding a silane coupling agent KH560, keeping the temperature and stirring for 30-40min, and carrying out ring opening reaction on epoxy groups at the molecular end of the silane coupling agent KH560 and the pentaerythritol under the initiation of the triethylamine to obtain a bridging compound;
further, the use amount ratio of the silane coupling agent KH560, pentaerythritol and triethylamine was 0.1mol:0.12-0.15mol:2-3mL.
The synthetic route for bridging compounds can be represented as follows:
step A2: mixing submicron silicon dioxide and ethanol solution, adding sodium carbonate to adjust the pH value to 9, carrying out ultrasonic dispersion to uniformly disperse the submicron silicon dioxide, then adding a bridging compound and DMF, applying mechanical stirring at 60-120rpm, heating to 40-50 ℃, stirring and reacting for 3-4 hours, wherein the submicron silicon dioxide generates active hydroxyl on the surface under an alkaline ethanol water environment, hydrolyzing methyl siloxane on the molecule of the bridging compound, condensing with the active hydroxyl, and grafting the bridging compound on the surface of the submicron silicon dioxide to obtain a load matrix;
further, the ratio of the amounts of submicron silica, bridging compound, DMF and ethanol solution was 100g:18-22g:1-3mL:500mL, the concentration of the ethanol solution is preferably 30%.
The structure of the load matrix can be expressed as follows:
step A3: stirring and dissolving m-aminobenzoic acid and acetone, adding N, N-dimethylaniline, mixing, keeping the temperature at 3-10 ℃, setting the stirring speed to 600-800rpm, slowly adding propenyl chloride, controlling the overall dropwise adding reaction time to be 1-2h, and reacting with N, N-dimethylaniline acid-binding agent, propenyl chloride and amino on m-aminobenzoic acid molecules to obtain a modified compound;
further, the dosage ratio of m-aminobenzoic acid, acryloyl chloride and N, N-dimethylaniline was 0.1mol:0.105-0.11mol:0.26-0.32mL.
The synthetic route for the modified compounds can be represented as follows:
step A4: and (3) stirring and mixing the load matrix, the modified compound, the thionyl chloride and the perfluorooctane at a high speed, heating to 98-105 ℃, setting the stirring speed to 200-300rpm, carrying out reflux reaction for 4-5h, and carrying out esterification reaction on the modified compound and the load matrix under the catalysis of the thionyl chloride to obtain the voltage stabilizer.
Further, the ratio of the amount of the supporting substrate, the modifying compound and the thionyl chloride is 100g:30-40g:5-8mL.
The structure of the voltage stabilizer can be expressed as follows:
further, the vulcanizing agent is preferably a vulcanizing agent DCP.
Further, the accelerator is preferably accelerator Q-BP-2.
Further, the antioxidant is preferably an antioxidant 4020.
The preparation method of the high-voltage-resistant insulating rubber plate specifically comprises the following steps:
step S1: adding raw vinyl silicone rubber, a voltage stabilizer, an accelerator, an anti-aging agent, white carbon black, stearic acid, microcrystalline paraffin and paraffin oil into a kneader, heating to 145-160 ℃, and kneading for 1-1.5h under 0.2-0.3MPa to obtain a rubber compound;
step S2: wrapping the rubber compound on a roll mill, adding a vulcanizing agent, carrying out thin pass for 5-8 times, and discharging to obtain a raw rubber sheet;
step S3: and vulcanizing and forming the green sheet on a vulcanizing machine, wherein the vulcanizing temperature is 150-160 ℃, the vulcanizing pressure is 6-8MPa, and the vulcanizing time is 3.5h, so that the high-voltage-resistant insulating rubber plate is obtained.
The invention has the beneficial effects that:
the invention self-makes a composite voltage stabilizer suitable for rubber, which takes submicron silicon dioxide as a matrix, disperses in the rubber matrix to form a large number of interfaces with the matrix, introduces deep trap bound carriers, increases the transfer path of electrons, and improves the voltage resistance of the rubber from the physical structure;
the preparation method comprises the steps of reacting a silane coupling agent KH570 with pentaerythritol to obtain a bridging compound with one end containing an active branched hydroxyl group and the other end containing a methylsiloxane group, hydrolyzing methylsiloxane of the bridging compound and condensing with silicon dioxide, esterifying the active branched hydroxyl group with a modifying compound to ensure that the outer end of the voltage stabilizer contains a large pi bond and an ester functional group of a conjugated structure, wherein the end structure has higher electron affinity and lower ionization potential, thereby having higher electron capturing capability, and cooperating with the silicon dioxide to introduce to obtain a long-path deep trap, forming a network which is tortuous and has electron capturing capability in a matrix, and preventing migration of electrons to cause the matrix to be broken down;
meanwhile, the modified compound is modified by propenyl acyl chloride, the end part of the modified voltage stabilizer contains a branch-shaped double bond, has good compatibility with a matrix, participates in rubber raw rubber crosslinking, and connects the voltage stabilizer with macromolecules of the matrix in a covalent bond mode, so that the voltage stabilizer is not easy to migrate in the matrix, and effectively and stably plays a role in the matrix.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment prepares a high-voltage-resistant insulating rubber plate, and the specific implementation process is as follows:
1) Preparation of voltage stabilizer
a1, adding pentaerythritol into a reaction kettle, adding dioxane for mixing, heating and stirring at 120rpm to completely dissolve the pentaerythritol, adding a small amount of triethylamine for stirring and mixing, then keeping the temperature at 75 ℃ in an oil bath, setting the stirring speed to 300rpm, adding a silane coupling agent KH560 into the reaction kettle within 5min, keeping the temperature and stirring for 40min to obtain a bridging compound, removing the dioxane after the reaction is finished by reduced pressure rotary evaporation, extracting with toluene, removing the toluene by rotary evaporation, and purifying the bridging compound;
in the above reaction, the use amount ratio of the silane coupling agent KH560, pentaerythritol and triethylamine was 0.1mol:0.12mol:2mL, quantified as 0.2mol of silane coupling agent KH 560.
a2, adding submicron silicon dioxide (provided by tin-free Ji bin nano material technology Co., ltd., median particle diameter of 0.3 mu m, adopting the same raw materials in the following example) and 30% ethanol solution into a reaction kettle, mixing, adding sodium carbonate to adjust pH value to 9, carrying out ultrasonic dispersion for 5min by 33kHz, uniformly dispersing submicron silicon dioxide, then adding a bridging compound and DMF, mechanically stirring at 60rpm, heating to 40 ℃, stirring and reacting for 4h to obtain a load matrix, centrifuging after the reaction is finished, washing a bottom sediment with methanol, centrifuging again, then placing in a drying oven, drying at 60 ℃ for 1h, and purifying the load matrix;
in the above reaction, the ratio of the amounts of submicron silica, bridging compound, DMF and ethanol solution was 100g:18g:1mL:500mL, quantified as 300g of submicron silica.
a3, adding m-aminobenzoic acid into a reaction kettle, adding acetone, stirring at 120rpm, dissolving m-aminobenzoic acid, adding N, N-dimethylaniline, mixing, keeping the temperature at 3 ℃ through an ice-water bath, setting the stirring speed to be 600rpm, adding propenyl chloride in 20min, continuing stirring for reaction, controlling the overall dropwise adding reaction time to be 2h, thus preparing a modified compound, reducing the pressure to-0.1 MPa after the reaction is finished, removing acetone and excessive propenyl chloride through rotary evaporation, and purifying the modified compound;
in the above reaction, the amount ratio of m-aminobenzoic acid, acryloyl chloride and N, N-dimethylaniline was 0.1mol:0.105mol:0.26mL, as 0.8mol of m-aminobenzoic acid.
a4, adding the load matrix, the modification compound and the thionyl chloride into a reaction kettle, adding 3 times of perfluorooctane of the reactant, stirring and mixing at a high speed of 1200rpm, heating to 98 ℃, setting the stirring speed to 200rpm, carrying out reflux reaction for 5 hours to obtain a voltage stabilizer, reducing the pressure to-0.1 MPa after the reaction is finished, removing the solvent by rotary evaporation, and purifying the voltage stabilizer;
in the above reaction, the ratio of the amount of the supporting substrate, the modifying compound and thionyl chloride was 100g:30g:5mL, quantified as 300g of the loaded matrix.
2) Preparation of rubber sheet
s1, batching: in this example, 3kg of gum material was formulated in the following weight proportions
Voltage stabilizer, self-made in this example, 6.5wt%
A vulcanizing agent selected from the group consisting of vulcanizing agent DCP,0.5wt%,
an accelerator selected from accelerator Q-BP-2,0.37wt%
An anti-aging agent selected from the group consisting of anti-aging agents 4020,0.3wt%
20wt% of carbon black
Stearic acid 1wt%
Microcrystalline paraffin 2wt%
Paraffin oil selected from 32# paraffin oil, 5wt%
The rest is vinyl silicone rubber raw rubber provided by Hemsl silicone Co.Ltd, and is selected from 110-2A type;
s2, rubber mixing: adding raw vinyl silicone rubber, a voltage stabilizer, an accelerator, an anti-aging agent, white carbon black, stearic acid, microcrystalline paraffin and paraffin oil into a kneader, heating to 145 ℃, and kneading for 1.5 hours under 0.2MPa to obtain a rubber compound;
s3, open mill: wrapping the rubber compound on a roll mill, adding a vulcanizing agent, carrying out thin pass for 8 times, and discharging to obtain a raw rubber sheet;
s4, vulcanization: and vulcanizing and forming the green sheet on a vulcanizing machine, wherein the vulcanizing temperature is 150 ℃, the vulcanizing pressure is 8MPa, and the vulcanizing time is 3.5 hours, so that the high-pressure-resistant insulating rubber plate is obtained.
Example 2
The embodiment prepares a high-voltage-resistant insulating rubber plate, and the specific implementation process is as follows:
1) Preparation of voltage stabilizer
a1, adding pentaerythritol into a reaction kettle, adding dioxane for mixing, heating and stirring at 120rpm to completely dissolve the pentaerythritol, adding a small amount of triethylamine for stirring and mixing, then keeping the temperature at 80 ℃ in an oil bath, setting the stirring speed to 400rpm, adding a silane coupling agent KH560 into the reaction kettle within 5min, keeping the temperature and stirring for 30min to obtain a bridging compound, removing the dioxane after the reaction is finished by reduced pressure rotary evaporation, extracting with toluene, removing the toluene by rotary evaporation, and purifying the bridging compound;
in the above reaction, the use amount ratio of the silane coupling agent KH560, pentaerythritol and triethylamine was 0.1mol:0.15mol:3mL, quantified as 0.2mol of silane coupling agent KH 560.
a2, adding submicron silicon dioxide and ethanol solution with the concentration of 30% into a reaction kettle for mixing, adding sodium carbonate to adjust the pH value to 9, adding 33kHz for ultrasonic dispersion for 5min, uniformly dispersing submicron silicon dioxide, adding a bridging compound and DMF, applying mechanical stirring at 120rpm, heating to 50 ℃, stirring for 3h to prepare a load matrix, centrifuging after the reaction, taking a bottom sediment for washing with methanol, centrifuging again, drying at 60 ℃ for 1h in a drying box, and purifying the load matrix;
in the above reaction, the ratio of the amounts of submicron silica, bridging compound, DMF and ethanol solution was 100g:22g:3mL:500mL, quantified as 300g of submicron silica.
a3, adding m-aminobenzoic acid into a reaction kettle, adding acetone, stirring at 120rpm, dissolving m-aminobenzoic acid, adding N, N-dimethylaniline, mixing, keeping the temperature at 10 ℃ through an ice-water bath, setting the stirring speed to 800rpm, adding propenyl chloride in 20min, continuing stirring for reaction, controlling the overall dropwise adding reaction time to be 1h, preparing a modified compound, reducing the pressure to-0.1 MPa after the reaction is finished, removing acetone and excessive propenyl chloride through rotary evaporation, and purifying the modified compound;
in the above reaction, the amount ratio of m-aminobenzoic acid, acryloyl chloride and N, N-dimethylaniline was 0.1mol:0.11mol:0.32mL, quantified as 0.8mol of m-aminobenzoic acid.
a4, adding the load matrix, the modification compound and the thionyl chloride into a reaction kettle, adding 3 times of perfluorooctane of the reactant, stirring and mixing at a high speed of 1200rpm, heating to 105 ℃, setting the stirring speed to 300rpm, carrying out reflux reaction for 4 hours to obtain a voltage stabilizer, reducing the pressure to-0.1 MPa after the reaction is finished, removing the solvent by rotary evaporation, and purifying the voltage stabilizer;
in the above reaction, the ratio of the amount of the supporting substrate, the modifying compound and thionyl chloride was 100g:40g:8mL, quantified as 300g of the loaded matrix.
2) Preparation of rubber sheet
s1, batching: in this example, 3kg of gum material was formulated in the following weight proportions
Voltage stabilizer, self-made in this example, 8.2wt%
A vulcanizing agent selected from the group consisting of vulcanizing agent DCP,0.6wt%,
an accelerator selected from accelerator Q-BP-2,0.45wt%
An anti-aging agent selected from the group consisting of anti-aging agents 4020,0.5wt%
15wt% of carbon black
Stearic acid 3wt%
Microcrystalline wax 5wt%
Paraffin oil selected from 32# paraffin oil, 2wt%
The rest is vinyl silicone rubber raw rubber provided by Hemsl silicone Co.Ltd, and is selected from 110-2A type;
s2, rubber mixing: adding raw vinyl silicone rubber, a voltage stabilizer, an accelerator, an anti-aging agent, white carbon black, stearic acid, microcrystalline paraffin and paraffin oil into a kneader, heating to 160 ℃, and kneading for 1h under 0.3MPa to obtain a rubber compound;
s3, open mill: wrapping the rubber compound on a roll mill, adding a vulcanizing agent, carrying out thin pass for 5 times, and discharging to obtain a raw rubber sheet;
s4, vulcanization: and vulcanizing and forming the green sheet on a vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, the vulcanizing pressure is 6MPa, and the vulcanizing time is 3.5 hours, so that the high-pressure-resistant insulating rubber plate is obtained.
Example 3
The embodiment prepares a high-voltage-resistant insulating rubber plate, and the specific implementation process is as follows:
1) Preparation of voltage stabilizer
a1, adding pentaerythritol into a reaction kettle, adding dioxane for mixing, heating and stirring at 120rpm to completely dissolve the pentaerythritol, adding a small amount of triethylamine for stirring and mixing, then keeping the temperature at 78 ℃ in an oil bath, setting the stirring speed to 400rpm, adding a silane coupling agent KH560 into the reaction kettle within 5min, keeping the temperature and stirring for 35min to obtain a bridging compound, removing the dioxane after the reaction is finished by reduced pressure rotary evaporation, extracting with toluene, removing the toluene by rotary evaporation, and purifying the bridging compound;
in the above reaction, the use amount ratio of the silane coupling agent KH560, pentaerythritol and triethylamine was 0.1mol:0.13mol:3mL, quantified as 0.2mol of silane coupling agent KH 560.
a2, adding submicron silicon dioxide and ethanol solution with the concentration of 30% into a reaction kettle for mixing, adding sodium carbonate to adjust the pH value to 9, adding 33kHz for ultrasonic dispersion for 5min, uniformly dispersing submicron silicon dioxide, adding a bridging compound and DMF, applying 120rpm mechanical stirring, heating to 42 ℃, stirring for reaction for 3.8h to obtain a load matrix, centrifuging after the reaction is finished, washing a bottom layer precipitate with methanol, centrifuging again, and then placing in a drying box for drying at 60 ℃ for 1h to purify the load matrix;
in the above reaction, the ratio of the amounts of submicron silica, bridging compound, DMF and ethanol solution was 100g:20g:2.5mL:500mL, quantified as 300g of submicron silica.
a3, adding m-aminobenzoic acid into a reaction kettle, adding acetone, stirring at 120rpm, dissolving m-aminobenzoic acid, adding N, N-dimethylaniline, mixing, keeping the temperature at 5 ℃ through an ice-water bath, setting the stirring speed to 800rpm, adding propenyl chloride in 20min, continuing stirring for reaction, controlling the overall dropwise adding reaction time to be 1.6h, preparing a modified compound, reducing the pressure to-0.1 MPa after the reaction is finished, removing acetone and excessive propenyl chloride through rotary evaporation, and purifying the modified compound;
in the above reaction, the amount ratio of m-aminobenzoic acid, acryloyl chloride and N, N-dimethylaniline was 0.1mol:0.11mol:0.30mL, quantified as 0.8mol of m-aminobenzoic acid.
a4, adding the load matrix, the modification compound and the thionyl chloride into a reaction kettle, adding 3 times of perfluorooctane of the reactant, stirring and mixing at a high speed of 1200rpm, heating to 102 ℃, setting the stirring speed to 300rpm, carrying out reflux reaction for 4.5h to obtain a voltage stabilizer, reducing the pressure to-0.1 MPa after the reaction is finished, removing the solvent by rotary evaporation, and purifying the voltage stabilizer;
in the above reaction, the ratio of the amount of the supporting substrate, the modifying compound and thionyl chloride was 100g:34g:6mL, quantified as 300g of the loaded matrix.
2) Preparation of rubber sheet
s1, batching: in this example, 3kg of gum material was formulated in the following weight proportions
Voltage stabilizer, self-made in this example, 7.5wt%
A vulcanizing agent selected from the group consisting of vulcanizing agent DCP,0.6wt%,
an accelerator selected from accelerator Q-BP-2,0.4wt%
An anti-aging agent selected from the group consisting of anti-aging agents 4020,0.5wt%
17wt% of carbon black
Stearic acid 2wt%
Microcrystalline wax 4wt%
Paraffin oil selected from 32# paraffin oil, 3.5wt%
The rest is vinyl silicone rubber raw rubber provided by Hemsl silicone Co.Ltd, and is selected from 110-2A type;
s2, rubber mixing: adding raw vinyl silicone rubber, a voltage stabilizer, an accelerator, an anti-aging agent, white carbon black, stearic acid, microcrystalline paraffin and paraffin oil into a kneader, heating to 145-160 ℃, and kneading for 1-1.5h under 0.2-0.3MPa to obtain a rubber compound;
s3, open mill: wrapping the rubber compound on a roll mill, adding a vulcanizing agent, carrying out thin pass for 5-8 times, and discharging to obtain a raw rubber sheet;
s4, vulcanization: and vulcanizing and forming the green sheet on a vulcanizing machine, wherein the vulcanizing temperature is 150-160 ℃, the vulcanizing pressure is 6-8MPa, and the vulcanizing time is 3.5h, so that the high-voltage-resistant insulating rubber plate is obtained.
Comparative example
The comparative example was carried out in the same manner as in example 3, substituting the self-made voltage stabilizer with the voltage stabilizer disclosed in chinese patent CN113831247a in an amount of 1.2wt% and adding 5.5wt% nano silica, the remaining raw materials being the same.
Taking the high voltage resistant insulating rubber plates provided in examples 1-3 and comparative examples, and carrying out a tensile test at a speed of 1mm/min by using an electronic universal tester according to the ASTM D412 standard to test the mechanical properties of the rubber plates;
the resistivity of the rubber sheet was measured with reference to the GB/T1410-2006 standard, and the dielectric strength test was performed with reference to the GB/T1408.1-2016 standard, and specific test data are shown in Table 1:
TABLE 1
As can be seen from the data in Table 1, the rubber plate prepared by the invention has the tensile strength of 78.6-81.3MPa, the elongation at break of 41.4-48.3%, good mechanical properties and the resistivity of 8.2-9.1X10 14 Omega.m, dielectric strength up to 58.4-65.2kV/mm, and excellent high-voltage-resistant insulation property.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (4)
1. The high-voltage-resistant insulating rubber plate is characterized by comprising the following components in percentage by weight:
6.5 to 8.2 weight percent of voltage stabilizer, 0.5 to 0.6 weight percent of vulcanizing agent, 0.37 to 0.45 weight percent of accelerator, 0.3 to 0.5 weight percent of age resister, 15 to 20 weight percent of carbon black, 1 to 3 weight percent of stearic acid, 2 to 5 weight percent of microcrystalline paraffin, 2 to 5 weight percent of paraffin oil and the balance of vinyl silicone rubber raw rubber;
the voltage stabilizer is prepared by the following method:
step A1: mixing pentaerythritol and dioxane, dissolving, adding triethylamine, then keeping the temperature at 75-80 ℃, adding a silane coupling agent KH560 in a stirring state, keeping the temperature, and stirring for 30-40min to obtain a bridging compound, wherein the dosage ratio of the silane coupling agent KH560 to the pentaerythritol to the triethylamine is 0.1mol:0.12-0.15mol:2-3mL;
step A2: mixing submicron silicon dioxide and ethanol solution, adjusting pH value to 9, adding bridging compound and DMF, heating to 40-50 ℃, stirring and reacting for 3-4h to obtain a load matrix, wherein the dosage ratio of submicron silicon dioxide, bridging compound, DMF and ethanol solution is 100g:18-22g:1-3mL:500mL, the concentration of the ethanol solution is preferably 30%;
step A3: dissolving m-aminobenzoic acid in acetone, adding N, N-dimethylaniline, adding propenyl chloride at the constant temperature of 3-10 ℃ under stirring, controlling the overall dropwise adding reaction time to be 1-2h, and obtaining a modified compound, wherein the dosage ratio of the m-aminobenzoic acid, the propenyl chloride and the N, N-dimethylaniline is 0.1mol:0.105-0.11mol:0.26-0.32mL;
step A4: stirring and mixing the load matrix, the modified compound, the thionyl chloride and the perfluorooctane, heating to 98-105 ℃, and stirring and refluxing for 4-5 hours to obtain the voltage stabilizer, wherein the dosage ratio of the load matrix, the modified compound and the thionyl chloride is 100g:30-40g:5-8mL.
2. A high voltage resistant insulation rubber sheet according to claim 1, characterized in that the vulcanizing agent is preferably a vulcanizing agent DCP.
3. A high voltage resistant insulation rubber sheet according to claim 2, characterized in that the accelerator is preferably accelerator Q-BP-2.
4. The method for preparing the high-voltage-resistant insulating rubber plate according to claim 3, which is characterized by comprising the following steps:
step S1: adding raw materials except vulcanizing agents into a kneader, heating to 145-160 ℃, and kneading for 1-1.5h under 0.2-0.3MPa to obtain a rubber compound;
step S2: wrapping the rubber compound on a roll mill, adding a vulcanizing agent, carrying out thin pass for 5-8 times, and discharging to obtain a raw rubber sheet;
step S3: and vulcanizing and forming the green sheet on a vulcanizing machine, wherein the vulcanizing temperature is 150-160 ℃, the vulcanizing pressure is 6-8MPa, and the vulcanizing time is 3.5h, so that the high-voltage-resistant insulating rubber plate is obtained.
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