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CN121005826B - A coolant-resistant capacitor sealing plate and capacitor - Google Patents

A coolant-resistant capacitor sealing plate and capacitor

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Publication number
CN121005826B
CN121005826B CN202511534931.4A CN202511534931A CN121005826B CN 121005826 B CN121005826 B CN 121005826B CN 202511534931 A CN202511534931 A CN 202511534931A CN 121005826 B CN121005826 B CN 121005826B
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China
Prior art keywords
hydrogenated nitrile
nitrile rubber
sealing plate
monomer
acid
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CN202511534931.4A
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Chinese (zh)
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CN121005826A (en
Inventor
严鳌
韦松
丁亚运
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Jiangsu Hils Electronic Materials Co ltd
Shenzhen Capchem Technology Co Ltd
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Jiangsu Hils Electronic Materials Co ltd
Shenzhen Capchem Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
    • H01G2/08—Cooling arrangements; Heating arrangements; Ventilating arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/224—Housing; Encapsulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Power Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a cooling liquid resistant capacitor sealing plate and a capacitor. The sealing plate comprises a sealing layer and a supporting layer, wherein the sealing layer is made of elastic hydrogenated nitrile rubber material, the hydrogenated nitrile rubber material is obtained by vulcanizing a hydrogenated nitrile rubber composition, the hydrogenated nitrile rubber composition comprises hydrogenated nitrile rubber, and the hydrogenated nitrile rubber is prepared by copolymerization of unsaturated nitrile monomer, conjugated diene monomer and aromatic vinyl acid monomer and then hydrogenation. According to the invention, the aromatic vinyl acid structural unit is introduced into the hydrogenated nitrile rubber, so that the sealing plate has good air tightness and good compatible effect on various cooling liquids on the premise of meeting the strength requirement of the sealing plate of the capacitor, and the cooling liquid cannot permeate into the capacitor element, so that the service lives of the sealing plate and the capacitor are prolonged.

Description

Cooling liquid-resistant capacitor sealing plate and capacitor
Technical Field
The invention belongs to the technical field of capacitors, and particularly relates to a cooling liquid-resistant capacitor sealing plate and a capacitor.
Background
With the development of electronic information industries such as middle-high end servers, data centers and the like at home and abroad, the heat dissipation mode of electronic components is gradually changed from traditional air cooling heat dissipation to spray-type or immersion-type liquid cooling heat dissipation, and common cooling liquid comprises hydrocarbon compounds, organic silicone oil, fluorinated liquid and the like. In this application scenario, the aluminum electrolytic capacitor needs to stably operate in an oil-containing environment, which puts new demands on the sealing performance of the aluminum electrolytic capacitor, and the sealing material (i.e., the capacitor sealing plate) thereof is required to block the volatilization of the internal electrolyte and also prevent the oil in the external environment and other impurities from entering the capacitor element.
The capacitor sealing plate comprises a sealing layer, and the sealing layer is made of rubber materials with certain elasticity, and is matched with the capacitor outer shell to form a sealing effect so as to prevent electrolyte leakage. The rubber material is generally selected from ethylene propylene diene monomer rubber, butyl rubber, silicone rubber, fluororubber, neoprene rubber or hydrogenated nitrile rubber, wherein hydrogenated nitrile rubber is of more interest due to its good heat resistance and excellent chemical resistance.
However, it is still difficult to consider various types of cooling liquids with the conventional hydrogenated nitrile rubber material, and when the sealing plate is immersed in the cooling liquid, the rubber material constituting the sealing plate absorbs the cooling liquid and expands, or the cooling liquid may infiltrate into the capacitor element to adversely affect.
Disclosure of Invention
In order to solve the problem that the existing hydrogenated nitrile rubber material is difficult to be compatible with various cooling liquids, the invention provides a cooling liquid resistant capacitor sealing plate and a capacitor.
The aim of the invention is realized by the following technical scheme.
In a first aspect, the present invention provides a cooling liquid resistant capacitor sealing plate, the sealing plate comprising a sealing layer and a supporting layer, the sealing layer being selected from hydrogenated nitrile rubber materials having elasticity, the hydrogenated nitrile rubber materials being vulcanized from a hydrogenated nitrile rubber composition, the hydrogenated nitrile rubber composition comprising a hydrogenated nitrile rubber, and the hydrogenated nitrile rubber being prepared by copolymerizing an unsaturated nitrile monomer, a conjugated diene monomer and an aromatic vinyl acid monomer represented by formula I below, followed by hydrogenation:
A formula I;
In the formula I, R is selected from H, phenyl or C1-C6 alkyl.
Further, in the polymerized monomer of the hydrogenated nitrile rubber, the weight ratio of the unsaturated nitrile monomer, the conjugated diene monomer and the aromatic vinyl acid monomer is (15-50): (40-85): (3-8).
Further, the unsaturated nitrile monomer includes acrylonitrile or methacrylonitrile, the conjugated diene monomer is selected from at least one of 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, and the aromatic vinyl acid includes at least one of styrene acid (CAS: 140-10-3), 3-methyl styrene acid (CAS: 3029-79-6), and 4-styrene acid (CAS: 13026-23-8).
Further, the hydrogenated nitrile rubber composition further comprises a vulcanizing agent, a filler and a processing aid, wherein the weight ratio of the hydrogenated nitrile rubber to the vulcanizing agent to the filler to the processing aid is 100 (3-7) (40-60) (0.5-2).
Further, the vulcanizing agent comprises at least one of dicumyl peroxide, di-tert-butyl dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, the filler comprises at least one of carbon black, clay, talcum, calcium carbonate and silicon dioxide, and the processing aid comprises at least one of fatty acid, fatty acid salt and fatty acid ester.
Further, the fatty acid comprises at least one of ricinoleic acid, stearic acid, palmitic acid and lauric acid, the fatty acid salt comprises at least one of barium stearate, calcium stearate and zinc stearate, and the fatty acid ester comprises at least one of ricinoleic acid ester, stearic acid ester, palmitic acid ester and lauric acid ester.
Further, the cooling liquid resistant capacitor sealing plate further comprises an isolation layer, wherein the isolation layer is located on the surface, away from the sealing layer, of the supporting layer, and the isolation layer is selected from a PP film and/or a PE film.
Further, the supporting layer is a phenolic resin laminated plate.
Further, the iodine value of the hydrogenated nitrile rubber is 5-20 mg/100mg, and the Mooney viscosity ML (1+4) ℃ is 30-160 ℃.
Further, the preparation method of the hydrogenated nitrile rubber material comprises the following steps:
S1, carrying out copolymerization reaction on an unsaturated nitrile monomer, a conjugated diene monomer and an aromatic vinyl acid monomer to prepare nitrile rubber containing an aromatic vinyl acid structural unit;
s2, hydrogenating the nitrile rubber prepared in the step S1 to form hydrogenated nitrile rubber;
and S3, mixing the hydrogenated nitrile rubber prepared in the step S2 with a vulcanizing agent, a filler and a processing aid, and vulcanizing at 140-180 ℃ to obtain the hydrogenated nitrile rubber material.
In a second aspect, the present invention provides a capacitor comprising a cooling fluid resistant capacitor seal plate as described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects.
According to the invention, an aromatic vinyl acid structural unit is introduced into the hydrogenated nitrile rubber, wherein the phenyl improves the thermal stability and the mechanical strength, and the unsaturated acid group increases the polarity of the hydrogenated nitrile rubber, so that the oil (cooling liquid) resistance of the capacitor sealing plate is improved. The filler in the hydrogenated nitrile rubber composition can improve the strength of the rubber material (capacitor sealing plate), and the processing aid can improve the dispersibility and flowability of each component in the rubber composition, thereby improving the molding processability.
The hydrogenated nitrile rubber material provided by the invention has good air tightness and good compatible effect on various cooling liquids on the premise of meeting the strength requirement of the sealing plate of the capacitor, and the cooling liquid cannot permeate into the capacitor element, so that the service lives of the sealing plate and the capacitor are prolonged.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the specific embodiments. It should be understood that the embodiments described herein are some, but not all, embodiments of the invention, and are intended to be illustrative of the invention and not limiting. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention, based on the embodiments herein.
In the present invention, as known to those skilled in the art of chemical synthesis, after the polymerization of the respective monomers, the corresponding structural units of the monomers are present in the resulting polymer (hydrogenated nitrile rubber). Wherein the mass ratio of each structural unit is the mass ratio of the monomers providing each structural unit.
In a first aspect, the invention provides a cooling fluid resistant capacitor seal plate comprising a seal layer and a support layer, the seal layer being selected from a hydrogenated nitrile rubber material having elasticity, the hydrogenated nitrile rubber material being vulcanized from a hydrogenated nitrile rubber composition comprising a hydrogenated nitrile rubber, and the hydrogenated nitrile rubber being prepared by copolymerization of an unsaturated nitrile monomer, a conjugated diene monomer and an aromatic vinyl acid monomer followed by hydrogenation.
In some specific embodiments, in the polymerized monomer of the hydrogenated nitrile rubber, the weight ratio of the unsaturated nitrile monomer, the conjugated diene monomer and the aromatic vinyl acid monomer is (15-50): (40-85): (3-8).
In some embodiments, the unsaturated nitrile monomer comprises acrylonitrile or methacrylonitrile, preferably acrylonitrile, and the higher the unsaturated nitrile monomer content, the better the oil resistance, but the lower the rebound resilience and the poorer the cold resistance.
In some embodiments, the conjugated diene monomer is selected from at least one of 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, preferably 1, 3-butadiene.
In some embodiments, the aromatic vinyl acid comprises at least one of styrene acid (CAS: 140-10-3), 3-methyl styrene acid (CAS: 3029-79-6), 4-styrene acid (CAS: 13026-23-8), preferably 4-styrene acid.
In some specific embodiments, the hydrogenated nitrile rubber composition further comprises a vulcanizing agent, a filler and a processing aid, wherein the weight ratio of the hydrogenated nitrile rubber to the vulcanizing agent, the filler and the processing aid is 100 (3-7): 40-60): 0.5-2.
In some embodiments, the vulcanizing agent includes at least one of dicumyl peroxide, di-t-butyldicumyl peroxide, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane. The filler includes at least one of carbon black, clay, talc, calcium carbonate and silica, and the silica may be surface-treated with a silane coupling agent, preferably carbon black, and may improve the strength of the rubber material (capacitor sealing plate). The processing aid comprises at least one of fatty acid, fatty acid salt and fatty acid ester.
In some embodiments, the fatty acid comprises at least one of ricinoleic acid, stearic acid, palmitic acid, and lauric acid, the fatty acid salt comprises at least one of barium stearate, calcium stearate, and zinc stearate, and the fatty acid ester comprises at least one of ricinoleic acid ester, stearic acid ester, palmitic acid ester, and lauric acid ester. Stearic acid is preferred, and the dispersibility and flowability of the components in the hydrogenated nitrile rubber composition can be improved, thereby improving the molding processability.
In some embodiments, the cooling liquid resistant capacitor seal plate further comprises an insulation layer located on a surface of the support layer facing away from the sealing layer, the insulation layer being selected from PP and/or PE films. The isolating layer is used for preventing the electrolyte from directly contacting with the supporting layer.
In some embodiments, the support layer is a phenolic resin laminate.
In some embodiments, the method of preparing the hydrogenated nitrile rubber material comprises the steps of:
s1, copolymerizing an unsaturated nitrile monomer, a conjugated diene monomer and an aromatic vinyl acid monomer to obtain nitrile rubber containing an aromatic vinyl acid structural unit, wherein any one of a well-known emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and a solution polymerization method can be adopted, preferably an emulsion polymerization method, and an emulsifier (sodium dodecyl benzene sulfonate), a molecular weight regulator (such as tertiary dodecyl mercaptan), a polymerization initiator (such as cumene hydroperoxide) and a polymerization terminator (such as hydroquinone) can be added in the copolymerization reaction;
S2, hydrogenating the nitrile rubber prepared in the step S1 to form hydrogenated nitrile rubber, wherein the hydrogenation method is not particularly limited, and a known method can be adopted, for example, an oil layer hydrogenation method of solidifying a latex of a copolymer (nitrile rubber) obtained by emulsion polymerization and then hydrogenating the oil layer, or a water layer hydrogenation method of directly hydrogenating the latex of the obtained copolymer, and the iodine value of the hydrogenated nitrile rubber is preferably 5-20 mg/100mg, and the Mooney viscosity ML (1+4) ℃ is preferably 30-160;
And S3, mixing the hydrogenated nitrile rubber prepared in the step S2 with a vulcanizing agent, a filler and a processing aid, and vulcanizing at 140-180 ℃ for 20-40 min to obtain the hydrogenated nitrile rubber material.
The preparation of the sealing plate for the capacitor is realized by overlapping the supporting layer and the hydrogenated nitrile rubber material and then carrying out hot pressing treatment.
In a second aspect, the present invention provides a capacitor comprising a cooling fluid resistant capacitor seal plate as described in the first aspect.
The following will explain the embodiments of the present invention further by way of examples and comparative examples.
The reagents, materials and instruments used in the following description are commercially available as conventional reagents, conventional materials and conventional instruments unless otherwise specified, and the reagents involved can also be synthesized by conventional synthetic methods. The methods in the examples, unless otherwise specified, are all conventional in the art. Monomers according to the invention are commercially available.
Example 1
1) Preparation of hydrogenated nitrile rubber
180 Parts by weight of ion-exchanged water, 25 parts by weight of 10wt% aqueous solution of sodium dodecylbenzenesulfonate, 25 parts by weight of acrylonitrile, 0.5 part by weight of tertiary dodecyl mercaptan were sequentially added to the reaction vessel, the internal gas was replaced with nitrogen 3 times, and 60 parts by weight of 1, 3-butadiene and 6 parts by weight of 4-styrene acid were added. The reaction vessel was kept at 5℃and 0.1 part by weight of cumene hydroperoxide was added thereto, and the polymerization was carried out for 16 hours while rotating the reaction vessel by emulsion polymerization. After terminating the polymerization by adding 0.1 part by weight of an aqueous hydroquinone solution having a mass fraction of 10% by weight, the residual monomers were removed by means of a rotary evaporator having a water temperature of 60℃to give a latex (solid content about 30% by weight) of a copolymer nitrile rubber.
Then, by a water layer hydrogenation method, a latex of a copolymer nitrile rubber and a palladium catalyst, which is a solution obtained by mixing a palladium acetate acetone solution having a mass fraction of 1wt% and an ion-exchanged water with an equal weight, are added to an autoclave, and the amount of the palladium catalyst to be used is preferably 1100ppm in terms of the amount of metal palladium based on 100 parts by weight of the copolymer nitrile rubber before hydrogenation as a hydrogenation object. And (3) carrying out hydrogenation reaction for 8 hours at the temperature of 60 ℃ under the pressure of 3.2MPa to obtain the hydrogenated nitrile rubber.
2) Preparation of hydrogenated nitrile rubber material
100 Parts by weight of hydrogenated nitrile rubber, 5 parts by weight of dicumyl peroxide, 50 parts by weight of carbon black and 1 part by weight of stearic acid are mixed and vulcanized for 30 minutes at 160 ℃ to obtain a hydrogenated nitrile rubber material.
Example 2
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the three monomers used to prepare the hydrogenated nitrile rubber are used in amounts of 50 parts by weight acrylonitrile, 85 parts by weight 1, 3-butadiene, and 8 parts by weight 4-styrene acid.
Example 3
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the three monomers used to prepare the hydrogenated nitrile rubber are used in amounts of 15 parts by weight acrylonitrile, 40 parts by weight 1, 3-butadiene, and 3 parts by weight 4-styrene acid.
Example 4
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the three monomers used to prepare the hydrogenated nitrile rubber are varied in amounts of 20 parts by weight methacrylonitrile, 50 parts by weight isoprene, and 5 parts by weight styrene acid.
Example 5
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the three monomers used to prepare the hydrogenated nitrile rubber differ in 25 parts by weight methacrylonitrile, 60 parts by weight 1, 3-pentadiene, and 6 parts by weight methyl styrene acid.
Example 6
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the three monomers used to prepare the hydrogenated nitrile rubber differ in 25 parts by weight methacrylonitrile, 60 parts by weight 2, 3-dimethyl-1, 3-butadiene, and 6 parts by weight 4-styrene acid.
Example 7
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the three monomers used to prepare the hydrogenated nitrile rubber differ in 25 parts by weight methacrylonitrile, 60 parts by weight 1, 3-butadiene, and 6 parts by weight 4-styrene acid.
Example 8
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the hydrogenated nitrile rubber used to prepare the hydrogenated nitrile rubber material is different from the vulcanizing agent, filler and processing aid used in 100 parts by weight of hydrogenated nitrile rubber, 3 parts by weight of dicumyl peroxide, 40 parts by weight of carbon black and 0.5 part by weight of stearic acid.
Example 9
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the hydrogenated nitrile rubber used to prepare the hydrogenated nitrile rubber material is different from the vulcanizing agent, filler and processing aid used in 100 parts by weight of hydrogenated nitrile rubber, 7 parts by weight of dicumyl peroxide, 60 parts by weight of carbon black and 2 parts by weight of stearic acid.
Example 10
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the hydrogenated nitrile rubber used to prepare the hydrogenated nitrile rubber material is different from the vulcanizing agent, filler and processing aid in 100 parts by weight of hydrogenated nitrile rubber, 5 parts by weight of di-t-butyl diisopropylbenzene peroxide, 50 parts by weight of calcium carbonate and 1 part by weight of stearate.
Example 11
This example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the hydrogenated nitrile rubber used to prepare the hydrogenated nitrile rubber material is different from the vulcanizing agent, filler and processing aid and is used in amounts of 100 parts by weight hydrogenated nitrile rubber, 4 parts by weight 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 45 parts by weight silica and 0.8 part by weight barium stearate.
Comparative example 1
This comparative example uses the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the monomers used to prepare the hydrogenated nitrile rubber do not contain aromatic vinyl acid monomers.
Comparative example 2
This comparative example used the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the hydrogenated nitrile rubber was prepared using an excess of aromatic vinyl acid monomer of 10 parts by weight 4-styrene acid.
Comparative example 3
This comparative example used the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the monomers used to prepare the hydrogenated nitrile rubber did not contain aromatic vinyl acid monomers, but increased acrylic acid.
Comparative example 4
This comparative example used the procedure comprising the majority of example 1 to prepare hydrogenated nitrile rubber and hydrogenated nitrile rubber materials, except that the monomers used to prepare the hydrogenated nitrile rubber did not contain aromatic vinyl acid monomers, but increased styrene.
Performance test:
In order to better understand the present invention, the hydrogenated nitrile rubber and the hydrogenated nitrile rubber material prepared in the above examples and comparative examples were subjected to the following test, and the test results of the iodine value, the mooney viscosity, and the tensile strength of the hydrogenated nitrile rubber material are shown in table 1.
Iodine value of hydrogenated nitrile rubber the iodine value of the hydrogenated nitrile rubber was measured in accordance with JIS K6235.
[ Mooney viscosity ] the Mooney viscosity of a hydrogenated nitrile rubber was measured in accordance with JIS K6300.
Tensile Strength test the hydrogenated nitrile rubber material was tested for tensile strength using the test method specified in GB/T528-2009.
Table 1 test results
[ Immersion test ] a hydrogenated nitrile rubber material was cut into sheets having an area of 2 x 2 square cm and a thickness of 5mm, and the hardness and volume before immersion were tested. Immersing the sheet in test tubes containing different coolants, hydrocarbon (poly alpha-olefin), silicone oil (polymethylphenylsiloxane), fluorinated liquid (1, 2, 3-hexafluoropropylmethyl ether), heating the test tubes in an oven set at 85 ℃ for 200 hours, taking out the test tubes from the oven, standing at room temperature for 1 hour for cooling, taking out the sheet after cooling, wiping off the test coolant adhered to the sheet, and testing hardness and volume after immersing. The Shore A hardness (Shore hardness) was measured by a GSD-719K type rubber hardness tester using the test method specified in GB/T531.1-2008. The test results are shown in Table 2. Calculating the hardness change rate and the volume change rate before and after immersion:
hardness change rate (%) = (hardness after immersion-hardness before immersion)/hardness before immersion 100%;
Volume change (%) = (post-immersion volume-pre-immersion volume)/pre-immersion volume 100%.
Table 2 test results of immersion test
From the test results in tables 1 and 2, the invention improves the heat stability and mechanical strength by introducing an aromatic vinyl acid structural unit into the hydrogenated nitrile rubber, and improves the oil (cooling liquid) resistance of the capacitor sealing plate by increasing the polarity of the hydrogenated nitrile rubber by an acid group. On the premise of meeting the strength requirement of the capacitor sealing plate, the hydrogenated nitrile rubber material has good air tightness and good compatibility effect on various cooling liquids, and after being immersed in different cooling liquids, the absolute value of the hardness change rate is less than 5%, and the volume change rate is less than 3%.
As can be seen from the test results of examples 1 to 11 and comparative examples 1 and 2, if the monomer used for preparing the hydrogenated nitrile rubber does not contain an aromatic vinyl acid monomer, the hydrogenated nitrile rubber material has lower tensile strength, has larger hardness change and volume change after being immersed in different cooling liquids, and has poorer oil resistance, and if the aromatic vinyl acid monomer is used in an excessive amount, the tensile strength and oil resistance of the hydrogenated nitrile rubber material are not obviously improved, the hardness change and the volume change after being immersed in different cooling liquids are still larger, and the compatibility with different cooling liquids is poor, but the hardness change and the volume change are smaller compared with those of comparative example 1. This also illustrates that aromatic vinyl acid monomer addition can improve compatibility with different coolants. When the addition amount of the aromatic vinyl acid monomer is in a proper range, the tensile strength and the compatibility with cooling liquid of the hydrogenated nitrile rubber material can be effectively improved, and the strength requirement of the capacitor sealing plate is met.
As can be seen from examples 1 to 11 and comparative examples 3 and 4, if the monomer used for preparing the hydrogenated nitrile rubber is replaced by a monomer containing only an acidic group, the tensile strength of the hydrogenated nitrile rubber material is not enhanced, and the hydrogenated nitrile rubber material has large hardness change and volume change after being immersed in different cooling liquids and poor compatibility with different cooling liquids, and if the monomer is replaced by a monomer containing only a benzene ring, the tensile strength of the hydrogenated nitrile rubber material is improved but the tensile strength of the hydrogenated nitrile rubber material is not significantly improved in oil resistance.
The invention has been further described with reference to specific embodiments, but it should be understood that the detailed description is not to be construed as limiting the spirit and scope of the invention, but rather as providing those skilled in the art with the benefit of this disclosure with the benefit of their various modifications to the described embodiments.

Claims (9)

1.一种耐冷却液电容器密封板，所述密封板包括密封层和支撑层，所述密封层选自具有弹性的氢化丁腈橡胶材料，其特征在于，所述氢化丁腈橡胶材料由氢化丁腈橡胶组合物硫化得到，所述氢化丁腈橡胶组合物包括氢化丁腈橡胶，且所述氢化丁腈橡胶由不饱和腈单体、共轭二烯单体和下述式I所示的芳香族乙烯酸单体进行共聚反应后加氢制备得到：1. A coolant-resistant capacitor sealing plate, the sealing plate comprising a sealing layer and a support layer, the sealing layer being selected from an elastic hydrogenated nitrile butadiene rubber material, characterized in that the hydrogenated nitrile butadiene rubber material is obtained by vulcanizing a hydrogenated nitrile butadiene rubber composition, the hydrogenated nitrile butadiene rubber composition comprising hydrogenated nitrile butadiene rubber, and the hydrogenated nitrile butadiene rubber is prepared by copolymerization of an unsaturated nitrile monomer, a conjugated diene monomer, and an aromatic vinyl acid monomer represented by Formula I, followed by hydrogenation: 式Ⅰ； Formula I; 式Ⅰ中，R选自苯基或C1~C6的烷基；所述氢化丁腈橡胶的聚合单体中，所述不饱和腈单体、共轭二烯单体与芳香族乙烯酸单体的重量比为（15~50）：（40~85）：（3~8）。In Formula I, R is selected from phenyl or C1~C6 alkyl groups; in the polymer monomers of the hydrogenated nitrile rubber, the weight ratio of the unsaturated nitrile monomer, the conjugated diene monomer and the aromatic vinyl acid monomer is (15~50):(40~85):(3~8). 2.根据权利要求1所述的耐冷却液电容器密封板，其特征在于，所述不饱和腈单体包括丙烯腈或甲基丙烯腈，所述共轭二烯单体选自包括1,3-丁二烯、异戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯中至少一种，所述芳香族乙烯酸单体包括3-甲基苯乙烯酸、4-苯乙烯酸中至少一种。2. The coolant-resistant capacitor sealing plate according to claim 1, characterized in that the unsaturated nitrile monomer includes acrylonitrile or methacrylonitrile, the conjugated diene monomer is selected from at least one of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene, and the aromatic vinyl acid monomer includes at least one of 3-methylstyrenic acid and 4-styrenic acid. 3.根据权利要求1所述的耐冷却液电容器密封板，其特征在于，所述氢化丁腈橡胶组合物还包括硫化剂、填料和加工助剂，所述氢化丁腈橡胶与硫化剂、填料和加工助剂的重量比为100：(3~7)：(40~60)：(0.5~2)。3. The coolant-resistant capacitor sealing plate according to claim 1, characterized in that the hydrogenated nitrile rubber composition further includes a vulcanizing agent, a filler and a processing aid, wherein the weight ratio of the hydrogenated nitrile rubber to the vulcanizing agent, the filler and the processing aid is 100:(3~7):(40~60):(0.5~2). 4.根据权利要求3所述的耐冷却液电容器密封板，其特征在于，所述硫化剂包括过氧化二异丙苯、双叔丁基过氧化二异丙基苯和2,5-二甲基-2,5-二(叔丁基过氧基)己烷中的至少一种，所述填料包括炭黑、粘土、滑石、碳酸钙和二氧化硅中的至少一种，所述加工助剂包括脂肪酸、脂肪酸盐、脂肪酸酯中的至少一种。4. The coolant-resistant capacitor sealing plate according to claim 3, characterized in that the vulcanizing agent includes at least one of dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, the filler includes at least one of carbon black, clay, talc, calcium carbonate, and silicon dioxide, and the processing aid includes at least one of fatty acids, fatty acid salts, and fatty acid esters. 5.根据权利要求4所述的耐冷却液电容器密封板，其特征在于，所述脂肪酸包括蓖麻油酸、硬脂酸、棕榈酸和月桂酸中的至少一种；所述脂肪酸盐包括硬脂酸钡、硬脂酸钙和硬脂酸锌中的至少一种；所述脂肪酸酯包括蓖麻油酸酯、硬脂酸酯、棕榈酸酯和月桂酸酯中的至少一种。5. The coolant-resistant capacitor sealing plate according to claim 4, wherein the fatty acid comprises at least one of ricinoleic acid, stearic acid, palmitic acid and lauric acid; the fatty acid salt comprises at least one of barium stearate, calcium stearate and zinc stearate; and the fatty acid ester comprises at least one of ricinoleic acid ester, stearic acid ester, palmitic acid ester and lauric acid ester. 6.根据权利要求1所述的耐冷却液电容器密封板，其特征在于，所述耐冷却液电容器密封板还包括隔离层，所述隔离层位于所述支撑层背离所述密封层的表面，所述隔离层选自PP膜和/或PE膜。6. The coolant-resistant capacitor sealing plate according to claim 1, wherein the coolant-resistant capacitor sealing plate further comprises an isolation layer, the isolation layer being located on the surface of the support layer opposite to the sealing layer, and the isolation layer being selected from PP film and/or PE film. 7.根据权利要求1所述的耐冷却液电容器密封板，其特征在于，所述氢化丁腈橡胶的碘值为5~20mg/100mg，其门尼粘度ML(1+4)100℃为30~160。7. The coolant-resistant capacitor sealing plate according to claim 1, characterized in that the hydrogenated nitrile rubber has an iodine value of 5~20mg/100mg and a Mooney viscosity ML (1+4) of 30~160 at 100℃. 8.根据权利要求3所述的耐冷却液电容器密封板，其特征在于，所述氢化丁腈橡胶材料的制备方法包括以下步骤：8. The coolant-resistant capacitor sealing plate according to claim 3, characterized in that the preparation method of the hydrogenated nitrile rubber material includes the following steps: S1、将不饱和腈单体、共轭二烯单体与芳香族乙烯酸单体进行共聚反应，制备得到含有芳香族乙烯酸结构单元的丁腈橡胶；S1. An nitrile rubber containing aromatic ethylene glycol structural units is prepared by copolymerizing unsaturated nitrile monomers, conjugated diene monomers and aromatic ethylene glycol monomers. S2、将步骤S1制备的丁腈橡胶氢化形成氢化丁腈橡胶；S2. The nitrile rubber prepared in step S1 is hydrogenated to form hydrogenated nitrile rubber; S3、将步骤S2制备的氢化丁腈橡胶与硫化剂、填料和加工助剂混炼，在140~180℃下硫化得到氢化丁腈橡胶材料。S3. The hydrogenated nitrile butadiene rubber prepared in step S2 is mixed with vulcanizing agent, filler and processing aid, and vulcanized at 140~180℃ to obtain hydrogenated nitrile butadiene rubber material. 9.一种电容器，其特征在于，包括如权利要求1至8任一所述的耐冷却液电容器密封板。9. A capacitor, characterized in that it comprises a coolant-resistant capacitor sealing plate as described in any one of claims 1 to 8.
CN202511534931.4A 2025-10-27 2025-10-27 A coolant-resistant capacitor sealing plate and capacitor Active CN121005826B (en)

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CN118888336A (en) * 2024-09-14 2024-11-01 丰宾电子科技股份有限公司 A new oil-resistant cover for snap-in capacitors

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