CN119219829B - High heat-resistant flexible graphite bipolar plate microporous sealing agent - Google Patents

High heat-resistant flexible graphite bipolar plate microporous sealing agent

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Publication number
CN119219829B
CN119219829B CN202411326017.6A CN202411326017A CN119219829B CN 119219829 B CN119219829 B CN 119219829B CN 202411326017 A CN202411326017 A CN 202411326017A CN 119219829 B CN119219829 B CN 119219829B
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methacrylate
weight
sealing agent
agent according
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CN119219829A (en
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郝建强
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Suzhou Howbond New Materials Co ltd
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Suzhou Howbond New Materials Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a high heat-resistant flexible graphite bipolar plate micropore plugging agent which comprises 20-40 parts by weight of (methyl) acrylated open ring compound of glycidol ether oxypropyl cyclotetrasiloxane and 60-80 parts by weight of high Tg methacrylate monomer, wherein the sum of the two is 100 parts by weight, 0.5-2 parts by weight of flatting agent and 0.2-1.0 part by weight of free radical thermal initiator. The plugging agent has excellent ethylene glycol resistance due to the organic siloxane structure, and the (methyl) acrylic acid-esterified open ring compound of the glycidyl ether oxypropyl cyclotetrasiloxane contains 4 (methyl) acryloyloxy groups capable of being polymerized by free radicals on each molecule, so that the plugging agent has high crosslinking density, has high heat resistance after being matched with high Tg methacrylate monomer for copolymerization, has low curing shrinkage rate and small residual stress, and is favorable for keeping good bending strength of the bipolar plate at high temperature.

Description

Microporous plugging agent for high heat-resistant flexible graphite bipolar plate
Technical Field
The invention belongs to the field of hydrogen fuel cells, and particularly relates to a thermosetting microporous plugging agent for a flexible graphite bipolar plate of a hydrogen fuel cell stack.
Background
The fuel cell bipolar plate is a core structural support of the hydrogen fuel cell stack and is divided into a metal bipolar plate and a graphite bipolar plate. The graphite bipolar plate has the advantages of easily available raw materials, low cost, good chemical corrosion resistance and long service life, and is widely used in fuel cell stacks of commercial vehicles. However, the flexible graphite sheet itself has a microporous structure, and must be impregnated with a plugging agent to ensure the gas tightness of the bipolar plate, and at the same time, the plugging agent should impart sufficient mechanical strength, chemical resistance (mainly ethylene glycol resistance) and long-term heat resistance to the flexible graphite sheet after curing.
The flexible graphite bipolar plate is generally prepared by compounding (methyl) acrylic ester monomer into impregnating resin liquid as a plugging agent (refer to Chinese patent CN 107706430B), a free radical thermal initiator is added before use, the flexible graphite plate is impregnated in the plugging agent, vacuum or pressurized impregnation is carried out, plugging agent molecules are permeated into micropores of the flexible graphite bipolar plate, and then the residual plugging agent on the surface of the bipolar plate is cleaned, so that the conductivity of graphite is influenced after the plugging agent is solidified on the surface of the bipolar plate. And then heating and curing the bipolar plate in a water bath, and forming a compact network structure after curing the plugging agent, thereby endowing the bipolar plate with air tightness, compressive strength, chemical resistance and heat resistance.
After the flexible graphite bipolar plates are assembled into a galvanic pile, the flexible graphite bipolar plates are in contact with an ethylene glycol aqueous solution cooling medium at the temperature of 80-95 ℃ for a long time in the operation process of the fuel cell, the flexible graphite bipolar plates are required to have resistance to the ethylene glycol aqueous solution at a high temperature for a long time, and the (methyl) acrylic ester polymer has a certain solubility in the ethylene glycol, so that after the fuel cell is operated for a long time, the bipolar plate plugging agent is partially dissolved in the ethylene glycol, and hole cracks are generated, so that gas leakage and failure occur.
In addition, the Tg of the methacrylate polymer or copolymer mentioned in the Chinese patent CN 107706430B is relatively low, few components with Tg exceeding 100 ℃ are included, the Tg of the long-chain alkyl acrylate polymer is lower than zero, the long-chain alkyl acrylate polymer is in a rubbery state at the operating temperature of the fuel cell, the bending strength of the graphite bipolar plate is greatly reduced, and the severe requirement of stable operation of the hydrogen fuel cell vehicle at high temperature for a long time is hardly met.
Disclosure of Invention
The invention aims to provide a flexible graphite bipolar plate micropore plugging agent with good heat resistance and glycol resistance.
The technical solution for realizing the purpose of the invention is as follows:
The invention provides a microporous plugging agent for a high heat-resistant flexible graphite bipolar plate, which comprises 20-40 parts by weight of (methyl) acrylated open ring compound of glycidyl ether oxypropyl cyclotetrasiloxane and 60-80 parts by weight of high Tg methacrylate monomer, wherein the sum of the two is 100 parts by weight, 0.5-2 parts by weight of flatting agent and 0.2-1.0 part by weight of free radical thermal initiator.
Preferably, the (meth) acrylated open ring compound of the glycidoxypropyl cyclotetrasiloxane has the following structure:
wherein R represents methyl or a hydrogen atom.
Preferably, the (methyl) acrylic acid ester open ring compound of the glycidyl ether oxypropyl cyclotetrasiloxane is prepared by epoxy ring opening esterification reaction of the glycidyl ether oxypropyl cyclotetrasiloxane with acrylic acid or methacrylic acid under the action of a catalyst:
specifically, the catalyst for epoxy ring-opening esterification reaction of acrylic acid or methacrylic acid comprises any one of tertiary amine, quaternary ammonium salt, common triethylamine, N-dimethylbenzylamine, N-dimethylaniline, trimethyl benzyl ammonium chloride, triphenylphosphine, triphenylantimony, chromium acetylacetonate, chromium isooctanoate, organic tin compounds, tetraethylammonium bromide and the like, and the dosage of the catalyst is 0.1-3% of the total mass of reactants.
Specifically, in order to ensure complete ring-opening esterification of the epoxy groups, the addition amount of acrylic acid or methacrylic acid should generally be 1.1 to 1.5 times the molar number of epoxy groups in the glycidoxypropyl cyclotetrasiloxane.
Specifically, in order to prevent the self-polymerization of acrylic acid or methacrylic acid during the ring-opening esterification reaction of epoxy groups, a small amount of free radical polymerization inhibitor can be added. The common free radical polymerization inhibitor is any one of p-Methoxyphenol (MEHQ), hydroquinone, 2, 5-dimethyl hydroquinone, 2, 6-di-tert-butyl-4-methylphenol (BHT) and the like, and the addition amount of the free radical polymerization inhibitor is 0.01% -1% of the total mass of reactants.
Specifically, the epoxy ring-opening esterification reaction is an exothermic reaction, so that the control of the temperature at the initial stage of the reaction is very important, glycidyl ether oxypropyl cyclotetrasiloxane is usually heated to 80-90 ℃, a mixture of acrylic acid or methacrylic acid, a catalyst and a free radical polymerization inhibitor is dropwise added, the reaction temperature is controlled to be 110-120 ℃ after the completion of the dropwise addition, the temperature is maintained for 5 hours, and the heating is stopped and the temperature is reduced to room temperature, so that the target product can be obtained.
Preferably, the high Tg methacrylate monomer is selected from any one of isobornyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, tetrahydrofuranyl methacrylate, tricyclodecyl (meth) acrylate, dicyclopentadiene (meth) acrylate, (meth) acryloylmorpholine, N-dimethylacrylamide, and the like. Isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate or tricyclodecaneyl methacrylate is preferable from the viewpoint of heat resistance, low viscosity and the like.
Preferably, any leveling agent with an infiltration effect on the flexible graphite bipolar plate can be selected as the leveling agent, and the leveling agent can be determined according to the impregnation amount of the plugging agent after the flexible graphite bipolar plate is infiltrated, and the higher the impregnation amount is, the better the effect of the leveling agent is. Preferred are the BYK-333 and BYK-3505 leveling agents and the hyperdispersants of tri-n-polymers, such as CH-1, CH-2, CH-3, CH-5, CH-6, CH-7, CH-8, CH-9, etc.
Preferably, the free radical thermal initiator is an initiator with a decomposition temperature of 80-95 ℃, and specifically azo and peroxide free radical thermal initiators are selected. Preference is given to free-radical thermal initiators such as azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide and the like.
Preferably, various antioxidants, fluorescent agents and the like may be added to the above composition in view of weather resistance, heat resistance, fluorescent recognition and the like.
Compared with the prior art, the invention has the advantages that:
(1) The (methyl) acrylic acid ester open ring compound of the glycidyl ether oxypropyl cyclotetrasiloxane has excellent ethylene glycol resistance due to the hydrophobic and oleophobic properties and low surface tension of the organosiloxane structure, can not be swelled and dissolved even being contacted with ethylene glycol aqueous solution at high temperature for a long time, and is particularly suitable for micropore plugging of the flexible graphite bipolar plate of a hydrogen fuel cell.
(2) One of the components of the flexible graphite bipolar plate plugging agent composition of the invention is a (methyl) acrylated open-loop compound of glycidol ether oxypropyl cyclotetrasiloxane, and each molecule contains 4 (methyl) groups capable of free radical polymerization
The acryloyloxy group has high heat resistance after being copolymerized with a high Tg methacrylate monomer, and meanwhile, the curing shrinkage rate is low, the residual stress is small, and the bipolar plate is favorable for keeping good bending strength at high temperature.
Detailed Description
The invention will be described in detail with reference to examples.
The (methyl) acrylic ester monomer has the advantages of low viscosity, strong permeability, low curing temperature and the like, and is the preferred compound of the microporous plugging agent of the graphite bipolar plate. Compared with acrylic ester compounds, methacrylic ester compounds are easier to carry out free radical heat curing reaction, and meanwhile, the cured product has higher Tg (glass transition temperature), namely higher heat resistance, so that most commercial microporous plugging agents adopt methacrylic ester monomers as main components. However, the methacrylate monomers rarely have Tg exceeding 100 ℃ after polymerization, and the heat resistance is inferior to that of epoxy resin cured products, and also the crosslinking density is not high enough, and the resistance to ethylene glycol is not good enough because of containing a large amount of polar ester bonds.
The invention introduces tetrafunctional monomer containing methyl siloxane structure, has high Tg and excellent ethylene glycol resistance.
The (methyl) acrylic acid ester open ring compound of the glycidoxypropyl cyclotetrasiloxane is prepared by epoxy ring-opening esterification reaction of the glycidoxypropyl cyclotetrasiloxane and acrylic acid or methacrylic acid under the action of a catalyst, and then washing with water, alkali and water until excessive acrylic acid or methacrylic acid is completely washed off, and then drying and filtering by a dehydrating agent to obtain the colorless transparent acrylic acid ester open ring compound of the glycidoxypropyl cyclotetrasiloxane or the methyl acrylic acid ester open ring compound of the glycidoxypropyl cyclotetrasiloxane.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
100G of glycidol ether oxypropyl cyclotetrasiloxane is added into a four-port glass reaction bottle with a teflon stirring paddle, the oil bath is heated to the liquid level temperature of 80-90 ℃, a mixture of methacrylic acid, triethylamine and BHT (the weight of the mixture of the methacrylic acid, the triethylamine and the BHT is 16g,1.0g and 0.1g in sequence) is dropwise added, the reaction temperature is controlled to be 110-120 ℃ after the dropwise addition is completed, the reaction is maintained for 5 hours, and the reaction is stopped and cooled to room temperature. The reactant is washed by water, alkali and water again until excessive methacrylic acid is completely washed, the pH value of the water phase reaches neutrality, and then the colorless transparent glycidol ether oxypropyl cyclotetrasiloxane methacrylate open-ring compound (called as tetra-functional organosilicon-1 for short) is obtained by drying and filtering with a dehydrating agent.
100G of glycidol ether oxypropyl cyclotetrasiloxane is added into a four-port glass reaction bottle with a teflon stirring paddle, the oil bath is heated to the liquid level temperature of 80-90 ℃, a mixture of acrylic acid, triphenylphosphine and MEHQ (13 g,1.0g and 0.1g in turn) is dropwise added, the reaction temperature is controlled to be 110-120 ℃ after the dropwise addition, the reaction is maintained for 5 hours, and the reaction is stopped and cooled to room temperature. And (3) washing the reactant for multiple times, washing with alkali, washing with water again until excessive acrylic acid is completely washed off, enabling the pH value of the water phase to be neutral, and drying and filtering with a dehydrating agent to obtain the colorless transparent acrylated open-loop compound (called as tetra-functional organic silicon-2 for short) of glycidol ether oxypropyl cyclotetrasiloxane.
The plugging agent formulas in the examples and the comparative examples are obtained by uniformly stirring the components after mixing, and dissolving solid substances into transparent liquid.
The formulations of the examples and comparative examples are shown in Table 1 below.
TABLE 1
The evaluation method of ethylene glycol resistance is as follows:
10g of plugging agent is poured into a teflon mold with the diameter of 4.0cm and the height of 2.0cm, and is placed into a drying oven with the temperature of 80 ℃ to be heated for 2 hours, and then the temperature is raised to 120 ℃ to be heated for 2 hours continuously, so that a colorless and transparent cylindrical solidified product is obtained. The cylindrical cured product was put into a glass bottle of 50% by weight of an aqueous ethylene glycol solution, sealed, transferred into a 90 ℃ oven, kept for 1000 hours, and taken out to examine the solubility of the cured product and the turbidity degree of the aqueous ethylene glycol solution, thereby evaluating the ethylene glycol resistance of the plugging agent.
Ethylene glycol resistance was classified into 4 classes:
1. excellent (the solidified matter is intact, the glycol aqueous solution is transparent, has no foreign matter and is not turbid)
2. Good (cured product was not significantly dissolved, and the aqueous ethylene glycol solution was slightly turbid)
3. General delta (the condensate was significantly dissolved and the glycol aqueous solution became turbid)
4. Poor X (the cured product had swelling and dissolution, and the glycol aqueous solution was slightly turbid)
According to Table 1, it was found from comparative examples-1 and-1 that the amount of the tetrafunctional silicone added had a critical effect on the ethylene glycol resistance, and that the better resistance could be achieved only by exceeding 20phr (Parts per hundred), whereas at 10phr of the tetrafunctional silicone added, the cured product had a significant dissolution after aging, the ethylene glycol aqueous solution became cloudy, and the resulting cured product had a lower Tg and poorer heat resistance.
The compositions of comparative example-2 were all methacrylates having a high Tg, and the Tg of the cured product was relatively high, but since the cured product did not contain an organosiloxane structure, the ethylene glycol resistance was poor, and the cured product was swollen and dissolved after aging, and the ethylene glycol aqueous solution was slightly cloudy.
The formulation of comparative example-3 contained a low Tg difunctional acrylate, and the resulting cured product had a relatively low Tg, poor heat resistance, and poor ethylene glycol resistance, and the cured product had swelling and dissolution after aging, and the aqueous ethylene glycol solution was very turbid.

Claims (13)

1.一种高耐热柔性石墨双极板微孔堵漏剂，其特征在于，包括：20~40重量份缩水甘油醚氧丙基环四硅氧烷的（甲基）丙烯酸酯化开环化合物和60~80重量份高Tg甲基丙烯酸酯单体，两者的总和为100重量份，以及0.5~2重量份流平剂和0.2~1.0重量份自由基热引发剂；1. A high heat-resistant flexible graphite bipolar plate micropore sealing agent, characterized in that it comprises: 20-40 parts by weight of a glycidyl etheroxypropylcyclotetrasiloxane (meth)acrylate ring-opening compound and 60-80 parts by weight of a high Tg methacrylate monomer, the total of which is 100 parts by weight, as well as 0.5-2 parts by weight of a leveling agent and 0.2-1.0 parts by weight of a free radical thermal initiator; 其中，所述的缩水甘油醚氧丙基环四硅氧烷的（甲基）丙烯酸酯化开环化合物具有如下结构：The glycidyl etheroxypropylcyclotetrasiloxane (meth)acrylate ring-opening compound has the following structure: ； ; 其中，R代表甲基或氢原子。In this context, R represents a methyl group or a hydrogen atom. 2.如权利要求1所述的堵漏剂，其特征在于，所述的缩水甘油醚氧丙基环四硅氧烷的（甲基）丙烯酸酯化开环化合物是由式Ⅰ结构的缩水甘油醚氧丙基环四硅氧烷在催化剂和自由基阻聚剂作用下和（甲基）丙烯酸进行环氧基开环酯化反应而制得：2. The sealing agent according to claim 1, characterized in that the glycidyl etheroxypropylcyclotetrasiloxane (meth)acrylate ring-opening compound is prepared by epoxy ring-opening esterification reaction of glycidyl etheroxypropylcyclotetrasiloxane of formula I with (meth)acrylic acid under the action of a catalyst and a free radical polymerization inhibitor: ； ; I。I. 3.如权利要求2所述的堵漏剂，其特征在于，催化剂选自叔胺、季铵盐、三苯基膦、三苯基锑、乙酰丙酮铬、异辛酸铬、有机锡类化合物中任意一种。3. The sealing agent according to claim 2, wherein the catalyst is selected from any one of tertiary amines, quaternary ammonium salts, triphenylphosphine, triphenylantimony, chromium acetylacetone, chromium isooctanoate, and organotin compounds. 4.如权利要求2所述的堵漏剂，其特征在于，催化剂选自三乙胺、N,N-二甲基苄胺、N,N-二甲基苯胺、三甲基苄基氯化铵、四乙基溴化铵中任意一种。4. The sealing agent according to claim 2, wherein the catalyst is selected from any one of triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, trimethylbenzylammonium chloride, and tetraethylammonium bromide. 5.如权利要求2所述的堵漏剂，其特征在于，催化剂用量为反应物总质量的0.1%～3%。5. The plugging agent according to claim 2, characterized in that the amount of catalyst used is 0.1% to 3% of the total mass of the reactants. 6.如权利要求2所述的堵漏剂，其特征在于，（甲基）丙烯酸的添加量为缩水甘油醚氧丙基环四硅氧烷中环氧基摩尔数的1.1~1.5倍。6. The sealing agent according to claim 2, characterized in that the amount of (meth)acrylic acid added is 1.1 to 1.5 times the number of epoxy groups in glycidyl etheroxypropylcyclotetrasiloxane. 7.如权利要求2所述的堵漏剂，其特征在于，自由基阻聚剂为对甲氧基苯酚、对苯二酚、2,5-二甲基对苯二酚、2,6-二叔丁基-4-甲基苯酚中任意一种，其加入量为反应物总质量的0.01%～1%。7. The plugging agent according to claim 2, wherein the free radical polymerization inhibitor is any one of p-methoxyphenol, hydroquinone, 2,5-dimethylhydroquinone, and 2,6-di-tert-butyl-4-methylphenol, and its addition amount is 0.01% to 1% of the total mass of the reactants. 8.如权利要求2所述的堵漏剂，其特征在于，具体反应过程为：将缩水甘油醚氧丙基环四硅氧烷加热至80～90℃，滴加（甲基）丙烯酸、催化剂和自由基阻聚剂的混合物，滴加完毕，控制反应温度为110～120℃，维持此温度5h，停止加热降至室温即可得到目标产物。8. The plugging agent according to claim 2, characterized in that the specific reaction process is as follows: heating glycidyl etheroxypropylcyclotetrasiloxane to 80-90°C, adding dropwise a mixture of (meth)acrylic acid, catalyst and free radical polymerization inhibitor, and after the addition is complete, controlling the reaction temperature to 110-120°C, maintaining this temperature for 5 hours, stopping the heating and cooling to room temperature to obtain the target product. 9.如权利要求1所述的堵漏剂，其特征在于，高Tg甲基丙烯酸酯单体选自甲基丙烯酸异冰片酯、邻苯基苯氧乙基甲基丙烯酸酯、甲基丙烯酸苄基酯、甲基丙烯酸苯酯、甲基丙烯酸叔丁酯、甲基丙烯酸环己酯、甲基丙烯酸四氢呋喃酯、甲基丙烯酸三环癸烷基酯、双环戊二烯甲基丙烯酸酯中任意一种。9. The sealing agent according to claim 1, characterized in that the high Tg methacrylate monomer is selected from any one of isobornyl methacrylate, o-phenylphenoxyethyl methacrylate, benzyl methacrylate, phenyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, tetrahydrofuran methacrylate, tricyclodecyl methacrylate, and dicyclopentadiene methacrylate. 10.如权利要求1所述的堵漏剂，其特征在于，高Tg甲基丙烯酸酯单体选自甲基丙烯酸异冰片酯、双环戊二烯甲基丙烯酸酯或甲基丙烯酸三环癸烷基酯。10. The sealing agent according to claim 1, wherein the high Tg methacrylate monomer is selected from isobornyl methacrylate, dicyclopentadiene methacrylate, or tricyclodecyl methacrylate. 11.如权利要求1所述的堵漏剂，其特征在于，所述的流平剂选自德国毕克流平剂BYK-333、BYK-3505，以及三正高分子的超分散剂CH-1、CH-2、CH-3、CH-5、CH-6、CH-7、CH-8、CH-9中任意一种。11. The sealing agent as described in claim 1, wherein the leveling agent is selected from any one of the following: BYK-333 and BYK-3505 (BYK leveling agents from Germany), and CH-1, CH-2, CH-3, CH-5, CH-6, CH-7, CH-8, and CH-9 (super-dispersants of tri-positive polymers). 12.如权利要求1所述的堵漏剂，其特征在于，自由基热引发剂选用分解温度在80~95℃的偶氮类或过氧化物类自由基热引发剂。12. The sealing agent as described in claim 1, characterized in that the free radical thermal initiator is selected from azo or peroxide free radical thermal initiators with a decomposition temperature of 80~95℃. 13.如权利要求1所述的堵漏剂，其特征在于，自由基热引发剂为偶氮二异丁腈、偶氮二异庚腈或过氧化苯甲酰中任意一种。13. The sealing agent according to claim 1, wherein the free radical thermal initiator is any one of azobisisobutyronitrile, azobisisoheptanenitrile, or benzoyl peroxide.
CN202411326017.6A 2024-09-23 2024-09-23 High heat-resistant flexible graphite bipolar plate microporous sealing agent Active CN119219829B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001043964A1 (en) * 1999-12-17 2001-06-21 Loctite Corporation Impregnation of a graphite sheet with a sealant
US6284401B1 (en) * 1999-04-19 2001-09-04 George A. Marchetti Thin graphite bipolar plate with associated gaskets and carbon cloth flow-field for use in an ionomer membrane fuel cell

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Publication number Priority date Publication date Assignee Title
WO2023055587A1 (en) * 2021-09-29 2023-04-06 Illuming Power Inc. Improved monomer compositions for temperature resistance after curing

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284401B1 (en) * 1999-04-19 2001-09-04 George A. Marchetti Thin graphite bipolar plate with associated gaskets and carbon cloth flow-field for use in an ionomer membrane fuel cell
WO2001043964A1 (en) * 1999-12-17 2001-06-21 Loctite Corporation Impregnation of a graphite sheet with a sealant

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