CN115785833B - Sealing material for hydrogen fuel cell and preparation method thereof - Google Patents
Sealing material for hydrogen fuel cell and preparation method thereof Download PDFInfo
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- 239000003566 sealing material Substances 0.000 title claims abstract description 54
- 239000000446 fuel Substances 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 21
- 239000004711 α-olefin Substances 0.000 claims abstract description 20
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 229920000098 polyolefin Polymers 0.000 claims abstract description 9
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 150000003440 styrenes Chemical class 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229940116351 sebacate Drugs 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims 2
- 230000002745 absorbent Effects 0.000 claims 2
- 150000008301 phosphite esters Chemical class 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 17
- 230000001070 adhesive effect Effects 0.000 abstract description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract description 9
- 239000012528 membrane Substances 0.000 abstract description 7
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 239000011112 polyethylene naphthalate Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to a sealing material for a hydrogen fuel cell and a preparation method thereof, wherein the sealing material comprises the following raw materials in parts by weight: 10-50 parts of butyl rubber; 10-50 parts of polyolefin thermoplastic elastomer (POE); 5-25 parts of amorphous alpha-olefin copolymer (APAO); 5-25 parts of anhydride modified hydrogenated styrene block polymer; 0-1 part of ultraviolet absorber; 0-1 part of antioxidant; 0-1 part of coupling agent. The sealing material has excellent acid resistance, can be kept stable in a proton membrane hydrogen fuel cell for a long time, and has excellent adhesive property and simple manufacturing process.
Description
Technical Field
The invention relates to a sealing material for a hydrogen fuel cell and a preparation method thereof, belonging to the technical field of fuel cells.
Background
The fuel cell is a system for directly converting chemical energy of fuel gas into electric energy, and has been widely focused and used due to the advantages of high conversion efficiency, no emission and the like. Under the action of the catalyst of the anode plate, the hydrogen generates protons and electrons, the protons penetrate through the proton exchange membrane to reach the cathode of the fuel cell, the electrons cannot pass through the proton exchange membrane and reach the cathode of the fuel cell through an external circuit, and therefore current is generated in the external circuit. The hydrogen fuel cell is easy to burn and explode due to the small molecular diameter of hydrogen gas, and the cell unit element is required to have good gas tightness, and particularly, the external sealing effect of the electric pile between the membrane electrode and the bipolar plate is good. In the prior art, unsaturated polyolefin rubber or adhesive tape or adhesive film with a multilayer structure is mostly used as a sealing material, and Chinese patent application with application number 202010614192.0 discloses a sealing material for a fuel cell and a preparation method thereof, wherein the adopted unsaturated rubber needs high-temperature vulcanization, has poor strong acid resistance, has poor bonding performance to various metals and inorganic materials, and is easy to cause interface bonding failure due to the soaking effect of warm water when being used for a long time. The Chinese patent application No. 201410014082.5 discloses a fuel cell sealing material and a preparation method thereof, wherein the adopted multilayer structure is an adhesive tape composite elastic sealing rubber layer, the material structure is complex, the preparation process is complex, and the cost is difficult to control. The chinese patent application No. 202080067157.X discloses a fuel cell joint body and a laminate, which are also multilayer structure sealing materials, the adhesive resin layer adopts acid modified polyolefin adhesive resin, the easy adhesive layer is used as a primer layer to coat both sides of a substrate first, then the adhesive resin is coated, and the preparation process is complicated.
Disclosure of Invention
The present invention has been made in view of the above problems of the prior art, and provides a sealing material for hydrogen fuel cells, which has excellent acid resistance, can be stably maintained for a long period in proton membrane hydrogen fuel cells, has excellent adhesion properties, and is simple in manufacturing process, and a method for manufacturing the same.
The technical scheme for solving the technical problems is as follows:
the sealing material for the hydrogen fuel cell comprises the following raw materials in parts by weight: 10-50 parts of butyl rubber; 10-50 parts of polyolefin thermoplastic elastomer (POE); 5-25 parts of amorphous alpha-olefin copolymer (APAO); 5-25 parts of anhydride modified hydrogenated styrene block polymer; 0-1 part of ultraviolet absorber; 0-1 part of antioxidant; 0-1 part of coupling agent.
Based on the technical scheme, the invention can also make the following improvements:
further, the Mooney viscosity ML (1+4) of the butyl rubber is 45-70 at 100 ℃; preferably, the Exxon Butyl 165, exxon Butyl 268 and Exxon Butyl269 manufactured by Exxon Mobil are selected according to the Mooney viscosity range of the Butyl rubber; 268 butyl rubber produced by JSR in Japan.
The beneficial effects of adopting the further technical scheme are as follows: the air permeability of butyl rubber is lower in hydrocarbon rubber, and the air permeability is not changed greatly at high temperature; the chemical unsaturation degree is low, and the heat resistance and the oxidation aging resistance are relatively good; the ultraviolet resistance is excellent, and the ultraviolet-resistant glass can be exposed to sunlight for a long time; low water permeability, water vapor resistance, acid and alkali resistance and good polar solvent resistance. Therefore, the butyl rubber can well play roles in water resistance, acid resistance, ageing resistance and gas sealing in the sealing material.
Further, the polyolefin thermoplastic elastomer is an ethylene-octene copolymer, the melt index of the ethylene-octene copolymer is 5-40 g/10min at 190 ℃, and the melting point is 60-100 ℃; preferably, the melt index and melting point ranges of the ethylene-octene copolymers according to the present invention may be selected from the commercially available U.S. Dow Engages 8401, engages 8402, engages 8407, engages 8411, engages 8200, etc.
The beneficial effects of adopting the further technical scheme are as follows: the ethylene-octene copolymer elastomer has the advantages of small density, high elasticity, good toughness, good bending property, excellent low-temperature impact resistance, low water vapor permeability and the like. Therefore, POE resin can improve the strength of the material body, the low-temperature impact resistance and the water resistance in a sealing material system.
Further, the amorphous alpha-olefin copolymer (APAO) has a softening point of 90 to 160 ℃ and a melt viscosity of 3000 to 10000mPas at 190 ℃. Preferably, the amorphous alpha-olefin copolymers according to the present invention may have melt viscosity and softening point ranges selected from the commercially available VESTOPLASET series, 308, 408, 508, 608, 703, 704, 708, etc.
The beneficial effects of adopting the further technical scheme are as follows: the amorphous alpha-olefin copolymer is a flexible olefin copolymer with low molecular weight, high fluidity, amorphous state and high randomness, which is obtained by taking alpha-olefin as a raw material and polymerizing the alpha-olefin and has the advantages of ultraviolet resistance, water resistance, aging resistance, solvent resistance and the like. Therefore, the APAO is adopted in the sealing material, so that the adhesive force after hot pressing can be improved, and the performances such as water resistance, solvent resistance and the like can be improved.
Further, the styrene content of the anhydride modified hydrogenated styrene block polymer is 10 to 30 weight percent, and the grafting ratio of maleic anhydride is 1.0 to 2.0 percent; preferably, the styrene content and the maleic anhydride grafting ratio of the anhydride-modified hydrogenated styrene block polymer according to the present invention may be selected from commercially available Koteng FG1901, FG1924, xuehua TUFTEL M1911, M1943, etc.
The beneficial effects of adopting the further technical scheme are as follows: the acid anhydride modified hydrogenated styrene block polymer adopted by the invention is a hydrogenated styrene-polybutadiene-styrene block copolymer (SEBS), has good oxidation resistance, weather resistance and temperature resistance, has excellent compatibility with polyolefin, and can improve the adhesion to metal after acid anhydride modification. Therefore, the acid anhydride modified hydrogenated styrene block polymer plays a role of a modifier in a sealing material system, and improves the bonding performance to metal.
Further, the coupling agent is a silane coupling agent or a titanate coupling agent.
Further, the ultraviolet absorber is one of bis (2, 6-tetramethyl-4-piperidinyl) sebacate (basf Tinuvin 770), 2- (2-hydroxy-5-benzyl) benzotriazole or 2, 4-di-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol.
Further, the antioxidant is one or two of hindered phenols or phosphites.
The invention also provides a preparation method of the sealing material for the hydrogen fuel cell, which comprises the steps of preparing raw materials into slurry, coating the slurry on a substrate film with the thickness of 25-125 mu m, and coating the substrate film with the thickness of 15-300 mu m to prepare the sealing material. The method specifically comprises the following steps:
(1) Weighing raw materials according to parts by weight, and dissolving the raw materials by using a solvent to prepare slurry with the solid content of 15-30wt%;
(2) And (3) adding the slurry into a comma scraper coater, placing the substrate film in an unreeling unit of the comma scraper coater, placing the substrate film into a corona machine for corona, coating the slurry on the corona side of the substrate film, drying, setting the drying temperature to be 80-110 ℃, drying for 3-5 min, compounding the protective film, and reeling to obtain a finished product.
The invention is not particularly limited in the type of the substrate film, and preferably, the substrate film material can be selected from materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyamide (PA), thermoplastic Polyurethane (TPU), and the like, and parameters such as physical and mechanical properties, gas barrier properties, chemical stability, heat resistance stability, surface coating property and the like are comprehensively considered.
The invention has the advantages that:
(1) The sealing material for the hydrogen fuel cell has the advantages that the raw materials adopted by the sealing material for the hydrogen fuel cell are easy to obtain, and the manufacturing process is simple;
(2) The sealing material disclosed by the invention has the advantages of excellent adhesive property, low water vapor transmittance, long-term soaking in hot water and good sealing effect;
(3) The sealing material has excellent acid resistance and can be kept stable for a long time in a proton membrane hydrogen fuel cell.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Raw materials used in the examples:
a1: butyl rubber, exxon Butyl 165;
a2: butyl rubber, exxon Butyl 268;
b1: POE, dow Engage 8401;
c1: amorphous alpha-olefin copolymer (APAO), which wins the creation of vesoproplaset 308;
d1: anhydride-modified hydrogenated styrene block polymer, koteng FG 1901;
e1: ultraviolet absorber, bis (2, 6-tetramethyl-4-piperidinyl) sebacate, basf Tinuvin 770;
f1: hindered phenol and phosphite compound antioxidant, basf Irganox B215;
g1: titanate coupling agent, kenrich KR-TTS, U.S.A.
Example 1
The sealing material for the hydrogen fuel cell is prepared from the following raw materials in parts by weight: 40g of butyl rubber (A1); 40g of POE (B1); 10g of an amorphous alpha-olefin copolymer (C1); 10g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of an antioxidant (F1); 1g of a coupling agent; 412g of toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until the raw materials are completely dissolved, and a sealing material solution with 20% of solid content is obtained.
And then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the sealing material with the thickness of 15 mu m, and drying in a drying oven at the temperature of 100 ℃ to obtain the sealing material product.
Example 2
The thickness of the coating dry adhesive is 100 μm, and the addition amount and the production process of other raw materials are the same as those of the example 1.
Example 3
The thickness of the coating dry adhesive was 300. Mu.m, and the addition amount of other raw materials and the production process were the same as those of example 1.
Example 4
The coating used a 125 μm PEN film as the substrate, and the other raw materials were added in the same amounts, coating thicknesses and production processes as in example 1.
Example 5
The sealing material for the hydrogen fuel cell is prepared from the following raw materials in parts by weight: 50g of butyl rubber (A2); 10g of POE (B1); 20g of an amorphous alpha-olefin copolymer (C1); 20g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of an antioxidant (F1); 1g of a coupling agent; 412g of toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until the raw materials are completely dissolved, and a sealing material solution with 20% of solid content is obtained.
And then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the sealing material with the thickness of 15 mu m, and drying in a drying oven at the temperature of 100 ℃ to obtain the sealing material product.
Example 6
The sealing material for the hydrogen fuel cell is prepared from the following raw materials in parts by weight: 10g of butyl rubber (A2); 50g of POE (B1); 20g of an amorphous alpha-olefin copolymer (C1); 20g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of an antioxidant; 1g of a coupling agent; 412g of toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until the raw materials are completely dissolved, and a sealing material solution with 20% of solid content is obtained.
And then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the sealing material with the thickness of 15 mu m, and drying in a drying oven at the temperature of 100 ℃ to obtain the sealing material product.
Example 7
The sealing material for the hydrogen fuel cell is prepared from the following raw materials in parts by weight: butyl rubber Exxon Butyl 268 g; 40g of POE (B1); amorphous alpha-olefin copolymer (C1) 1g; 19g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of an antioxidant; 1g of a coupling agent; 412g of toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until the raw materials are completely dissolved, and a sealing material solution with 20% of solid content is obtained.
And then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the sealing material with the thickness of 15 mu m, and drying in a drying oven at the temperature of 100 ℃ to obtain the sealing material product.
Example 8
The sealing material for the hydrogen fuel cell is prepared from the following raw materials in parts by weight: 40g of butyl rubber (A2); 40g of POE (B1); 19g of an amorphous alpha-olefin copolymer (C1); 1g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of an antioxidant; 1g of a coupling agent; 412g of toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until the raw materials are completely dissolved, and a sealing material solution with 20% of solid content is obtained.
And then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the sealing material with the thickness of 15 mu m, and drying in a drying oven at the temperature of 100 ℃ to obtain the sealing material product.
Comparative example 1
The amount of POE (B1) added was 80g, and no butyl rubber was added, and the other raw materials were added in the same amount and production process as in example 1.
Comparative example 2
80g of butyl rubber (A1) was added without POE raw material, and the other raw materials were added in the same amount and production process as in example 1.
Comparative example 3
The addition amount of other raw materials and the production process were the same as in example 1 without adding amorphous alpha-olefin copolymer (APAO).
Comparative example 4
The addition amount and production process of other raw materials were the same as in example 1 without adding the acid anhydride-modified hydrogenated styrene block polymer.
The sealing material products obtained in examples 1 to 8 and comparative examples 1 to 4 were subjected to performance tests as follows:
1) Peel strength test:
the test base materials are respectively aluminum plates (thickness is 1 mm) and PEN films (the dyne value is more than 48), a flat plate hot press machine is used for sample preparation, the hot press condition is 140 ℃/0.6MPa/30S, the sample preparation is cooled to 25 ℃ and then placed for 24 hours, 180 DEG peel strength test is carried out according to the method described by national standard GB/T2792-2014, the test condition temperature is 25 ℃, the stretching rate is 300mm/min, and the test width is 20mm.
2) Water vapor transmission rate test:
the temperature and humidity are 40 ℃/RH90 and 80 ℃/RH90 water vapor transmittance respectively according to the national standard GB/T1037-2021 test conditions.
3) Hot water soaking aging test:
preparing a test sample with an adhesive substrate being an aluminum plate according to the test method 1), immersing the aluminum plate in hot water at 90 ℃ for 1000 hours, observing whether the adhesive surface has bubbles and other anomalies, and testing 180-degree peel strength.
4) Solvent soaking aging test:
test samples with the adhesive base material being an aluminum plate were prepared according to the test method 1), and after 50% of ethylene glycol was heated and soaked for 1000 hours at 90 ℃, whether the adhesive surface had bubbles or not was observed, and 180 ° peel strength was tested.
5) Acid soaking aging test:
test samples with an aluminum plate as a bonding substrate were prepared according to test method 1), and after heating and immersing in sulfuric acid solution with ph=3 for 1000 hours at 90 ℃, the bonding surface was observed for anomalies such as bubbles, and 180 ° peel strength was tested.
6) High-low temperature impact performance test:
preparing a test sample with an adhesive substrate being an aluminum plate according to the test method 1), placing the test sample into a high-low temperature impact test box for testing, taking cold and hot impact at-40 ℃ to 85 ℃ and 40 ℃ to 0.5h to 85 ℃ as one cycle, testing 1000 cycles, observing whether the adhesive surface has bubbles and other anomalies, and testing 180-DEG peel strength.
The results of the above tests are shown in tables 1-2:
table 1 example performance test results
Table 2 comparative example performance test results
As can be seen from the results shown in the comparative examples in Table 2, comparative example 1 was free from the addition of butyl rubber, and had lowered water resistance, solvent resistance and acid resistance, and water vapor, solvent and acidic substances easily entered into the bonding interface to generate bubbles, resulting in lowered bonding force; comparative example 2 has reduced acid resistance and high and low temperature impact resistance; in the comparative example 3, no main raw material APAO with a bonding effect is added, the peeling strength is low, more bubbles are generated after an aging test, and the bonding force is low; comparative example 4 without the addition of the anhydride-modified hydrogenated styrene block polymer, adhesion to metallic aluminum was reduced.
As can be seen from the results shown in the examples in Table 1, the sealing material for hydrogen fuel cells provided by the invention has good adhesion to aluminum and PEN, has low water vapor transmittance under the conditions of low temperature and high temperature, has good sealing effect after long-term soaking and aging in hot water, has excellent solvent resistance and acid corrosion resistance, is resistant to high and low temperature impact cycles, can be kept stable for a long time in proton membrane hydrogen fuel cells, and has practical value.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (3)
1. The sealing material for the hydrogen fuel cell is characterized by comprising the following raw materials in parts by weight:
40 parts of butyl rubber;
40 parts of polyolefin thermoplastic elastomer;
10 parts of amorphous alpha-olefin copolymer;
10 parts of anhydride modified hydrogenated styrene block polymer;
1 part of ultraviolet absorbent bis (2, 6-tetramethyl-4-piperidyl) sebacate;
1 part of hindered phenol and phosphite ester composite antioxidant;
1 part of titanate coupling agent;
412 parts of toluene solvent;
the Mooney viscosity ML (1+4) of the butyl rubber is 45-70 at 100 ℃;
the polyolefin thermoplastic elastomer is an ethylene-octene copolymer, the melt index of the ethylene-octene copolymer is 5-40 g/10min at 190 ℃, and the melting point is 60-100 ℃;
the softening point of the amorphous alpha-olefin copolymer is 90-160 ℃, and the melt viscosity of the amorphous alpha-olefin copolymer is 3000-10000 mPas at 190 ℃;
the styrene content of the anhydride modified hydrogenated styrene block polymer is 10-30wt% and the maleic anhydride grafting ratio is 1.0-2.0%;
the raw materials are prepared into slurry, the slurry is coated on PEN substrate film with the thickness of 25 mu m, the coating thickness is 300 mu m, and the sealing material is prepared by drying in a baking oven at the temperature of 100 ℃.
2. The sealing material for the hydrogen fuel cell is characterized by comprising the following raw materials in parts by weight:
40 parts of butyl rubber;
40 parts of polyolefin thermoplastic elastomer;
10 parts of amorphous alpha-olefin copolymer;
10 parts of anhydride modified hydrogenated styrene block polymer;
1 part of ultraviolet absorbent bis (2, 6-tetramethyl-4-piperidyl) sebacate;
1 part of hindered phenol and phosphite ester composite antioxidant;
1 part of titanate coupling agent;
412 parts of toluene solvent;
the Mooney viscosity ML (1+4) of the butyl rubber is 45-70 at 100 ℃;
the polyolefin thermoplastic elastomer is an ethylene-octene copolymer, the melt index of the ethylene-octene copolymer is 5-40 g/10min at 190 ℃, and the melting point is 60-100 ℃;
the softening point of the amorphous alpha-olefin copolymer is 90-160 ℃, and the melt viscosity of the amorphous alpha-olefin copolymer is 3000-10000 mPas at 190 ℃;
the styrene content of the anhydride modified hydrogenated styrene block polymer is 10-30wt% and the maleic anhydride grafting ratio is 1.0-2.0%;
the raw materials are prepared into slurry, the slurry is coated on a PEN substrate film with the thickness of 125 mu m, the coating thickness is 15 mu m, and the sealing material is prepared by drying in a baking oven at the temperature of 100 ℃.
3. A method for producing the sealing material for a hydrogen fuel cell according to claim 1 or 2, comprising the steps of:
(1) Weighing raw materials according to parts by weight, and dissolving the raw materials by using a solvent to prepare slurry with the solid content of 20 weight percent;
(2) And (3) adding the slurry into a comma scraper coater, placing the substrate film in an unreeling unit of the comma scraper coater, placing the substrate film into a corona machine for corona, coating the slurry on the corona side of the substrate film, drying, setting the drying temperature to 100 ℃, drying for 3-5 min, compounding the protective film, and reeling to obtain a finished product.
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