CN115785833A - 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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- CN115785833A CN115785833A CN202211464982.0A CN202211464982A CN115785833A CN 115785833 A CN115785833 A CN 115785833A CN 202211464982 A CN202211464982 A CN 202211464982A CN 115785833 A CN115785833 A CN 115785833A
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- 239000003566 sealing material Substances 0.000 title claims abstract description 51
- 239000000446 fuel Substances 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 15
- 239000004711 α-olefin Substances 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 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
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 229920000098 polyolefin Polymers 0.000 claims abstract description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 150000003440 styrenes Chemical class 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229940116351 sebacate Drugs 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 7
- 230000002745 absorbent Effects 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011112 polyethylene naphthalate Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal 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
- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 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
- 230000009471 action Effects 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
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 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
- 238000011056 performance test Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- -1 polyethylene terephthalate 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 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
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 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
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 absorbent; 0-1 part of antioxidant; 0-1 part of coupling agent. The sealing material has excellent acid resistance, can be stably kept in a proton membrane hydrogen fuel cell for a long time, has excellent bonding performance and is simple in 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
A fuel cell is a system that directly converts chemical energy of fuel gas into electric energy, and has attracted attention and been widely used due to its advantages of high conversion efficiency, no emission, and the like. The hydrogen generates proton and electron under the action of catalyst of anode plate, the proton penetrates proton exchange membrane to reach the cathode of fuel cell, the electron can not pass through proton exchange membrane, and reaches the cathode plate of fuel cell through external circuit, so as to generate current in external circuit. The hydrogen fuel cell is easy to combust and explode due to the small molecular diameter of hydrogen gas, requires the cell unit to have good gas tightness, and particularly has good external sealing effect of a galvanic pile between a membrane electrode and a bipolar plate. The present invention relates to a sealing material for fuel cell and its preparation method, and is characterized by that the unsaturated rubber is vulcanized at high temp., and its strong acid resistance is poor, and its adhesive property for various metals and inorganic materials is poor, and when it is used for a long period, it is easy to make interface adhesive failure due to warm water soaking action. The Chinese patent with application number 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. Chinese patent application No. 202080067157.X discloses an assembly for a fuel cell, and a laminate, which are also multilayer-structured sealing materials, wherein an acid-modified polyolefin adhesive resin is used as an adhesive resin layer, and easy-adhesion layers are first applied to both sides of a base material as a primer layer, and then the adhesive resin is applied, and the production process is complicated.
Disclosure of Invention
The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a sealing material for a hydrogen fuel cell, which has excellent acid resistance, can be stably maintained for a long period of time in a proton membrane hydrogen fuel cell, has excellent adhesion properties, and is simple in manufacturing process, and a method for preparing the same.
The technical scheme for solving the technical problems is as follows:
a sealing material for a 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 absorbent; 0-1 part of antioxidant; 0-1 part of coupling agent.
On the basis of 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, commercially available Exxon Butyl 165, exxon Butyl 268 and Exxon Butyl269 from Exxon Mobil can be used depending on the Mooney viscosity range of the Butyl rubber; 268 butyl rubber manufactured by JSR of japan.
The beneficial effects of adopting the further technical scheme are as follows: the air permeability of the butyl rubber is lower in hydrocarbon rubber, and the air permeability does not change greatly at high temperature; the chemical unsaturation degree is low, and the heat resistance and the oxidation and aging resistance are good; the ultraviolet resistance is excellent, and the paint can be exposed to the sun for a long time; low water permeability, good water vapor resistance, acid and alkali resistance and polar solvent resistance. Therefore, the butyl rubber can well play a role in water resistance, acid resistance, ageing resistance and gas sealing in the sealing material.
Further, the polyolefin thermoplastic elastomer is an ethylene-octene copolymer, and the ethylene-octene copolymer has a melt index of 5-40 g/10min at 190 ℃ and a melting point of 60-100 ℃; preferably, the melt index and melting point range of the ethylene-octene copolymer according to the present invention may be selected from commercially available dow Engage8401, engage8402, engage8407, engage8411, engage8200, 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 transmission rate and the like. Therefore, the 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 α -olefin copolymers according to the present invention have melt viscosities and softening points in the range selected from the commercially available vestoplast series, 308, 408, 508, 608, 703, 704, 708, and the like.
The beneficial effects of adopting the further technical scheme are as follows: the amorphous alpha-olefin copolymer is a flexible olefin copolymer which is obtained by polymerizing alpha-olefin serving as a raw material and has the advantages of ultraviolet resistance, waterproofness, aging resistance, solvent resistance and the like, and the low molecular weight, high fluidity, amorphous state and high randomness are obtained. Therefore, the use of APAO in the sealing material can improve the adhesion after hot pressing and also improve the properties such as water resistance and solvent resistance.
Further, the styrene content of the anhydride modified hydrogenated styrene block polymer is 10 to 30 weight percent, and the grafting rate of maleic anhydride is 1.0 to 2.0 percent; preferably, the styrene content and maleic anhydride graft ratio of the acid anhydride-modified hydrogenated styrene block polymer according to the present invention can be selected from commercially available kraton FG1901, FG1924, asahi chemical TUFTEL M1911, M1943, and the like.
The beneficial effects of adopting the further technical scheme are as follows: the anhydride modified hydrogenated styrene block polymer adopted by the invention is hydrogenated styrene-polybutadiene-styrene block copolymer (SEBS), which has good oxidation resistance, weather resistance and temperature resistance, has excellent compatibility with polyolefin, and can improve the adhesion to metal after anhydride modification. Therefore, the anhydride modified hydrogenated styrene block polymer is adopted to play a role of a modifier in a sealing material system, and the bonding performance to metal is improved.
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-piperidyl) 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 the 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 obtain the sealing material. The method specifically comprises the following steps:
(1) Weighing raw materials in parts by weight, dissolving the raw materials by using a solvent to prepare slurry with the solid content of 15-30 wt%;
(2) Adding the slurry into a comma knife coater, simultaneously placing a substrate film in an unwinding unit of the comma knife coater, placing the substrate film into a corona machine, coating the slurry on the corona side of the substrate film, drying at the drying temperature of 80-110 ℃, compounding a protective film after drying for 3-5 min, and winding to obtain a finished product.
The type of the substrate film is not specifically limited, preferably, the substrate film material may be polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyamide (PA), thermoplastic Polyurethane (TPU), and the like, and the physical and mechanical properties, gas barrier properties, chemical stability, heat resistance stability, surface coating properties, and other parameters are comprehensively considered.
The invention has the advantages that:
(1) The sealing material for the hydrogen fuel cell is easy to obtain raw materials and simple in manufacturing process;
(2) The sealing material has excellent bonding performance, low water vapor transmission rate, good sealing effect after being soaked in hot water for a long time;
(3) The sealing material of the present invention has excellent acid resistance and can be stable in proton membrane hydrogen fuel cells for a long period of time.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Raw materials used in the examples:
a1: butyl rubber, exxon Butyl 165 Exxon;
a2: butyl rubber, exxon Butyl 268, exxon mexon;
b1: POE, dow Engage 8401;
c1: amorphous alpha-olefin copolymer (APAO), pioneer veto plaset 308;
d1: anhydride-modified hydrogenated styrene block polymer, kraton FG 1901;
e1: uv absorbers, bis (2, 6-tetramethyl-4-piperidinyl) sebacate, basf Tinuvin 770;
f1: hindered phenol and phosphite complex antioxidant, basf Irganox B215;
g1: titanate coupling agent, kenrich KR-TTS, USA.
Example 1
The sealing material for the hydrogen fuel cell is prepared by the following raw materials in parts by weight: 40g of butyl rubber (A1); POE (B1) 40g; 10g of an amorphous α -olefin copolymer (C1); 10g of the acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of an ultraviolet absorber (E1); 1g of antioxidant (F1); 1g of coupling agent; 412g of a toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until being completely dissolved, and the sealing material solution with the solid content of 20% is obtained.
Then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the dry glue with the thickness of 15 mu m, and drying in an oven at 100 ℃ to obtain the sealing material product.
Example 2
The thickness of the coated dry glue 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 coated dry glue is 300 μm, and the addition amount and the production process of other raw materials are the same as those of the example 1.
Example 4
The coating was carried out using a 125 μm PEN film as a substrate, and the amounts of other raw materials added, the coating thickness and the production process were the same as in example 1.
Example 5
The sealing material for the hydrogen fuel cell is prepared by the following raw materials in parts by weight: 50g of butyl rubber (A2); 10g of POE (B1); 20g of amorphous α -olefin copolymer (C1); 20g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of an ultraviolet absorber (E1); 1g of antioxidant (F1); 1g of coupling agent; 412g of a toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until being completely dissolved, and the sealing material solution with the solid content of 20% is obtained.
Then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the dry glue with the thickness of 15 mu m, and drying in an oven at 100 ℃ to obtain the sealing material product.
Example 6
The embodiment prepares a sealing material for a hydrogen fuel cell, which is prepared from the following raw materials in parts by weight: 10g of butyl rubber (A2); POE (B1) 50g; 20g of amorphous α -olefin copolymer (C1); 20g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of antioxidant; 1g of coupling agent; 412g of a toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until being completely dissolved, and the sealing material solution with the solid content of 20% is obtained.
And then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the dry glue with the thickness of 15 mu m, and drying in an oven at 100 ℃ to obtain the sealing material product.
Example 7
The sealing material for the hydrogen fuel cell is prepared by the following raw materials in parts by weight: butyl rubber Exxon Butyl 268 40g; POE (B1) 40g; amorphous α -olefin copolymer (C1) 1g; 19g of the acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of ultraviolet absorber (E1); 1g of antioxidant; 1g of coupling agent; 412g of a toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, and stirred and mixed until the raw materials are completely dissolved to obtain a sealing material solution with the solid content of 20%.
Then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the dry glue with the thickness of 15 mu m, and drying in an oven at 100 ℃ to obtain the sealing material product.
Example 8
The sealing material for the hydrogen fuel cell is prepared by the following raw materials in parts by weight: 40g of butyl rubber (A2); POE (B1) 40g; 19g of amorphous α -olefin copolymer (C1); 1g of an acid anhydride-modified hydrogenated styrene block polymer (D1); 1g of an ultraviolet absorber (E1); 1g of antioxidant; 1g of coupling agent; 412g of a toluene solvent; the raw materials are added into a 1000mL three-neck flask, heated to 80 ℃ in a water bath, stirred and mixed until being completely dissolved, and the sealing material solution with the solid content of 20% is obtained.
Then coating the prepared sealing material on a PEN film with the thickness of 25 mu m, coating the dry glue with the thickness of 15 mu m, and drying in an oven at 100 ℃ to obtain the sealing material product.
Comparative example 1
The POE (B1) addition was 80g, no butyl rubber was added, and the other raw materials addition and production process were the same as in example 1.
Comparative example 2
80g of butyl rubber (A1), POE raw material is not added, and the addition amount and the production process of other raw materials are the same as those of the butyl rubber (A1).
Comparative example 3
The amorphous alpha-olefin copolymer (APAO) was not added, and the amounts of other raw materials and the production process were the same as in example 1.
Comparative example 4
The amount of other raw materials and the production process were the same as in example 1, except that the acid anhydride-modified hydrogenated styrene block polymer was not added.
We performed performance tests on the sealing material products obtained in examples 1 to 8 and comparative examples 1 to 4, according to the following methods:
1) And (3) testing the peel strength:
the test base materials are respectively an aluminum plate (with the thickness of 1 mm) and a PEN film (with the dyne value of more than 48), a flat plate hot press is used for preparing samples, the hot pressing condition is 140 ℃/0.6MPa/30S, the samples are cooled to 25 ℃ and then placed for 24h, and 180-degree peel strength test is carried out according to the method of the national standard GB/T2792-2014, the test condition temperature is 25 ℃, the stretching rate is 300mm/min, and the test width is 20mm.
2) Testing the water vapor transmission rate:
according to the test conditions of the national standard GB/T1037-2021, the temperature and the humidity are respectively 40 ℃/RH90 and 80 ℃/RH90 water vapor transmission rates.
3) And (3) hot water immersion resistance aging test:
a test sample with an aluminum plate as an adhesive base material is prepared according to the test method 1), and is soaked in hot water for 1000 hours at 90 ℃ to observe whether the adhesive surface has abnormalities such as bubbles and the like, and the 180-degree peel strength is tested.
4) And (3) solvent soaking aging resistance test:
a test sample with an aluminum plate as an adhesive base material was prepared according to test method 1), and after heating and soaking with 50% ethylene glycol at 90 ℃ for 1000 hours, whether or not there was any abnormality such as bubbles on the adhesive surface was observed, and 180 ° peel strength was tested.
5) Acid soaking aging resistance test:
a test sample in which the bonding base material was an aluminum plate was prepared according to test method 1), and after heating and soaking in a sulfuric acid solution having a PH =3 at 90 ℃ for 1000 hours, whether or not there was abnormality such as bubbles on the bonding surface was observed, and 180 ° peel strength was tested.
6) And (3) testing high and low temperature impact properties:
preparing a test sample with an aluminum plate as a bonding base material according to the test method 1), placing the test sample in a high-low temperature impact test box for testing, testing the test sample in a cycle of-40-85 ℃ cold-hot impact-40 ℃ @0.5h to 85 ℃ @0.5h, testing for 1000 cycles, observing whether the bonding surface has bubble and other abnormalities, and testing the 180-degree peel strength.
The above test results are shown in tables 1-2:
table 1 results of performance test of examples
Table 2 comparative examples property test results
As can be seen from the results shown in table 2, in comparative example 1, since butyl rubber was not added, the water resistance, solvent resistance, and acid resistance were lowered, and water vapor, solvent, and acidic substances were easily impregnated into the bonding interface to generate bubbles, which resulted in lowering of the bonding strength; comparative example 2 is reduced in acid resistance and high and low temperature impact resistance; in comparative example 3, no raw material APAO mainly having an adhesive effect was added, the peel strength was low, a large amount of bubbles were generated after the aging test, and the adhesive force was low; comparative example 4, in which no acid anhydride-modified hydrogenated styrene block polymer was added, the adhesion to metal aluminum was reduced.
From the results shown in the example in table 1, it can be seen that the sealing material for hydrogen fuel cells provided by the invention has good adhesion to aluminum and PEN, low water vapor transmission rate under low temperature and high temperature conditions, good sealing effect after long-term soaking and aging in hot water, excellent solvent resistance and acid corrosion resistance, high and low temperature impact cycle resistance, stability in proton membrane hydrogen fuel cells for a long time, and practical value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The sealing material for the hydrogen fuel cell is characterized by comprising the following raw materials in parts by weight:
10-50 parts of butyl rubber;
10-50 parts of polyolefin thermoplastic elastomer;
5-25 parts of amorphous alpha-olefin copolymer;
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.
2. The seal material for a hydrogen fuel cell according to claim 1, characterized in that the mooney viscosity ML (1 + 4) of the butyl rubber at 100 ℃ is 45 to 70.
3. The seal material for a hydrogen fuel cell according to claim 1, wherein the polyolefin thermoplastic elastomer is an ethylene-octene copolymer having a melt index of 5 to 40g/10min at 190 ℃ and a melting point of 60 to 100 ℃.
4. The sealing material for a hydrogen fuel cell according to claim 1, wherein the amorphous α -olefin copolymer has a softening point of 90 to 160 ℃ and a melt viscosity of 3000 to 10000mPas at 190 ℃.
5. The sealing material for a hydrogen fuel cell according to claim 1, wherein the acid anhydride-modified hydrogenated styrene block polymer has a styrene content of 10 to 30wt% and a maleic anhydride graft ratio of 1.0 to 2.0%.
6. The sealing material for a hydrogen fuel cell according to claim 1, wherein the coupling agent is a silane coupling agent or a titanate coupling agent.
7. The sealing material for a hydrogen fuel cell according to claim 1, wherein the ultraviolet absorber is one of bis (2, 6-tetramethyl-4-piperidyl) sebacate, 2- (2-hydroxy-5-benzyl) benzotriazole, or 2, 4-di-t-butyl-6- (5-chloro-2H-benzotriazol-2-yl) phenol.
8. The sealing material for a hydrogen fuel cell according to claim 1, wherein the antioxidant is one or both of hindered phenols and phosphites.
9. A method for producing the sealing material for a hydrogen fuel cell according to any one of claims 1 to 8, wherein the raw material is prepared into a slurry, and the slurry is applied to a substrate film having a thickness of 25 to 125 μm and applied to a substrate film having a thickness of 15 to 300 μm to obtain the sealing material.
10. The method of producing a sealing material for a hydrogen fuel cell according to claim 9, characterized by comprising the steps of:
(1) Weighing raw materials in parts by weight, dissolving the raw materials by using a solvent to prepare slurry with the solid content of 15-30 wt%;
(2) Adding the slurry into a comma knife coater, simultaneously placing a substrate film in an unwinding unit of the comma knife coater, placing the substrate film into a corona machine, coating the slurry on the corona side of the substrate film, drying at the drying temperature of 80-110 ℃, compounding a protective film after drying for 3-5 min, and winding to obtain a finished product.
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