CN112877027A - Hydrolysis-resistant sealant for proton membrane of fuel cell, and sealing membrane - Google Patents

Hydrolysis-resistant sealant for proton membrane of fuel cell, and sealing membrane Download PDF

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CN112877027A
CN112877027A CN202110056042.7A CN202110056042A CN112877027A CN 112877027 A CN112877027 A CN 112877027A CN 202110056042 A CN202110056042 A CN 202110056042A CN 112877027 A CN112877027 A CN 112877027A
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sealant
fuel cell
weight
parts
hydrolysis
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叶爱磊
戴玮洁
韩仲友
谈纪金
祁浩
周枫韵
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Suzhou Tailun Electronic Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • 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)
  • 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)
  • Fuel Cell (AREA)

Abstract

The present invention provides a hydrolysis resistant sealant for a proton membrane of a fuel cell, comprising: 100 parts by weight of active polydimethylsiloxane, wherein the end group of the polydimethylsiloxane is a hydroxyl group; 1 to 50 parts by weight of a silicone compound having an acryloyloxy group at one end; 10-100 parts by weight of a reactive diluent; 0.01 to 15 parts by weight of a crosslinking agent; 0.01 to 0.8 part by weight of at least one platinum catalyst. The invention also provides a sealing film using the sealant. According to the invention, the hydrolysis resistance of the sealant is improved by adding the hydrolysis-resistant siloxane, so that the adhesive tape containing the sealant is effectively prevented from falling off or wrinkling too early; in addition, the formed sealing film is formed in a one-step coating mode in a thousand-level dust-free environment, the temperature control of precise curing, the glue thickness control are precise (reaching 0.0001mm), the foot surface is controlled to prevent static electricity, and the product cleanliness reaches 100%.

Description

Hydrolysis-resistant sealant for proton membrane of fuel cell, and sealing membrane
Technical Field
The invention relates to the field of fuel cells, in particular to a hydrolysis-resistant sealant for a proton membrane of a fuel cell.
Background
In recent years, fuel cells have become a focus of attention for new energy vehicles. The proton conduction membrane is the core of the proton exchange membrane fuel cell in order to realize advanced chemical reaction of hydrogen and oxygen, a sealant or an adhesive tape needs to be coated on the proton conduction membrane in order to provide support for the proton conduction membrane and ensure the sealing property of the proton conduction membrane, and a binder on the sealant or the adhesive tape needs to have good thermal shock performance, very good high-temperature holding power and holding viscosity.
In addition, because water is generated after the reaction of hydrogen and oxygen, compared to other adhesives, the sealing compound on the proton-conducting membrane is required to have a certain hydrolysis resistance to prevent the sealant from falling off after a certain period of time and affecting the performance of the proton-conducting membrane.
Thus, there is a need for an improved sealant composition that provides a new type of hydrolysis resistant sealant.
Disclosure of Invention
In order to overcome the deficiencies of the prior art, it is an object of the present invention to provide a hydrolysis resistant sealant for a proton membrane of a fuel cell, the sealant comprising:
100 parts by weight of active polydimethylsiloxane, wherein the end group of the polydimethylsiloxane is a hydroxyl group;
1 to 50 parts by weight of a silicone compound having an acryloyloxy group at one end;
10-100 parts by weight of a reactive diluent;
0.01 to 15 parts by weight of a crosslinking agent;
0.01 to 0.8 part by weight of at least one platinum catalyst.
Preferably, the siloxane compound having an acryloyloxy group at one end has the formula:
R1(R2R3SiO)a(R4R5SiO)bSi(CH3)2UV
wherein R1 is an alkyl group having 1 to 10 carbon atoms, R2 is a compound containing an ether bond, i.e., C3H7OC4H9, R3, R4, and R5 are alkyl groups having 1 to 4 carbon atoms, U is bonded to Si, U is allyl (meth) acrylate, and the end thereof not bonded to V is C ═ C; v is an acryloyloxy group; a + b is less than or equal to 3000.
Preferably, the viscosity of the organosiloxane polymer whose terminal groups are hydroxyl groups at 25 ℃ is in the range of 20000-50000 mPa.s.
Preferably, 0.1-3 parts by weight of inhibitor is also included.
Preferably, the inhibitor is at least one silylated alkynol.
Preferably, the MQ resin is also included in an amount of 1 to 50 parts by mass.
Preferably, the MQ resin consists of a monofunctional chain R6SiO1/2 group and a tetrafunctional chain SiO4/2 group, and the molar ratio of the R6SiO1/2 group to the SiO4/2 group is 1:0.6-1: 1.
Preferably, the reactive diluent is dodecene.
Preferably, the crosslinking agent is an organohydrogenpolysiloxane containing at least two Si-H groups.
The second purpose of the invention is to provide a sealing film, which comprises a substrate layer, and an adhesive layer and a release film layer which are sequentially arranged on the substrate layer; wherein the adhesive layer is prepared by mixing, coating and baking the materials of each component in the sealant as claimed in claim 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the sealant disclosed by the invention, the siloxane compound with one end being the acryloxy group is added, so that the overall hydrolysis resistance of the sealant is improved, and premature falling, failure and the like after the sealant is coated are effectively avoided.
(2) Through continuous test and adjustment of the formula of the sealant, the sealant with stable viscosity, high cohesion, high continuous adhesion, good thermal shock performance, strong adsorbability, hydrolysis resistance, good tearing, no adhesive residue and good sealing performance is prepared.
(3) By adding the inhibitor, the curing rate of the sealant is controlled, and the phenomenon that the whole glue layer formed is fragile and cannot have good impact resistance due to too fast curing of the sealant is avoided; in addition, the inhibitor is set to be 0.1-3 parts by weight, so that the problem that the curing of the sealant is too slow after the inhibitor is more than 3 parts by weight is avoided.
(4) By adding MQ resin, the viscosity of the sealant is increased.
(5) When the sealant is specifically coated, multiple coating processes are combined, and the product has the advantages of one-step coating forming, a thousand-level dust-free environment, precise curing temperature control, accurate glue thickness control (reaching 0.0001mm), controllable and antistatic foot surface and 100% product cleanliness.
The foregoing description is only an overview of the technical solutions of the present invention, and some embodiments are described in detail below in order to make the technical solutions of the present invention more clearly understood and to implement the technical solutions according to the content of the description. Specific embodiments of the present invention are given in detail by the following examples.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a schematic view showing the structure of a sealing film for a membrane electrode assembly of a fuel cell according to the present invention.
In the figure:
1. a sealing film;
11. a release film layer 12, an adhesive layer 13 and a base material layer.
Detailed Description
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings, which will enable those skilled in the art to practice the present invention with reference to the accompanying specification. In the drawings, the shape and size may be exaggerated for clarity, and the same reference numerals will be used throughout the drawings to designate the same or similar components. In the following description, terms such as center, thickness, height, length, front, back, rear, left, right, top, bottom, upper, lower, and the like are used based on the orientation or positional relationship shown in the drawings. In particular, "height" corresponds to the dimension from top to bottom, "width" corresponds to the dimension from left to right, and "depth" corresponds to the dimension from front to back. These relative terms are for convenience of description and are not generally intended to require a particular orientation. Terms concerning attachments, coupling and the like (e.g., "connected" and "attached") refer to a relationship wherein structures are secured or attached, either directly or indirectly, to one another through intervening structures, as well as both movable or rigid attachments or relationships, unless expressly described otherwise.
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example one
The hydrolysis-resistant sealant for the proton membrane of the fuel cell comprises the following components:
component A: 100 parts by weight of active polydimethylsiloxane, wherein the end group of the polydimethylsiloxane is a hydroxyl group;
component B: 1 to 50 parts by weight of a silicone compound having an acryloyloxy group at one end;
component C: 10-100 parts by weight of a reactive diluent;
component D: 0.01 to 15 parts by weight of a crosslinking agent;
component E: 0.01 to 0.8 part by weight of at least one platinum catalyst.
Wherein the component A has a molecular formula shown as (I).
R1 2Si(OH)O(R1 2SiO)pSiR1 2(OH) (Ⅰ)
And R1 is an alkyl group or aryl group having 1 to 10 carbon atoms, or the like. m has a value of between 20 and 1500, preferably between 600 and 1200. The viscosity of component A is 20000-50000 mPas at 25 ℃. Component A can be prepared by chemical methods, such as by hydrolysis of organosiloxanes.
The molecular formula of the component B is shown as (II).
R1(R2R3SiO)a(R4R5SiO)bSi(CH3)2UV (Ⅱ)
In the formula, R1Is an alkyl radical having from 1 to 10 carbon atoms, R2Is a compound containing an ether bond, i.e. C3H7OC4H9，R3、R4、R5Is an alkyl group containing 1 to 4 carbon atoms, U is bonded to Si, U is allyl (meth) acrylate, the end of which not bonded to V is C ═ C; v is an acryloyloxy group; a + b.ltoreq.3000, preferably a + B between 1200 and 2500, so that the viscosity of component B at 25 ℃ is between 20000 and 50000 mPas. The component B obtained by the method contains compatible and hydrolysis-resistant substituent groups at the siloxane structure so as to ensure high oxygen permeability and stability of the component B, and oxygen has better transmission performance in a fuel cell.
The component C can be silicone oil, and the viscosity of the silicone oil is 50-10,000 mPa.s at 25 ℃; in other embodiments, component C is a hydrocarbon compound including at least 8 to 18 carbon atoms and at least one site of aliphatic unsaturation, which may be linear or branched, and which may be pendant or terminal. If component C can be dodecene.
Component D is a crosslinking agent which is an organohydrogenpolysiloxane containing at least two Si-H groups in the molecule. Component E is a platinum catalyst, which may be any one or combination of platinum catalysts. As in some embodiments, the platinum catalyst is selected from the group consisting of SYL-OFF, available from Dupont DowTM4000 (f).
The sealant according to the present invention may further include one or more other additives such as adhesion promoter, filler, flame retardant, defoaming agent, etc. in addition to the above components.
In some embodiments, an inhibitor can be further added into the sealant, and the curing rate of the sealant is controlled by adding the inhibitor, so that the sealant is prevented from being cured too fast to influence the performance of the final product; the inhibitor may be in particular a silylated alkynol; preferably, the inhibitor is present in an amount of 0.1 to 3 parts by weight to ensure that the curing efficiency of the sealant is not too slow.
In some embodiments, an MQ resin is also included in the sealant composition, and the tackiness of the sealant is enhanced by the use of the MQ resin. The MQ resin is composed of monofunctional chain members R6SiO1/2Radical, tetrafunctional mer SiO4/2Group composition R6Is a monovalent radical having from 1 to 6 carbon atoms, R6SiO1/2Radical, SiO4/2The molar ratio of the groups is preferably 1:0.6 to 1:1, and when within this range, the MQ resin has better compatibility with silicone rubber and better cohesion.
Through continuous test and adjustment of the formula of the sealant, the sealant with stable viscosity, high cohesion, high continuous adhesion, good thermal shock performance, hydrolysis resistance, strong adsorbability, good tearing, no adhesive residue and good sealing performance is prepared.
The invention also relates to a preparation method of the sealant, which comprises the following steps:
mixing 100 parts by mass of active polydimethylsiloxane, 1-50 parts by mass of a siloxane compound with one end being an acryloyloxy group and 10-100 parts by mass of a reactive diluent, and uniformly stirring to obtain a base adhesive; adding 0.01-15 parts by weight of cross-linking agent and 0.01-0.8 part by weight of at least one platinum catalyst into the base rubber and uniformly mixing. And curing the mixed glue at 150 ℃ for 5 minutes to obtain the solvent-free sealant, wherein the sealant has better pressure sensitivity compared with other sealants, and when the sealant is made into a tape, the re-bonding of the tape after misapplication is facilitated.
Reference example:
mixing 100 parts by mass of active polydimethylsiloxane, 50 parts by mass of a siloxane compound with one end being an acryloyloxy group and 50 parts by mass of a reactive diluent, and uniformly stirring to obtain a base rubber; to the base rubber, 10 parts by weight of a crosslinking agent and 0.4 part by weight of a platinum catalyst were added and mixed. The mixed glue was cured at 150 ℃ for 5 minutes to obtain a solvent-free sealant.
Comparative example 1: mixing 100 parts by mass of active polydimethylsiloxane and 50 parts by weight of reactive diluent, and uniformly stirring to obtain base rubber; to the base rubber, 10 parts by weight of a crosslinking agent and 0.4 part by weight of a platinum catalyst were added and mixed. The mixed glue was cured at 150 ℃ for 5 minutes to obtain a solvent-free sealant.
Comparative example 2:
mixing 100 parts by mass of active polydimethylsiloxane, 50 parts by mass of acrylic pressure-sensitive adhesive and 50 parts by mass of reactive diluent, and uniformly stirring to obtain base adhesive; to the base rubber, 10 parts by weight of a crosslinking agent and 0.4 part by weight of a platinum catalyst were added and mixed. The mixed glue was cured at 150 ℃ for 5 minutes to obtain a solvent-free sealant.
Comparative example 3:
mixing 100 parts by mass of active polydimethylsiloxane, 50 parts by mass of an anti-hydrolysis agent PU811F (chemical name: N, N' -bis (2, 6-diisopropylphenyl) carbodiimide) and 50 parts by mass of a reactive diluent, and uniformly stirring to obtain a base adhesive; to the base rubber, 10 parts by weight of a crosslinking agent and 0.4 part by weight of a platinum catalyst were added and mixed. The mixed glue was cured at 150 ℃ for 5 minutes to obtain a solvent-free sealant.
The relevant test methods are as follows:
1) initial tack test: selecting a 6032 adhesive tape retention tester (MIDEL KJ-6032, detection instrument Co., Ltd. of Dongguan), testing according to GB/T4852-2002, and using a ball number to represent the initial adhesion;
2) viscosity retention: selecting a temperature type adhesive tape retention force testing machine (MIDEL KJ-6012, Kokai detection instrument Co., Ltd. of Dongguan), testing according to GB/T4851-2014, and calculating the permanent adhesive force according to the time of adhesive tape shearing damage and falling;
3)180 ° peel strength: selecting a computer type tensile testing machine (MIDEL KJ-1065A, detection instrument Co., Ltd. of Dongguan city), and testing according to GB/T2792-2014;
4) high-temperature permanent adhesion: selecting a temperature type adhesive tape retention force testing machine (MIDEL KJ-6012, detection instrument Co., Ltd. of Dongguan), and performing a permanent adhesion force test at 100 ℃ to evaluate the high temperature resistance of the pressure sensitive adhesive tape;
5) hydrolysis resistance: uniformly coating the obtained sealant on a uniform surface, such as a PEN film, standing at 85 ℃ and 85% relative humidity, and observing whether cracks or wrinkles appear on the rubber surface or whether watermark residues exist.
Table 1 table of performance test results for different sealants
Figure BDA0002900646950000071
Figure BDA0002900646950000081
Example two
A sealing film 1 comprises a substrate layer 13, and an adhesive layer 12 and a release film layer 11 which are sequentially arranged on the substrate layer 13; the adhesive layer 12 is formed by mixing, coating and baking the materials of the components in the sealant in the first embodiment.
As shown in fig. 1, a sealing film 1 for a fuel cell membrane electrode comprises a substrate layer 13, and an adhesive layer 12 and a release film layer 11 which are sequentially arranged on the substrate layer 13; wherein the composition for forming the adhesive layer 12 includes a siloxane compound having an acryloxy group at one end; when the sealing film is used, the release film layer 11 needs to be removed, and the adhesive layer 12 is attached to the membrane electrode of the fuel cell, so as to form a sealing structure around the membrane electrode.
The base material layer 13 is used to support the adhesive layer 12, and generally has an antistatic function. The substrate layer may be a PEN (polyethylene naphthalate) film, a PET (polyethylene terephthalate) film, a PI (polyimide) film, or the like, and preferably, the substrate layer 13 is a PEN film because the PEN film has advantages in mechanical properties, high temperature resistance, gas barrier, environmental protection, and hydrolysis resistance. The shape of substrate layer 13 can set up wantonly, and for the convenience of the transportation of final seal membrane 1, substrate layer 13 sets up to microscler to the curling of substrate layer 13 becomes similar to circular sticky tape form, convenient storage and transportation.
The composition for forming the adhesive layer 12 includes at least a siloxane compound having an acryloxy group at one end to improve the overall hydrolysis resistance of the adhesive layer 12. The size (profile) of the adhesive layer 12 does not exceed the size (profile) of the base material layer 13, the shape of the adhesive layer 12 can be set arbitrarily, the shape of the adhesive layer 12 can be the same as or different from the shape of the base material layer 13, and only care needs to be taken that the outer contour of the adhesive layer 12 does not exceed the profile of the base material layer 13.
The size and the outline of the release film layer 11 are consistent with those of the substrate layer 13, and on one hand, the release film layer 11 can form a sealing film with the adhesive layer 12 and the substrate layer 13 under the action of pressure; on the other hand, the release film layer 11 can be easily separated from the adhesive layer 12 and/or the substrate layer 13 by an external force.
In some embodiments, the adhesive layer 12 has a thickness of between 12 μm and 188 μm; preferably, the thickness of the adhesive layer is 13 μm to ensure that the thickness of the film formed after the adhesive layer is adhered to the proton exchange membrane is moderate. And this substrate layer 13, the thickness of leaving type rete 11 are 50 mu m to make substrate layer 13, adhesive layer 12, the seal membrane that forms from type rete 11 have moderate thickness, can keep good result of use when using, can conveniently curl again and form circular sticky tape so that transportation, storage.
In some embodiments, a high temperature resistant layer (not shown) is further included, and the high temperature resistant layer is disposed between the substrate layer 13 and the adhesive layer 12 to ensure that the sealing film has good high temperature resistance during use.
In some embodiments, the area of the substrate layer 13 near the peripheral edge further includes a number of first through holes (not shown); the area of the contact surface between the adhesive layer 12 and the substrate layer 13, which is close to the peripheral edge of the adhesive layer 12, comprises at least one second through hole communicated with the first through hole. Preferably, the more the number of the second through holes is with respect to the first through holes, the more the discharge of the gas is facilitated. In the actual process coating, the adhesive layer 12 is coated while avoiding the first through hole, and in particular, the coating may be performed intermittently. When the base material layer 13 is square, a through hole may be provided at four sides of the square away from the center.
It should be understood that the reason why the first through hole and the second through hole are disposed at the edges of the substrate layer 13 and the adhesive layer 12 is that when the sealing film 1 is used, the substrate layer 13 and the adhesive layer 12 together form a tape mainly used for sealing the periphery of the fuel cell, i.e. the sealing film 1 to be finally used needs to be cut off the middle part of the sealing film 1 by a film cutting machine or the like to form a hollow sealing film; specifically, a square sealing membrane 1 is cut off in the square sealing membrane 1 according to the size of the proton membrane of the fuel cell, so that the cut hollow sealing membrane 1 can be attached to the periphery of the proton membrane of the fuel cell, and the hollow part can be used for proton exchange.
In some embodiments, the first through holes and the second through holes have a contour that is consistent, so that when the adhesive layer 12 is attached to the substrate layer 13, the second through holes on the adhesive layer 12 and the first through holes on the substrate layer 13 are completely overlapped, so as to facilitate the discharge of the gas.
In other embodiments, the shapes of the first through hole and the second through hole can be set arbitrarily, and preferably, the outline of the second through hole is larger than or equal to the outline of the first through hole. Specifically, when the first through hole and the second through hole are circular, the diameter of the second through hole is larger than or equal to that of the first through hole, and at this time, during actual bonding, the adhesive layer 12 can more easily close the first through hole, so as to ensure that when the sealing film 1 is bonded to the membrane electrode in actual use, the membrane electrode of the fuel cell and the sealing film 1 have better sealing performance.
It will be appreciated that in some embodiments the number of first through holes corresponds to the number of second through holes to ensure the escape of gas and to ensure a good sealing of the sealing membrane during use.
In some embodiments, the release film layer 11 is further printed with at least one shape or pattern, which can be used to beautify the appearance of the release film on one hand, and can be used as a mark to indicate to a user to remove the release film layer 11 on the other hand.
In some embodiments, the adhesive layer 12 further includes a protrusion (not shown), the protrusion is located between the substrate layer 13 and the release film layer 11, and the protrusion and the gap between the substrate layer 13 and the release film layer 11 together form a receiving area of the adhesive layer 12. Specifically, the protrusion and the substrate layer are integrally formed or assembled, and when integrally formed, the formed substrate layer is conveniently and quickly produced so as to facilitate the direct application of the glue coating process; when selecting the assembly molding, can choose the arch of different thickness to install on substrate layer 13 for the thickness of the gluey of final requirement, this installation is including fixed modes such as bonding. At this moment, after guaranteeing that the arch is located the substrate layer 13 and from type rete 11, control spreading machine is glued on the substrate layer 13 at arch place, and the back is accomplished in the glueing, utilizes the round brush to roll the substrate layer 13 side at arch place to make protruding surperficial glue scraped or rolled to bellied edge all around by the round brush, after the stoving cooling, should be from the shape of the adhesive layer 12 between type rete 11 and the substrate layer 13 and be the shape of the required frame sticky tape of fuel cell promptly.
EXAMPLE III
A method of preparing a sealing film for a fuel cell membrane electrode of example 1 comprising the steps of: and coating the adhesive layer 12 and the release film layer 11 on the substrate layer 13 in sequence, and then baking and cooling to obtain the sealing film 1 for the fuel cell membrane electrode.
When the coating is specifically implemented, multiple coating processes (roll coating, spray coating, spot coating and the like) are combined, and the obtained product has the advantages of one-step coating forming, thousands of levels of dust-free environments, precise curing temperature control, precise glue thickness control (reaching 0.0001mm), controllable foot surface and anti-static property, and the product cleanliness reaching 100%.
In some embodiments, the method comprises the steps of:
the first step is as follows: mixing 100 parts by mass of active polydimethylsiloxane, 50 parts by mass of a siloxane compound with one end being an acryloyloxy group and 50 parts by mass of a reactive diluent, and uniformly stirring to obtain a base rubber; to the base rubber, 10 parts by weight of a crosslinking agent and 0.4 part by weight of a platinum catalyst were added and mixed.
The second step is that: uniformly coating the mixed glue on the substrate layer 13 which is placed flatly;
the third step: baking the mixed glue in the second step to form a glue layer 12;
the fourth step: attaching a release film layer 11 to the adhesive layer 12 formed in the third step to form a sealing film 1;
the fifth step: and rolling the sealing film 1.
When the prepared sealing film is used specifically, the size of a sealing adhesive tape required by a fuel cell proton film frame required by the cell needs to be determined according to the specific model of the fuel cell, the sealing film 1 is cut by a film cutting machine according to the size so that the shape of the cut sealing film is matched with that of the fuel cell proton film frame, and after the release film layer 13 is removed, the adhesive layer 12 is attached to the peripheral frame of the fuel cell proton film according to the fuel cell proton film frame.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of adaptation of the invention, and further modifications can be easily implemented by those skilled in the art, so that the invention is not limited to the specific details and the examples shown herein, without departing from the general concept defined by the claims and the scope of equivalents.

Claims (10)

1. A hydrolysis-resistant sealant for a proton membrane of a fuel cell, said sealant comprising a composition comprising:
100 parts by weight of active polydimethylsiloxane, wherein the end group of the polydimethylsiloxane is a hydroxyl group;
1 to 50 parts by weight of a silicone compound having an acryloyloxy group at one end;
10-100 parts by weight of a reactive diluent;
0.01 to 15 parts by weight of a crosslinking agent;
0.01 to 0.8 part by weight of at least one platinum catalyst.
2. The hydrolysis resistant sealant for a fuel cell proton membrane as claimed in claim 1, wherein said acryloxy terminated siloxane compound has the formula:
R1(R2R3SiO)a(R4R5SiO)bSi(CH3)2UV
wherein R is1Is an alkyl radical having from 1 to 10 carbon atoms, R2Is a compound containing an ether bond, i.e. C3H7OC4H9，R3、R4、R5Is an alkyl group containing 1 to 4 carbon atoms, U is bonded to Si, U is allyl (meth) acrylate, the end of which not bonded to V is C ═ C; v is an acryloyloxy group; a + b is less than or equal to 3000.
3. The hydrolysis resistant sealant for a fuel cell proton membrane as claimed in claim 1, wherein said hydroxyl terminated organosiloxane polymer has a viscosity in the range of 20000-50000mpa.s at 25 ℃.
4. The solvent-free sealant for a fuel cell proton membrane according to claim 1 further comprising 0.1 to 3 parts by weight of an inhibitor.
5. The hydrolysis resistant sealant for a fuel cell proton membrane as claimed in claim 4 wherein said inhibitor is at least one silylated alkynol.
6. The hydrolysis resistant sealant for a fuel cell proton membrane as claimed in claim 1, further comprising 1 to 50 parts by mass of MQ resin.
7. The solvent-free pressure-sensitive adhesive for fuel cell proton membranes of claim 6 wherein said MQ resin is composed of monofunctional mer R6SiO1/2Radical, tetrafunctional mer SiO4/2The group consisting of6SiO1/2Radical, SiO4/2The molar ratio of the groups is 1:0.6-1: 1.
8. The hydrolysis resistant sealant for a fuel cell proton membrane as claimed in claim 1 wherein said reactive diluent is dodecene.
9. The hydrolysis resistant sealant for a fuel cell proton membrane as claimed in claim 1, wherein said crosslinking agent is an organohydrogenpolysiloxane containing at least two Si-H groups.
10. A sealing film is characterized by comprising a substrate layer, and an adhesive layer and a release film layer which are sequentially arranged on the substrate layer; wherein the adhesive layer is prepared by mixing, coating and baking the materials of each component in the sealant as claimed in claim 1.
CN202110056042.7A 2021-01-15 2021-01-15 Hydrolysis-resistant sealant for proton membrane of fuel cell, and sealing membrane Pending CN112877027A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524589A (en) * 2016-01-18 2016-04-27 矽时代材料科技股份有限公司 LOCA (Liquid Optical Clear Adhesive) and preparation method thereof
US20170226392A1 (en) * 2016-02-09 2017-08-10 GM Global Technology Operations LLC Seal material with latent adhesive properties and a method of sealing fuel cell components with same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105524589A (en) * 2016-01-18 2016-04-27 矽时代材料科技股份有限公司 LOCA (Liquid Optical Clear Adhesive) and preparation method thereof
US20170226392A1 (en) * 2016-02-09 2017-08-10 GM Global Technology Operations LLC Seal material with latent adhesive properties and a method of sealing fuel cell components with same

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