CN109233715A - The double-component epoxy adhesive and preparation method thereof of resistance to lithium-ion battery electrolytes - Google Patents
The double-component epoxy adhesive and preparation method thereof of resistance to lithium-ion battery electrolytes Download PDFInfo
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- CN109233715A CN109233715A CN201811018356.2A CN201811018356A CN109233715A CN 109233715 A CN109233715 A CN 109233715A CN 201811018356 A CN201811018356 A CN 201811018356A CN 109233715 A CN109233715 A CN 109233715A
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of double-component epoxy adhesives and preparation method thereof of resistance to lithium-ion battery electrolytes, the adhesive is mixed by component A and B component 2:1 in mass ratio, wherein, component A is made of following raw material by weight: 40~60 parts of bisphenol A type epoxy resin, 10~25 parts of polyurethane-modified bisphenol A epoxide resin, 1~4 part of coupling agent, 2~8 parts of reactive diluent, 15~35 parts of filler, B component is made of following raw material by weight: 50~70 parts of modified amine curing agent, 2~8 parts of fatty amines curing agent, 0~2 part of imidazole curing agent, 1~3 part of promotor, 20~40 parts of filler.The double-component epoxy adhesive of the invention performance in electrolyte environment is stablized, with excellent resistance to lithium-ion battery electrolytes corrosivity, it is able to maintain higher intensity in electrolyte environment, can be applied in lithium ion battery manufacture process be exposed to the bonding and sealing of electrolyte environment lower component.
Description
Technical field
The present invention relates to field of adhesive technology, are to be related to a kind of pair of resistance to lithium-ion battery electrolytes more specifically
Component epoxy adhesive and preparation method thereof.
Background technique
With the development of society, chargeable secondary lithium battery is because having, energy density is high, operating voltage is high, circulation
Service life length, memory-less effect, environmentally protective and size shape size can according to actual needs flexible design many advantages, such as, got over
Power supply, especially mobile appliance equipment, energy storage station and new-energy automobile etc. are selected as come more electrical equipments.Wide application neck
Domain pushes lithium ion battery in fast development always.The research of positive and negative pole material is carrying out always, and electrolyte is from liquid electrolytic
Matter is to solid electrolyte developmental research, cylinder and square battery of the battery external form from typical case with hard shell, to the flat plate cell of Soft Roll
And laminated batteries；The patent (CN105826612A) of entitled " a kind of edge bonding method of serondary lithium battery " more proposes a kind of different
The edge bonding method of the battery of property, applies 3D printing technique, the structure that can more make the design of battery no longer adhere closely to the regulation.City
Pursuit to application performance and the higher lithium battery of security performance promotes lithium battery series of new techniques, new equipment and newly
The exploitation of system, more efficient battery manufacturing process is also developing together and is applying, therefore all kinds of materials in lithium battery manufacturing process
The bonding of material and sealing also have more diversified demand.
In lithium battery manufacturing process, it is Nian Jie that the bonding of various types of materials, which needs the one of main problem solved with sealing,
The performance for sealing material needing that there are resistance to lithium-ion battery electrolytes.Electrolyte as lithium ion battery core component it
One, battery major part element can be touched, main component includes lithium hexafluoro phosphate, ethylene carbonate, diethyl carbonate, carbonic acid
Dimethyl ester and methyl ethyl carbonate etc..Lithium-ion battery electrolytes have etching characteristic.Currently used resistance to lithium-ion electrolyte
Adhesives is rubber/polyacrylic double-sided pressure-sensitive adhesive tape, but adhesion strength, high temperature bond performance and weather resistance have
Limit, is not able to satisfy diversified application demand.
The patent (CN104245872A) of entitled " heat sealing adhesive for electric installation " discloses a kind of with excellent
Different resistance to battery electrolyte performance heat sealing adhesive, can be used for the sealing of lithium battery electrolytes packaging material.But for work
The application of the higher environment of temperature, heat sealing adhesive is obviously limited with security performance.It is entitled " a kind of lithium battery room temperature without
It is inviscid close that the patent (CN104559846A) of adhesive seal adhesive and preparation method thereof " discloses a kind of lithium battery room temperature
Seal adhesive, it is inviscid to polypropylene based material under room temperature, it can produce adhesive property under 85 DEG C of high temperature and pressure.High temperature and pressure
Condition limit the application of the adhesive.Two above patent, the former the adhesive main component are improved polyalkene, after
Adhesive main component described in person is polyolefin copolymers, is limited to the adhesion principle and the cohesive force of itself of material, only
It can be used to seal, heavily stressed structural bond occasion can not be applied to.
To adapt to be widely applied demand, while meeting the application demand of sealing and structural bond, research people of the invention
Member is studied for the adhesive of epoxy-resin systems.Epoxy resin have good bonding, corrosion-resistant, electrical apparatus insulation,
The performances such as high intensity, have a wide range of applications.Toughening and high temperature resistance are concentrated mainly on to the research of epoxy adhesive at present
Aspect, the corrosion resistance based on epoxy resin itself, researcher of the invention is the study found that variety classes and modified ring
Oxygen resin cooperates, and can keep other superperformances, while having excellent resistance to lithium-ion battery electrolytes performance.
The patent of entitled " the filling polymer composition of lithium ion battery, packaging process and lithium battery and application "
(CN103872276A) disclose a kind of filling polymer composition of lithium battery, can be used epoxy resin be as main ingredient,
Electrolyte, which is reinjected, after filling to the combination progress of naked battery core monomer obtains lithium battery monomer or component.
The patent (CN103333629B) of entitled " energy storage, the dedicated adhesive tape of dynamic lithium battery and its production method " is open
A kind of energy storage, dynamic lithium battery dedicated adhesive tape, which is PP type pressure with the gluing oxidant layer that electrolyte directly contacts
Quick glue is epoxy cure coating under gluing oxidant layer, base's puncture strength can be improved.
The patent of entitled " a kind of soft package lithium battery anti-corrosion protective film and its preparation method and application "
(CN105244455A) a kind of soft package lithium battery anti-corrosion protective film is disclosed, main component is arranged in pairs or groups for epoxy resin, and other are set
Rouge, the protective film is for providing the protection of anti-electrolytic corrosion in Production Process of Lithium Battery for lithium battery wicking surface.
The patent (CN104979581A) of entitled " capsule and lithium ion battery " disclose one kind can be contained in lithium from
Capsule in sub- battery, the capsule are used to improve the security performance of lithium ion battery.Capsule-wall material is gelatin, Arab
One or more of glue, sodium alginate, polyureas, polyamide, polyacrylamide, polyurethane and epoxy resin, fusing point 90
DEG C~160 DEG C and the electrolyte insoluble in lithium ion battery.
Document above applies the corrosion resistant performance of epoxy resin, in addition in patent " capsule and lithium ion battery "
Material outside, epoxide resin material applied by remaining each patent and electrolyte there is no direct long term contact, epoxy resin
Adhesive property does not deeply develop.
The patent of entitled " a kind of lithium battery flexible packaging epoxy adhesive and lithium battery flexible packaging material "
(CN102703010A) a kind of lithium battery flexible packaging epoxy adhesive is disclosed, aluminium foil layer (the surface warp for packaging material
Chromium scoria processing) with the high-strength composite of hot sealing layer, to improve the barrier property and electrolyte resistance of lithium battery Soft Roll material
Energy.The packaging material interlayer that the epoxy adhesive of the patent is applied to lithium battery is bonded, but has no directly contact electrolyte, cannot
Illustrate that adhesive itself has enough electrolyte resistance performances.
The patent (CN205657098U) of entitled " ceramic seal battery " discloses a kind of ceramic seal battery, wherein making pottery
Ceramic seal glue is provided between porcelain sealing ring and electrode column and between ceramic-seal ring and cover board.In the embodiment of the patent
In directly used market now to sell sealant product, main component epoxy resin, thermoplastic resin, silicone, polyurethane/phenol
One or more of aldehyde-acetal resin.One of which selection of the epoxide resin material as sealant raw material herein, only
The application of epoxy resin traditional performance can not embody the performance of its electrolyte resistance.
The patent (CN105885753A) of entitled " a kind of lithium metal battery insulative glue and preparation method thereof " is open
One kind is based on epoxy resin, the glue for other resins such as organic siliconresin and butyronitrile resin of arranging in pairs or groups, for substituting traditional lithium
The adhesive tape of positive/negative plate short circuit is prevented in ion battery manufacturing process.The glue have the characteristics that thermal conductivity it is good with it is corrosion-resistant, answer
It is sealing and electric insulation with point, adhesive strength is not enough.
In summary the different performance of each patent document, epoxy resin is applied in lithium ion battery industry, but answers
It is more single with occasion, not by properties integrated application and development.With the development of lithium-ion electric pool process, all kinds of sealings
Use glue demand with structural bond can be more and more, it is therefore desirable to can satisfy various close under the electrolyte environment of lithium ion battery
The adhesive of envelope and structural bond demand.
Summary of the invention
It is an object of the invention to overcome drawbacks described above in the prior art, a kind of resistance to lithium-ion battery electrolytes are provided
Double-component epoxy adhesive and preparation method thereof, performance is stablized in lithium-ion battery electrolytes environment, possesses excellent resistance to
Lithium-ion battery electrolytes corrosivity, heat resistance and electrochemical stability are able to maintain higher intensity in electrolyte environment.
To achieve the above object, the first aspect of the present invention provides a kind of two-component ring of resistance to lithium-ion battery electrolytes
Oxygen adhesive, the adhesive are mixed by component A and B component 2:1 in mass ratio, wherein component A is by weight by following original
Material composition: 40~60 parts of bisphenol A type epoxy resin, 10~25 parts of polyurethane-modified bisphenol A epoxide resin, 1~4 part of coupling agent,
2~8 parts of reactive diluent, 15~35 parts of filler, B component is made of following raw material by weight: modified amine curing agent 50~
70 parts, 2~8 parts of fatty amines curing agent, 0~2 part of imidazole curing agent, 1~3 part of promotor, 20~40 parts of filler.
Preferably, the bisphenol A type epoxy resin be one of epoxy resin E54, E51, E44 and E42 or its
Combination.
Preferably, the polyurethane-modified bisphenol A epoxide resin by polyether polyol, 2,2- dihydromethyl propionic acid,
P-methyl benzenesulfonic acid, Toluene-2,4-diisocyanate, 4- diisocyanate, bisphenol A type epoxy resin E51, two fourth of acetone, polymerization inhibitor and tin dilaurate
Ji Xi is made.
Preferably, the molecular weight of the polyether polyol, between 500~2000, average functionality is 2~3, ether
Chain is at least one of ethylene oxide, propylene oxide and epoxy butane.
Preferably, the coupling agent is silane coupling agent, the silane coupling agent is γ-aminopropyl trimethoxy silicon
Alkane, γ-(2,3- glycidoxy) propyl trimethoxy silicane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 3-
Mercaptopropyltriethoxysilane, 3- mercaptopropyl trimethoxysilane, 3- urea propyl trimethoxy silicane, 3- urea propyl triethoxy
One of silane or combinations thereof.
Preferably, to be that 1,4-butanediol diglycidyl ether, 1,6- hexylene glycol two shrink sweet for the reactive diluent
One of oily ether, butyl glycidyl ether or combinations thereof.
Preferably, the promotor is 2,4,6- tri- (dimethylamino methyl) phenol.
Preferably, the filler is heavy calcium carbonate superfine powder, activated Calcium carbonate or combinations thereof.
The second aspect of the present invention provides a kind of preparation of the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes
Method, comprising the following steps:
The preparation of component A:
Step a1, bisphenol A type epoxy resin, polyurethane-modified bisphenol A epoxide resin, coupling agent and reactive diluent are pressed
Ratio is added in blender and is uniformly mixed；
Step a2, filler is added in the mixture that step a1 is obtained, dispersion stirs evenly under vacuum, obtains component A；
The preparation of B component:
Step b1, modified amine curing agent, fatty amines curing agent, imidazole curing agent and promotor are proportionally added into
It is uniformly mixed in blender；
Step b2, filler is added in the mixture that step b1 is obtained, dispersion stirs evenly under vacuum, obtains B component；
Component A and B component 2:1 in mass ratio are uniformly mixed, mixed proportion error ± 10% can be prepared by resistance to lithium ion
The double-component epoxy adhesive of battery electrolyte.
Preferably, the preparation method of the polyurethane-modified bisphenol A type epoxy resin the following steps are included:
(1) reaction kettle is added in polyether polyol, 2,2- dihydromethyl propionic acid, p-methyl benzenesulfonic acid, while stirring by kettle
Temperature rise is reacted 2~3 hours to 135~145 DEG C, and then the lower reaction of vacuum distillation is 9mg/g KOH hereinafter, cooling purifying to acid value
After obtain superbrnaching end-hydroxy polyether type polyester；
(2) by Toluene-2,4-diisocyanate, 4- diisocyanate, bisphenol A type epoxy resin E51, two fourth of acetone, polymerization inhibitor and tin dilaurate
Another reaction kettle is added in Ji Xi, measures initial nco value, and after normal-temperature reaction 2~4 hours, being warming up to 45~55 DEG C, the reaction was continued, until
Nco value stops when being initial value half, is cooled to room temperature；
(3) second step reaction kettle is added in superbrnaching end-hydroxy polyether type polyester obtained by step (1), while adds two laurels
Sour dibutyl tin, be warming up to 50~55 DEG C of reactions to NCO mass content lower than 0.1% when, vacuum outgas obtains polyurethane-modified
Bisphenol A type epoxy resin.
Compared with prior art, the beneficial effects of the present invention are:
The two-component epoxy resin adhesive of the invention performance in lithium-ion battery electrolytes environment is stablized, and possesses excellent
Resistance to lithium-ion battery electrolytes corrosivity, heat resistance, electrochemical stability is able to maintain higher strong in electrolyte environment
Degree can be applied in lithium ion battery manufacture process be exposed to electrolyte environment lower component bonding and sealing, meet lithium battery system
Make the diversified demand of industry glue.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The preparation of polyurethane-modified bisphenol A type epoxy resin B1:
In 500 milliliters of the glass four-hole boiling flask equipped with blender, thermometer and condenser pipe, polyether polyol is added
93 grams of VORANOL 2070 (Dow Chemical, average molecular weight 700, degree of functionality 3, intermediate molecular weight triol), 2,2- bis-
375 grams of hydroxymethyl propionic acid, 0.47 gram of p-methyl benzenesulfonic acid, kettle temperature is risen to 142 DEG C under stirring and is reacted 2 hours, then decompression is steamed
Evaporating lower reaction to acid value is 9mg/g KOH hereinafter, cooling obtains superbrnaching end-hydroxy polyether type polyester A1 after purification.
In the glass four-hole boiling flask of 500 milliliters of the clean dried equipped with blender, thermometer and condenser pipe, it is added
140 grams of Toluene-2,4-diisocyanates, 4- diisocyanate, 178 grams of E51,0.25 gram of hydroquinone and 0.3 gram of dibutyl tin dilaurate, 125 millis
The acetone risen, measures initial nco value, and after normal-temperature reaction 3 hours, being warming up to 48 DEG C, the reaction was continued, until nco value is initial value half
When stop, being cooled to room temperature；96 grams of superbrnaching end-hydroxy polyether type polyester A1 and 0.15 gram of dibutyl tin dilaurate are added, rise
When temperature to 52 DEG C of reactions to NCO mass content is lower than 0.1%, vacuum outgas obtains polyurethane-modified bisphenol A type epoxy resin
B1。
The preparation of the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes:
(1) in planet stirred tank, 54 parts by weight of E51 epoxy resin, polyurethane-modified bisphenol A type epoxy resin B1 is added
For 18 parts by weight, 1.5 parts by weight of γ-(2,3- glycidoxy) propyl trimethoxy silicane, 1,4-butanediol 2-glycidyl
3.6 parts by weight of ether stir 10min with 45rpm revolving speed.
(2) 22 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain component A.
(3) in planet stirred tank, 60 parts by weight of modified amine curing agent, 5 parts by weight of fatty amines curing agent, miaow is added
1 parts by weight of azole curing agent, 2,4,6- tri- (dimethylamino methyl) phenol, 1.5 parts by weight stir 10min with 45rpm revolving speed.
(4) 35 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain B component.
(5) above-mentioned A, B component are uniformly mixed at room temperature with the ratio of mass ratio 2:1, mixed proportion error ± 10%,
It is tested.
Embodiment 2
The preparation of polyurethane-modified bisphenol A type epoxy resin B2:
In 500 milliliters of the glass four-hole boiling flask equipped with blender, thermometer and condenser pipe, polyether polyol is added
200 grams of VORANOL 2120 (Dow Chemical, average molecular weight 2000, degree of functionality 2, polypropylene glycol), 2,2- dihydroxy first
187.5 grams of base propionic acid, 0.39 gram of p-methyl benzenesulfonic acid, kettle temperature is risen to 145 DEG C under stirring and is reacted 2.5 hours, then decompression is steamed
Evaporating lower reaction to acid value is 9mg/g KOH hereinafter, cooling obtains superbrnaching end-hydroxy polyether type polyester A2 after purification.
In the glass four-hole boiling flask of 500 milliliters of the clean dried equipped with blender, thermometer and condenser pipe, it is added
140 grams of Toluene-2,4-diisocyanates, 4- diisocyanate, 178 grams of E51,0.3 gram of p-hydroxyanisole and 0.3 gram of dibutyl tin dilaurate,
150 milliliters of acetone measures initial nco value, and after normal-temperature reaction 2 hours, being warming up to 55 DEG C, the reaction was continued, until nco value is initial
Stop when value half, is cooled to room temperature；148 grams of superbrnaching end-hydroxy polyether type polyester A2 and 0.1 gram of two fourth of tin dilaurate are added
Ji Xi, be warming up to 55 DEG C of reactions to NCO mass content lower than 0.1% when, vacuum outgas obtains polyurethane-modified bisphenol-A type ring
Oxygen resin B 2.
The preparation of the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes:
(1) in planet stirred tank, 40 parts by weight of E51 epoxy resin are added, polyurethane-modified bisphenol A epoxide resin B2 is
10 parts by weight, 1 parts by weight of γ-(2,3- glycidoxy) propyl trimethoxy silicane, 2 weight of 1,4-butanediol diglycidyl ether
Part is measured, 10min is stirred with 45rpm revolving speed.
(2) 15 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain component A.
(3) in planet stirred tank, addition 50 parts by weight of modified amine curing agent, 2 parts by weight of fatty amines curing agent, 2,
4,6- tri- (dimethylamino methyl) phenol, 1 parts by weight stir 10min with 45rpm revolving speed.
(4) 20 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain B component.
(5) above-mentioned A, B component are uniformly mixed at room temperature with the ratio of mass ratio 2:1, mixed proportion error ± 10%,
It is tested.
Embodiment 3
The preparation of polyurethane-modified bisphenol A type epoxy resin B3:
In 500 milliliters of the glass four-hole boiling flask equipped with blender, thermometer and condenser pipe, polyether polyol is added
200 grams of VORANOL 222-056 (Dow Chemical, average molecular weight 2000, degree of functionality 2, polyethylene glycol), 2,2- dihydroxies
187.5 grams of methylpropanoic acid, 0.39 gram of p-methyl benzenesulfonic acid, kettle temperature is risen to 135 DEG C under stirring and is reacted 3 hours, then decompression is steamed
Evaporating lower reaction to acid value is 9mg/g KOH hereinafter, cooling obtains superbrnaching end-hydroxy polyether type polyester A3 after purification.
In the glass four-hole boiling flask of 500 milliliters of the clean dried equipped with blender, thermometer and condenser pipe, it is added
140 grams of Toluene-2,4-diisocyanates, 4- diisocyanate, 178 grams of E51,0.25 gram of hydroquinone and 0.25 gram of dibutyl tin dilaurate, 150
The acetone of milliliter, measures initial nco value, and after normal-temperature reaction 4 hours, being warming up to 45 DEG C, the reaction was continued, until nco value is initial value one
Stop when half, is cooled to room temperature；145 grams of superbrnaching end-hydroxy polyether type polyester A3 and 0.2 gram of dibutyl tin dilaurate are added,
Be warming up to 50 DEG C of reactions to NCO mass content lower than 0.1% when, vacuum outgas obtains polyurethane-modified bisphenol A type epoxy resin
B3。
The preparation of the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes:
(1) in planet stirred tank, 60 parts by weight of E51 epoxy resin are added, polyurethane-modified bisphenol A epoxide resin B3 is
25 parts by weight, 4 parts by weight of γ-(2,3- glycidoxy) propyl trimethoxy silicane, 8 weight of 1,4-butanediol diglycidyl ether
Part is measured, 10min is stirred with 45rpm revolving speed.
(2) 35 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain component A.
(3) in planet stirred tank, 70 parts by weight of modified amine curing agent, 8 parts by weight of fatty amines curing agent, miaow is added
2 parts by weight of azole curing agent, 2,4,6- tri- (dimethylamino methyl) phenol, 3 parts by weight stir 10min with 45rpm revolving speed.
(4) 40 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain B component.
(5) above-mentioned A, B component are uniformly mixed at room temperature with the ratio of mass ratio 2:1, mixed proportion error ± 10%,
It is tested.
Comparative example:
(1) 60 parts by weight of E51 epoxy resin, 2 weight of γ-(2,3- glycidoxy) propyl trimethoxy silicane is added
Part, 10min is stirred with 45rpm revolving speed.
(2) 20 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain component A.
(3) in planet stirred tank, 60 parts by weight of modified amine curing agent, 2,4,6- tri- (dimethylamino methyl) benzene are added
1 parts by weight of phenol stir 10min with 45rpm revolving speed.
(4) 20 parts by weight of activated Calcium carbonate are added, in 0.090Mpa vacuum degree with 45rpm mixing speed and 2000rpm points
It dissipates and is dispersed with stirring under speed, obtain B component.
(5) above-mentioned A, B component are uniformly mixed at room temperature with the ratio of mass ratio 2:1, mixed proportion error ± 10%,
It is tested.
By the following method testing example 1~3, electrolyte impregnates the hardness of front and back two-component epoxy glue, draws in comparative example
Stretch shear bond strength and change rate.According to GB/T 2411-2008, " plastics and hard rubber use hardometer measurement impression to hardness
Hardness (shore hardness) " test.Tensile shear strength is according to the GB/T 7124-2008 " measurement of adhesive tensile shear strength
(rigid material is to rigid material) " test.Test electrolyte used is lithium hexafluorophosphate electrolyte solution, and electrolyte is impregnated in test piece
Test condition are as follows: impregnated 7 days at 60 DEG C.Test result is as shown in table 1:
The performance test results of 1 two-component epoxy glue of table
| Product type | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Appearance | Ecru | Ecru | Ecru | Ecru |
| Appearance after immersion electrolyte | Yellow | Yellow | Yellow | Yellow |
| Mass change after immersion electrolyte | 112% | 107% | 110% | 122% |
| Hardness (ShoreD) | 90 | 87 | 88 | 78 |
| Hardness (ShoreD) after immersion electrolyte | 87 | 85 | 85 | 60 |
| Firmness change rate after immersion electrolyte | - 3.3% | - 2.3% | - 3.4% | - 23.1% |
| Tensile shear strength | 11.0MPa | 10.8MPa | 13.3MPa | 7.9MPa |
| Impregnate electrolyte post-tensioning shear strength | 9.5MPa | 8.9MPa | 11.0MPa | 5.0MPa |
| Tensile shear strength change rate | - 13.6% | - 17.6% | - 17.2% | - 36.7% |
Seen from table 1, a kind of resistance to lithium-ion battery electrolytes two-component epoxy resin adhesive produced by the present invention, in electricity
It solves performance in pendular ring border to stablize, is resistant to lithium-ion battery electrolytes corrosion and intensity with higher.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of double-component epoxy adhesive of resistance to lithium-ion battery electrolytes, which is characterized in that the adhesive is by component A and B
Component 2:1 in mass ratio is mixed, wherein component A is made of following raw material by weight: bisphenol A type epoxy resin 40~
60 parts, 10~25 parts of polyurethane-modified bisphenol A epoxide resin, 1~4 part of coupling agent, 2~8 parts of reactive diluent, filler 15~35
Part, B component is made of following raw material by weight: 50~70 parts of modified amine curing agent, 2~8 parts of fatty amines curing agent, and miaow
0~2 part of azole curing agent, 1~3 part of promotor, 20~40 parts of filler.
2. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 1, which is characterized in that described
Bisphenol A type epoxy resin is one of epoxy resin E54, E51, E44 and E42 or combinations thereof.
3. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 1, which is characterized in that described
Polyurethane-modified bisphenol A epoxide resin is by polyether polyol, 2,2- dihydromethyl propionic acid, p-methyl benzenesulfonic acid, Toluene-2,4-diisocyanate, 4- bis-
Isocyanates, bisphenol A type epoxy resin E51, acetone, polymerization inhibitor and dibutyl tin dilaurate are made.
4. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 3, which is characterized in that described
The molecular weight of polyether polyol between 500~2000, average functionality be 2~3, ether chain be ethylene oxide, propylene oxide and
At least one of epoxy butane.
5. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 1, which is characterized in that described
Coupling agent is silane coupling agent, and the silane coupling agent is γ-aminopropyltrimethoxysilane, γ-(2,3- glycidoxy)
Propyl trimethoxy silicane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3- mercapto
One of propyl trimethoxy silicane, 3- urea propyl trimethoxy silicane, 3- urea propyl-triethoxysilicane or combinations thereof.
6. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 1, which is characterized in that described
Reactive diluent is 1,4- butanediol diglycidyl ether, in 1,6 hexanediol diglycidylether, butyl glycidyl ether
One kind or combinations thereof.
7. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 1, which is characterized in that described
Promotor is 2,4,6- tri- (dimethylamino methyl) phenol.
8. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 1, which is characterized in that described
Filler is heavy calcium carbonate superfine powder, activated Calcium carbonate or combinations thereof.
9. the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes as claimed in any of claims 1 to 8
Preparation method, which comprises the following steps:
The preparation of component A:
Step a1, in proportion by bisphenol A type epoxy resin, polyurethane-modified bisphenol A epoxide resin, coupling agent and reactive diluent
It is added in blender and is uniformly mixed；
Step a2, filler is added in the mixture that step a1 is obtained, dispersion stirs evenly under vacuum, obtains component A；
The preparation of B component:
Step b1, modified amine curing agent, fatty amines curing agent, imidazole curing agent and promotor are proportionally added into and are stirred
It mixes in machine and is uniformly mixed；
Step b2, filler is added in the mixture that step b1 is obtained, dispersion stirs evenly under vacuum, obtains B component；
Component A and B component 2:1 in mass ratio are uniformly mixed, mixed proportion error ± 10% can be prepared by resistance to lithium ion battery
The double-component epoxy adhesive of electrolyte.
10. the preparation method of the double-component epoxy adhesive of resistance to lithium-ion battery electrolytes according to claim 9, special
Sign is, the preparation method of the polyurethane-modified bisphenol A type epoxy resin the following steps are included:
(1) reaction kettle is added in polyether polyol, 2,2- dihydromethyl propionic acid, p-methyl benzenesulfonic acid, while stirring by kettle temperature liter
It is reacted 2~3 hours to 135~145 DEG C, being then evaporated under reduced pressure lower reaction to acid value is 9mg/g KOH hereinafter, cooling obtains after purification
To superbrnaching end-hydroxy polyether type polyester；
(2) by Toluene-2,4-diisocyanate, 4- diisocyanate, bisphenol A type epoxy resin E51, acetone, polymerization inhibitor and dibutyl tin dilaurate
Another reaction kettle is added, measures initial nco value, after normal-temperature reaction 2~4 hours, being warming up to 45~55 DEG C, the reaction was continued, until NCO
Value stops when being initial value half, is cooled to room temperature；
(3) second step reaction kettle is added in superbrnaching end-hydroxy polyether type polyester obtained by step (1), while adds tin dilaurate two
Butyl tin, be warming up to 50~55 DEG C of reactions to NCO mass content lower than 0.1% when, vacuum outgas obtains polyurethane-modified bis-phenol
A type epoxy resin.
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| CN116790220A (en) * | 2023-08-21 | 2023-09-22 | 广州布鲁奥申新材料科技有限公司 | Environment-friendly high-toughness epoxy adhesive, preparation method and application thereof |
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