CN110041880A - A kind of heavy-duty battery sealant and preparation method thereof - Google Patents
A kind of heavy-duty battery sealant and preparation method thereof Download PDFInfo
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- CN110041880A CN110041880A CN201910181298.3A CN201910181298A CN110041880A CN 110041880 A CN110041880 A CN 110041880A CN 201910181298 A CN201910181298 A CN 201910181298A CN 110041880 A CN110041880 A CN 110041880A
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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
- C09J11/04—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
- 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
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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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
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Chemical Kinetics & Catalysis (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a kind of heavy-duty battery sealants and preparation method thereof, belong to battery sealing material field.Nucleation heat-resisting additive prepared by the present invention promotes sealant rubber to have preferable heat-resistant stability in crystallization process, and can crystallize in wider crystallization range, promotes sealant to obtain temperature resistance deformability and gets a promotion；The graphene oxide of preparation, the preferable mechanical performance having, is added into sealant and is doped, and so that its surface is had preferable ion exchange capacity, addition battery promotes proton exchange and improves conductivity, to promote the enhancing of battery performance；The liquid silastic of preparation is improved sealant crosslink density, crosslinking rate, and mechanical property is remarkably improved, and finally by tackifying resin is added in the encapsulant, increases sealant glueability, increases the performance that is sealing adhesive of sealant systems.The present invention solves the problems, such as that current battery sealant crosslinking rate is slow, bad mechanical property.
Description
Technical field
The present invention relates to battery sealing material technical fields, and in particular to a kind of heavy-duty battery sealant and its preparation side
Method.
Background technique
With the development of modern electronics industry, the battery as new energy also obtains development by leaps and bounds.It is especially high
Energy, chargeable alkaline battery develop more swift and violent.Alkaline battery it is electro-hydraulic be high concentration KOH or NaOH solution.Lye
It is very easy to be climbed along battery seal along leakage is caused, scraps battery.Therefore, alkaline battery sealant is alkaline battery production
In one of indispensable material.Fuel cell is efficient, clean electricity generation system, in recent years, as the new of automobile and household
Type energy resource system attracts attention.Battery sealing material etc. as fuel cell, it is desirable that heat resistance, acid resistance, air permeation resistance and
High-rate forming excellent lower cost materials in status, from heat resistance, acid resistance angle, are suitble to use fluorubber；From resistance to gas
Permeability angle is suitble to use butyl rubber；From heat resistance and formability angle, be suitble to use silicon rubber, but for high speed at
The requirement of shape, common material is all insufficient, in this case, considers to be suitble to the silicon rubber using liquid, using LIM
The method etc. of (Liquid Injection Molding: liquid injection forming) forming.But although the heat resistance of silicon rubber,
High-rate forming is excellent, but acid resistance, air permeation resistance are poor, therefore the power generation performance of existing fuel cell is low, changes with to it
Kind research is goed deep into, and has from now on the raised trend of reaction temperature of the raising inside battery of power generation performance etc..Because
For sealing material, its performance at a higher temperature is also required.Therefore, develop and solve the above problems, that is, solve at
The rubber composition of the problem of shape and heat resistance.The rubber composition high-rate forming is excellent, is suitable for heat resistance, acid resistance
With air permeation resistance excellently fuel cell sealant.But in specific fuel cell sealant, mechanical property sometimes
It is insufficient.With the miniaturization of electric mechanical product, high performance, it is desirable that component parts is smaller, thinner.But work as constituting portion
When part becomes smaller, the combination operation of manufacture is deteriorated, therefore requires the integration of various parts, Composite.But using one
It when the method for body, while realizing the lightness of metal cover, being thinning, when the hardness (reaction force) of liner is high, will generate
The problem of metal cover deforms.Wire connector is the equipment for connection and separated time between electric wire, by can one touch type connection
A pair of convex/concavity resin framework, electric wire and sealing material are constituted.Sealing material be mainly used as electric wire/resin framework it
Between dust-sealing material.Electric connector for this purposes requires the leakproofness relative to thin electric wire with sealing material
With insertion property, currently, using the draining type silicon rubber or nitrile rubber of soft.But these rubber mainly contain silicone oil work
For plasticizer, it will appear plasticizer in use and be attached on electric contact, electric contact is made to insulate, lead to unsmooth etc ask that be powered
Topic.Therefore, it develops suitable for wire connector sealing material.But as the mechanical property to wire connector mentions
It is surging, the case where existing sealing material there is the crosslinking rate after vacuum defoamation in addition to reducing of high requirement, mechanical special
Property is also insufficient, and therefore, it is desirable to improve its performance.
Summary of the invention
The technical problems to be solved by the invention: the slow, mechanical performance for current heavy-duty battery sealant crosslinking rate
The problem of difference provides a kind of heavy-duty battery sealant and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of heavy-duty battery sealant, including nucleation heat-resisting additive, graphene oxide, liquid silastic, tackifying resin, friendship
Join additive.
It is described nucleation heat-resisting additive the preparation method comprises the following steps:
(1) it takes acid anhydrides additive 1 ~ 5:10 in mass ratio ~ 15 that toluene is added to be stirred, the ring penta of toluene quality 10 ~ 15% is added
Diene is stirred, and is kept the temperature then at 1 ~ 3 DEG C, and filtering takes filter residue 1 ~ 5:5 in mass ratio ~ 10 that toluene is added, and stands, and takes precipitating dry
It is dry, obtain dried object；
(2) it takes dried object 2 ~ 5:10 in mass ratio ~ 20 that toluene is added to be stirred, adds the benzylamine of dried object quality 70 ~ 80%
It being stirred, filters, filter cake is taken to wash through toluene, rotary evaporation obtains rotary evaporation object, take rotary evaporation object in mass ratio 3 ~ 6:
2 ~ 5:10 ~ 20 is added lithium hydroxide, deionized water and is stirred, and obtains stirring mixture, take stirring mixture in mass ratio 30 ~
40:2 ~ 7 is added aluminium chloride and is stirred, and filters, and takes and takes out filter residue and drying to get nucleation heat-resisting additive.
Acid anhydrides additive in the step (1) are as follows: take phthalic anhydride 3 ~ 8:2 in mass ratio ~ 5 that benzoyl oxide is added
Mixing to get.
The graphene oxide are as follows: take graphene oxide 1 ~ 3:100 in mass ratio ~ 120 that deionized water is added, oxidation is added
The ethylenediamine and 1 ~ 3 times of graphene oxide quality of amyl nitrite that 3 ~ 6 times of graphene are stirred, and obtain mixture, are added mixed
The reduction activation agent for closing amount of substance 2 ~ 5% is stirred, and is cooled to room temperature, and is filtered, is taken filter cake washed, dry, obtains dried object,
It takes dried object 1 ~ 3:10 in mass ratio ~ 20 that tetrahydrofuran is added, is passed through nitrogen protection, the 1,3- of 2 ~ 4 times of dried object quality is added dropwise
Propyl sulfonic acid lactone is kept the temperature in 40 ~ 50 DEG C, is filtered, and is taken and is taken out filter residue and drying to get graphene oxide.
The reduction activation agent are as follows: take vitamin C 5 ~ 10:2 in mass ratio ~ 5 be added anthocyanidin mixing to get.
The liquid silastic the preparation method comprises the following steps: take tetramethylammonium hydroxide 1 ~ 3:5 in mass ratio ~ 10 be added deionization
Water is passed through nitrogen protection, is stirred, and obtains mixed liquor, takes mixed liquor 1 ~ 5:5 in mass ratio ~ 10 that dimethyl carbonate is added, and is added
The auxiliary material that 4 ~ 8 times of mixed liquor quality, is passed through nitrogen protection, is stirred, and must stir mixture a, take stirring mixture a by
80 ~ 100:3 of mass ratio ~ 9 is added cyclotrisilazane and is stirred, and is cooled to room temperature to get liquid silastic.
The auxiliary material are as follows: take octamethylcy-clotetrasiloxane 5 ~ 10:1 in mass ratio ~ 3 that bis- (3- aminopropyls)-is added
1,1,3,3- tetramethyl disiloxane mixing to get.
The tackifying resin are as follows: terpene phenolic resin, coumarone-indene resin, any one in dcpd resin are taken,
To obtain the final product.
The crosslinking additives the preparation method comprises the following steps: according to the mass fraction, taking 5 ~ 10 parts of potassium acrylates, 0.5 ~ 1.5 part four
Butyl ammonium chloride, 1 ~ 3 part of 4,4' methylene bis (2,6 di t butyl phenol), 3 ~ 5 parts of methyltrimethoxysilane, 50 ~ 70 parts
Toluene is stirred, and filters, smoke filtrate is taken to be evaporated under reduced pressure to get crosslinking additives.
The preparation method includes the following steps:
A. the crosslinking additives 3 ~ 6:1 in mass ratio ~ addition of 3:10 ~ 20 dimethyldimethoxysil,ne, ethyl alcohol is taken to be stirred, then
The hydrochloric acid of crosslinking additives quality 0.5 ~ 1%, heat preservation is added dropwise, rotary evaporation collects rotary evaporation residue, takes rotary evaporation surplus
Ether is added in excess 2 ~ 5:10 in mass ratio ~ 15, stands, and collects upper liquid drying, obtains dried object a；
B. according to the mass fraction, 5 ~ 10 parts of nucleation heat-resisting additives, 20 ~ 40 parts of graphene oxides, 100 ~ 150 parts of liquid silicon rubbers are taken
Glue, 30 ~ 40 parts of tackifying resins are stirred, and obtain matrix object, take matrix object 10 ~ 30:1 in mass ratio ~ 3 that dried object a stirring is added
Mixing is to get heavy-duty battery sealant.
The present invention is compared with other methods, and advantageous effects are:
(1) nucleation heat-resisting additive prepared by the present invention is reacted using acid anhydrides additive, cyclopentadiene as raw material, is added
Benzylamine with aromatic group forms amic acid, is eventually adding lithium hydroxide, aluminium chloride neutralizes to obtain, and aromatic group promotes to seal
Agent rubber has preferable heat-resistant stability in crystallization process, constitutes three by intermolecular hydrogen bond action by free hydroxyl
The gel network structure of dimension, fixed member segment, and can be in wider crystallizations to accelerate the crystalline rate of sealant rubber
Crystallization, promotes sealant to obtain temperature resistance deformability and gets a promotion in temperature range；
(2) graphene oxide prepared by the present invention first carries out amido modification through ethylenediamine etc., adds 1,3- propyl sulfonic acid lactone
It is modified, so that graphene oxide has amino and sulfonic group, makes grafting hydrophilic group on the hydrophobic lamella of graphene oxide, shape
At amphiprotic substance, the preferable mechanical performance having using graphene oxide itself is added into sealant and is doped, makes it
Surface has preferable ion exchange capacity, and addition battery promotes proton exchange and improves conductivity, to promote cell performance
The enhancing of energy；
(3) liquid silastic prepared by the present invention is raw material through tetramethylammonium hydroxide, octamethylcy-clotetrasiloxane, is added small point
Bis- (3- aminopropyls) -1 of son amount, 1,3,3- tetramethyl disiloxane carry out blocking to be prepared obtaining base rubber as sealant,
It is had preferable mobility in sealant preparation process and thixotropy, promotes crosslinking, while with potassium acrylate, methyl trimethoxy oxygen
The crosslinking agent of low molecular weight is prepared in base silane etc., and crosslinking agent has preferable point since molecular weight is low during crosslinking
It dissipates, the acryloxypropyl in crosslinking agent is reacted with the aminopropyl in liquid silica gel, so that sealant base rubber molecule exhibition
It opens, does not cause to crimp, full cross-linked rear sealant crosslink density is improved, and crosslinking rate is also because of preferable flowing bridging property
It is improved, so that sealant obtains mechanical property and is significantly improved, the present invention is finally by addition thickening tree in the encapsulant
Rouge increases sealant glueability, increases the performance that is sealing adhesive of sealant systems.
Specific embodiment
Acid anhydrides additive are as follows: take phthalic anhydride 3 ~ 8:2 in mass ratio ~ 5 be added benzoyl oxide mixing to get.
Be nucleated heat-resisting additive the preparation method comprises the following steps:
(1) it takes acid anhydrides additive 1 ~ 5:10 in mass ratio ~ 15 that toluene is added, 20 ~ 30min is stirred in -3 ~ 1 DEG C, first is added
The cyclopentadiene of benzene quality 10 ~ 15% is stirred 60 ~ 90min in 10 ~ 15 DEG C, then at 1 ~ 3 DEG C of 20 ~ 30min of heat preservation, filters,
It takes filter residue 1 ~ 5:5 in mass ratio ~ 10 that toluene is added, stands 2 ~ 4h, take precipitating drying, obtain dried object；
(2) take dried object 2 ~ 5:10 in mass ratio ~ 20 be added toluene, be stirred 20 ~ 30min, add dried object quality 70 ~
80% benzylamine is stirred 1 ~ 3h in 40 ~ 50 DEG C, and filtering takes filter cake to wash through toluene, and rotary evaporation obtains rotary evaporation object,
Take rotary evaporation object 3 ~ 6:2 in mass ratio ~ 5:10 ~ 20 that lithium hydroxide, deionized water is added, it is stirred 30 in 60 ~ 70 DEG C ~
60min obtains stirring mixture, takes stirring mixture 30 ~ 40:2 in mass ratio ~ 7 that aluminium chloride is added, is stirred in 60 ~ 70 DEG C
20 ~ 40min is filtered, and is taken and is taken out filter residue and drying to get nucleation heat-resisting additive.
Reduction activation agent are as follows: take vitamin C 5 ~ 10:2 in mass ratio ~ 5 be added anthocyanidin mixing to get.
Graphene oxide are as follows: take graphene oxide 1 ~ 3:100 in mass ratio ~ 120 that deionized water is added, graphite oxide is added
The ethylenediamine and 1 ~ 3 times of graphene oxide quality of amyl nitrite that 3 ~ 6 times of alkene, are stirred 8 ~ 10h in 70 ~ 80 DEG C, obtain mixed
Object is closed, the reduction activation agent of mixture quality 2 ~ 5% is added, is warming up to 80 ~ 100 DEG C and is stirred 12 ~ 15h, be cooled to room temperature,
Filtering takes filter cake to wash through deionized water and n,N-Dimethylformamide, dry, obtains dried object, take dried object in mass ratio 1 ~
Tetrahydrofuran is added in 3:10 ~ 20, is passed through nitrogen protection, and 2 ~ 4 times of dried object quality of 1,3- propyl sulfonic acid lactone is added dropwise, in 40 ~
50 DEG C of 60 ~ 90min of heat preservation are filtered, and are taken and are taken out filter residue and drying to get graphene oxide.
Auxiliary material are as follows: take octamethylcy-clotetrasiloxane 5 ~ 10:1 in mass ratio ~ 3 that bis- (3- aminopropyls) -1,1 are added,
3,3- tetramethyl disiloxanes mixing to get.
Liquid silastic the preparation method comprises the following steps: take tetramethylammonium hydroxide 1 ~ 3:5 in mass ratio ~ 10 be added deionized water,
It is passed through nitrogen protection, 20 ~ 30min is stirred in 50 ~ 60 DEG C, obtains mixed liquor, mixed liquor 1 ~ 5:5 in mass ratio ~ 10 is taken to be added
Dimethyl carbonate is added 4 ~ 8 times of mixed liquor quality of auxiliary material, is passed through nitrogen protection, be warming up to 70 ~ 80 DEG C be stirred 8 ~
10h must stir mixture a, take stirring mixture a 80 ~ 100:3 in mass ratio ~ 9 that cyclotrisilazane is added, it is stirred 20 ~
30min is warming up to 140 ~ 150 DEG C and is stirred 20 ~ 30min, is cooled to room temperature to get liquid silastic.
Tackifying resin are as follows: take terpene phenolic resin, coumarone-indene resin, any one in dcpd resin, i.e.,
?.
Crosslinking additives the preparation method comprises the following steps: according to the mass fraction, taking 5 ~ 10 parts of potassium acrylates, 0.5 ~ 1.5 part of tetrabutyl
Ammonium chloride, 1 ~ 3 part of 4,4' methylene bis (2,6 di t butyl phenol), 3 ~ 5 parts of methyltrimethoxysilane, 50 ~ 70 parts of first
Benzene is stirred 30 ~ 50min in 70 ~ 80 DEG C, then is warming up to 100 ~ 110 DEG C and is stirred 3 ~ 6h, filters, smoke filtrate is taken to depressurize
Distillation is to get crosslinking additives.
A kind of preparation method of heavy-duty battery sealant, includes the following steps:
A. take crosslinking additives 3 ~ 6:1 in mass ratio ~ 3:10 ~ 20 that dimethyldimethoxysil,ne is added, mass fraction is 80%
Ethyl alcohol is stirred 20 ~ 30min in 70 ~ 80 DEG C, then the salt that the mass fraction of crosslinking additives quality 0.5 ~ 1% is 36% is added dropwise
Acid keeps the temperature 1 ~ 3h, and rotary evaporation collects rotary evaporation residue, and rotary evaporation residue 2 ~ 5:10 in mass ratio ~ 15 is taken to be added
Ether stands 30 ~ 50min, collects upper liquid drying, obtains dried object a；
B. according to the mass fraction, 5 ~ 10 parts of nucleation heat-resisting additives, 20 ~ 40 parts of graphene oxides, 100 ~ 150 parts of liquid silicon rubbers are taken
Glue, 30 ~ 40 parts of tackifying resins, are stirred 30 ~ 50min in 120 ~ 150 DEG C, obtain matrix object, take matrix object in mass ratio 10 ~
Dried object a is added in 30:1 ~ 3, is stirred 2 ~ 4h in 90 ~ 100 DEG C to get heavy-duty battery sealant.
Acid anhydrides additive are as follows: take phthalic anhydride 3:2 in mass ratio be added benzoyl oxide mixing to get.
Be nucleated heat-resisting additive the preparation method comprises the following steps:
(1) it takes acid anhydrides additive 1:10 in mass ratio that toluene is added, 20min is stirred in -3 DEG C, toluene quality 10% is added
Cyclopentadiene is stirred 60min in 10 DEG C, and then at 1 DEG C of heat preservation 20min, filtering takes filter residue 1:5 in mass ratio that toluene is added,
2h is stood, precipitating drying is taken, obtains dried object；
(2) it takes dried object 2:10 in mass ratio that toluene is added, is stirred 20min, adds the benzylamine of dried object quality 70%,
It is stirred 1h in 40 DEG C, filters, takes filter cake to wash through toluene, rotary evaporation obtains rotary evaporation object, takes rotary evaporation object by matter
Lithium hydroxide, deionized water is added than 3:2:10 in amount, is stirred 30min in 60 DEG C, obtains stirring mixture, takes stirring mixture
Aluminium chloride is added in 30:2 in mass ratio, is stirred 20min in 60 DEG C, filters, and takes and takes out filter residue and drying to get heat-resisting addition is nucleated
Agent.
Reduction activation agent are as follows: take vitamin C 5:2 in mass ratio be added anthocyanidin mixing to get.
Graphene oxide are as follows: take graphene oxide 1:100 in mass ratio that deionized water is added, be added 3 times of graphene oxide
Ethylenediamine and 1 times of graphene oxide quality of amyl nitrite, be stirred 8h in 70 DEG C, obtain mixture, mixture is added
The reduction activation agent of quality 2% is warming up to 80 DEG C and is stirred 12h, is cooled to room temperature, and filtering takes filter cake through deionized water and N,
Dinethylformamide washing, it is dry, dried object is obtained, takes dried object 1:10 in mass ratio that tetrahydrofuran is added, is passed through nitrogen guarantor
2 times of dried object quality of 1,3- propyl sulfonic acid lactone is added dropwise in shield, in 40 DEG C of heat preservation 60min, filters, take pumping filter residue and drying to get
Graphene oxide.
Auxiliary material are as follows: take octamethylcy-clotetrasiloxane 5:1 in mass ratio that bis- (3- aminopropyl) -1,1,3,3- four are added
Tetramethyldisiloxane mixing to get.
Liquid silastic the preparation method comprises the following steps: take tetramethylammonium hydroxide 1:5 in mass ratio be added deionized water, be passed through nitrogen
Gas shielded is stirred 20min in 50 DEG C, obtains mixed liquor, takes mixed liquor 1:5 in mass ratio that dimethyl carbonate is added, and is added mixed
The auxiliary material for closing 4 times of liquid quality, is passed through nitrogen protection, is warming up to 70 DEG C and is stirred 8h, must stir mixture a, take stirring
Cyclotrisilazane is added in mixture a 80:3 in mass ratio, is stirred 20min, is warming up to 140 DEG C and is stirred 20min, cooling
To room temperature to get liquid silastic.
Tackifying resin are as follows: take terpene phenolic resin.
Crosslinking additives the preparation method comprises the following steps: according to the mass fraction, taking 5 parts of potassium acrylates, 0.5 part of tetrabutylammonium chloride, 1
Part 4,4'- di-2-ethylhexylphosphine oxide (2,6- DI-tert-butylphenol compounds), 3 parts of methyltrimethoxysilane, 50 parts of toluene, are stirred in 70 DEG C
30min, then be warming up to 100 DEG C and be stirred 3h, it filters, smoke filtrate is taken to be evaporated under reduced pressure to get crosslinking additives.
A kind of preparation method of heavy-duty battery sealant, includes the following steps:
A. the ethyl alcohol that dimethyldimethoxysil,ne is added in crosslinking additives 3:1:10 in mass ratio, mass fraction is 80% is taken, in
70 DEG C are stirred 20min, then the hydrochloric acid that the mass fraction of crosslinking additives quality 0.5% is 36% is added dropwise, and keep the temperature 1h, and rotation is steamed
Hair collects rotary evaporation residue, takes rotary evaporation residue 2:10 in mass ratio that ether is added, and stands 30min, collects upper layer
Liquid is dry, obtains dried object a；
B. according to the mass fraction, 5 parts of nucleation heat-resisting additives, 20 parts of graphene oxides, 100 parts of liquid silastics, 30 parts of increasings are taken
Viscosity resin is stirred 30min in 120 DEG C, obtains matrix object, takes matrix object 10:1 in mass ratio that dried object a is added, stirs in 90 DEG C
Mixing 2h is mixed to get heavy-duty battery sealant.
Acid anhydrides additive are as follows: take phthalic anhydride 8:5 in mass ratio be added benzoyl oxide mixing to get.
Be nucleated heat-resisting additive the preparation method comprises the following steps:
(1) it takes acid anhydrides additive 5:15 in mass ratio that toluene is added, 30min is stirred in 1 DEG C, toluene quality 15% is added
Cyclopentadiene is stirred 90min in 15 DEG C, and then at 3 DEG C of heat preservation 30min, filtering takes filter residue 5:10 in mass ratio that first is added
Benzene stands 4h, takes precipitating drying, obtain dried object；
(2) it takes dried object 5:20 in mass ratio that toluene is added, is stirred 30min, adds the benzylamine of dried object quality 80%,
It is stirred 3h in 50 DEG C, filters, takes filter cake to wash through toluene, rotary evaporation obtains rotary evaporation object, takes rotary evaporation object by matter
Lithium hydroxide, deionized water is added than 6:5:20 in amount, is stirred 60min in 70 DEG C, obtains stirring mixture, takes stirring mixture
Aluminium chloride is added in 40:7 in mass ratio, is stirred 40min in 70 DEG C, filters, and takes and takes out filter residue and drying to get heat-resisting addition is nucleated
Agent.
Reduction activation agent are as follows: take vitamin C 10:5 in mass ratio be added anthocyanidin mixing to get.
Graphene oxide are as follows: take graphene oxide 3:120 in mass ratio that deionized water is added, be added 6 times of graphene oxide
Ethylenediamine and 3 times of graphene oxide quality of amyl nitrite, be stirred 10h in 80 DEG C, obtain mixture, mixture is added
The reduction activation agent of quality 5% is warming up to 100 DEG C and is stirred 15h, is cooled to room temperature, filtering, take filter cake through deionized water and
N,N-Dimethylformamide washing, it is dry, dried object is obtained, takes dried object 3:20 in mass ratio that tetrahydrofuran is added, is passed through nitrogen
4 times of dried object quality of 1,3- propyl sulfonic acid lactone is added dropwise in protection, in 50 DEG C of heat preservation 90min, filters, takes pumping filter residue and drying, i.e.,
Obtain graphene oxide.
Auxiliary material are as follows: take octamethylcy-clotetrasiloxane 10:3 in mass ratio that bis- (3- aminopropyl) -1,1,3,3- are added
Tetramethyl disiloxane mixing to get.
Liquid silastic the preparation method comprises the following steps: take tetramethylammonium hydroxide 3:10 in mass ratio be added deionized water, be passed through
Nitrogen protection is stirred 30min in 60 DEG C, obtains mixed liquor, takes mixed liquor 5:10 in mass ratio that dimethyl carbonate is added, and is added
The auxiliary material that 8 times of mixed liquor quality, is passed through nitrogen protection, is warming up to 80 DEG C and is stirred 10h, must stir mixture a, take and stir
It mixes mixture a 100:9 in mass ratio and cyclotrisilazane is added, be stirred 30min, be warming up to 150 DEG C and be stirred 30min,
It is cooled to room temperature to get liquid silastic.
Tackifying resin are as follows: take coumarone-indene resin.
Crosslinking additives the preparation method comprises the following steps: according to the mass fraction, take 10 parts of potassium acrylates, 1.5 parts of tetrabutylammonium chlorides,
3 parts of 4,4'- di-2-ethylhexylphosphine oxides (2,6- DI-tert-butylphenol compounds), 5 parts of methyltrimethoxysilane, 70 parts of toluene, it is mixed in 80 DEG C of stirrings
50min is closed, then is warming up to 110 DEG C and is stirred 6h, filters, smoke filtrate is taken to be evaporated under reduced pressure to get crosslinking additives.
A kind of preparation method of heavy-duty battery sealant, includes the following steps:
A. the ethyl alcohol that dimethyldimethoxysil,ne is added in crosslinking additives 6:3:20 in mass ratio, mass fraction is 80% is taken, in
80 DEG C are stirred 30min, then the hydrochloric acid that the mass fraction of crosslinking additives quality 1% is 36% is added dropwise, and keep the temperature 3h, and rotation is steamed
Hair collects rotary evaporation residue, takes rotary evaporation residue 5:15 in mass ratio that ether is added, and stands 50min, collects upper layer
Liquid is dry, obtains dried object a；
B. according to the mass fraction, 10 parts of nucleation heat-resisting additives, 40 parts of graphene oxides, 150 parts of liquid silastics, 40 parts of increasings are taken
Viscosity resin is stirred 50min in 150 DEG C, obtains matrix object, takes matrix object 30:3 in mass ratio that dried object a is added, in 100 DEG C
4h is stirred to get heavy-duty battery sealant.
Acid anhydrides additive are as follows: take phthalic anhydride 5:3 in mass ratio be added benzoyl oxide mixing to get.
Be nucleated heat-resisting additive the preparation method comprises the following steps:
(1) it takes acid anhydrides additive 3:13 in mass ratio that toluene is added, 25min is stirred in 0 DEG C, toluene quality 11% is added
Cyclopentadiene is stirred 80min in 12 DEG C, and then at 2 DEG C of heat preservation 23min, filtering takes filter residue 3:7 in mass ratio that toluene is added,
3h is stood, precipitating drying is taken, obtains dried object；
(2) it takes dried object 3:15 in mass ratio that toluene is added, is stirred 25min, adds the benzylamine of dried object quality 75%,
It is stirred 2h in 30 DEG C, filters, takes filter cake to wash through toluene, rotary evaporation obtains rotary evaporation object, takes rotary evaporation object by matter
Lithium hydroxide, deionized water is added than 5:3:13 in amount, is stirred 50min in 65 DEG C, obtains stirring mixture, takes stirring mixture
Aluminium chloride is added in 35:5 in mass ratio, is stirred 30min in 65 DEG C, filters, and takes and takes out filter residue and drying to get heat-resisting addition is nucleated
Agent.
Reduction activation agent are as follows: take vitamin C 7:3 in mass ratio be added anthocyanidin mixing to get.
Graphene oxide are as follows: take graphene oxide 2:110 in mass ratio that deionized water is added, be added 5 times of graphene oxide
Ethylenediamine and 2 times of graphene oxide quality of amyl nitrite, be stirred 9h in 75 DEG C, obtain mixture, mixture is added
The reduction activation agent of quality 3% is warming up to 90 DEG C and is stirred 13h, is cooled to room temperature, and filtering takes filter cake through deionized water and N,
Dinethylformamide washing, it is dry, dried object is obtained, takes dried object 2:15 in mass ratio that tetrahydrofuran is added, is passed through nitrogen guarantor
3 times of dried object quality of 1,3- propyl sulfonic acid lactone is added dropwise in shield, in 45 DEG C of heat preservation 80min, filters, take pumping filter residue and drying to get
Graphene oxide.
Auxiliary material are as follows: take octamethylcy-clotetrasiloxane 7:2 in mass ratio that bis- (3- aminopropyl) -1,1,3,3- four are added
Tetramethyldisiloxane mixing to get.
Liquid silastic the preparation method comprises the following steps: take tetramethylammonium hydroxide 2:7 in mass ratio be added deionized water, be passed through nitrogen
Gas shielded is stirred 25min in 55 DEG C, obtains mixed liquor, takes mixed liquor 3:7 in mass ratio that dimethyl carbonate is added, and is added mixed
The auxiliary material for closing 6 times of liquid quality, is passed through nitrogen protection, is warming up to 75 DEG C and is stirred 9h, must stir mixture a, take stirring
Cyclotrisilazane is added in mixture a 90:7 in mass ratio, is stirred 25min, is warming up to 145 DEG C and is stirred 25min, cooling
To room temperature to get liquid silastic.
Tackifying resin are as follows: take dcpd resin.
Crosslinking additives the preparation method comprises the following steps: according to the mass fraction, taking 7 parts of potassium acrylates, 0.9 part of tetrabutylammonium chloride, 2
Part 4,4'- di-2-ethylhexylphosphine oxide (2,6- DI-tert-butylphenol compounds), 4 parts of methyltrimethoxysilane, 60 parts of toluene, are stirred in 75 DEG C
40min, then be warming up to 105 DEG C and be stirred 5h, it filters, smoke filtrate is taken to be evaporated under reduced pressure to get crosslinking additives.
A kind of preparation method of heavy-duty battery sealant, includes the following steps:
A. the ethyl alcohol that dimethyldimethoxysil,ne is added in crosslinking additives 5:2:15 in mass ratio, mass fraction is 80% is taken, in
75 DEG C are stirred 25min, then the hydrochloric acid that the mass fraction of crosslinking additives quality 0.7% is 36% is added dropwise, and keep the temperature 2h, and rotation is steamed
Hair collects rotary evaporation residue, takes rotary evaporation residue 3:12 in mass ratio that ether is added, and stands 40min, collects upper layer
Liquid is dry, obtains dried object a；
B. according to the mass fraction, 7 parts of nucleation heat-resisting additives, 30 parts of graphene oxides, 120 parts of liquid silastics, 35 parts of increasings are taken
Viscosity resin is stirred 40min in 130 DEG C, obtains matrix object, takes matrix object 20:2 in mass ratio that dried object a is added, stirs in 95 DEG C
Mixing 3h is mixed to get heavy-duty battery sealant.
Comparative example 1: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking nucleation heat-resisting additive.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking graphene oxide.
Comparative example 3: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking liquid silastic.
Comparative example 4: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking tackifying resin.
Comparative example 5: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that lacking crosslinking additives.
Comparative example 6: the heavy-duty battery sealant of company, Shenzhen production.
Above-described embodiment and heavy-duty battery sealant made of comparative example are detected, JISA hardness: JIS K6253
(1997), the instant value measured with spring hardness tester A type；Compression Set: JISK6262(1997), use thickness
The cylindrical sample of 12.7mm, diameter 29.0mm, in 25% compression, the residual deformation after 70 DEG C × 22 hours；Tensile strength:
JISK6251(1993), the tensile strength of tension test is carried out with tensile speed 200mm/min using JIS3 dumbbell shape sample；
Permanent elongation rate: JIS K6301(1971), JIS3 dumbbell shape sample is stretched 100% and is kept for 10 minutes, 10 points of removal weight bearing
Residual strain after clock, obtains that the results are shown in Table 1.
Table 1:
In summary, heavy-duty battery sealant effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, above
Described is only preferred mode of the invention, is not intended to limit the invention, all within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc. should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of heavy-duty battery sealant, which is characterized in that including being nucleated heat-resisting additive, graphene oxide, liquid silicon rubber
Glue, tackifying resin, crosslinking additives.
2. heavy-duty battery sealant according to claim 1, which is characterized in that the preparation of the nucleation heat-resisting additive
Method are as follows:
(1) it takes acid anhydrides additive 1 ~ 5:10 in mass ratio ~ 15 that toluene is added to be stirred, the ring penta of toluene quality 10 ~ 15% is added
Diene is stirred, and is kept the temperature then at 1 ~ 3 DEG C, and filtering takes filter residue 1 ~ 5:5 in mass ratio ~ 10 that toluene is added, and stands, and takes precipitating dry
It is dry, obtain dried object；
(2) it takes dried object 2 ~ 5:10 in mass ratio ~ 20 that toluene is added to be stirred, adds the benzylamine of dried object quality 70 ~ 80%
It being stirred, filters, filter cake is taken to wash through toluene, rotary evaporation obtains rotary evaporation object, take rotary evaporation object in mass ratio 3 ~ 6:
2 ~ 5:10 ~ 20 is added lithium hydroxide, deionized water and is stirred, and obtains stirring mixture, take stirring mixture in mass ratio 30 ~
40:2 ~ 7 is added aluminium chloride and is stirred, and filters, and takes and takes out filter residue and drying to get nucleation heat-resisting additive.
3. heavy-duty battery sealant according to claim 2, which is characterized in that the acid anhydrides addition in the step (1)
Agent are as follows: take phthalic anhydride 3 ~ 8:2 in mass ratio ~ 5 be added benzoyl oxide mixing to get.
4. heavy-duty battery sealant according to claim 1, which is characterized in that the graphene oxide are as follows: take oxidation
Deionized water is added in graphene 1 ~ 3:100 in mass ratio ~ 120, and 3 ~ 6 times of graphene oxide of ethylenediamine and graphene oxide is added
The amyl nitrite that 1 ~ 3 times of quality is stirred, and obtains mixture, and the reduction activation agent stirring that mixture quality 2 ~ 5% is added is mixed
It closes, is cooled to room temperature, filter, take filter cake washed, it is dry, dried object is obtained, dried object 1 ~ 3:10 in mass ratio ~ 20 is taken to be added four
Hydrogen furans is passed through nitrogen protection, and 2 ~ 4 times of dried object quality of 1,3- propyl sulfonic acid lactone is added dropwise, and keeps the temperature in 40 ~ 50 DEG C, filters,
It takes and takes out filter residue and drying to get graphene oxide.
5. heavy-duty battery sealant according to claim 4, which is characterized in that the reduction activation agent are as follows: dimension is taken to give birth to
Plain C 5 ~ 10:2 in mass ratio ~ 5 be added anthocyanidin mixing to get.
6. heavy-duty battery sealant according to claim 1, which is characterized in that the preparation method of the liquid silastic
Are as follows: it takes tetramethylammonium hydroxide 1 ~ 3:5 in mass ratio ~ 10 that deionized water is added, is passed through nitrogen protection, is stirred, must mix
Liquid takes mixed liquor 1 ~ 5:5 in mass ratio ~ 10 that dimethyl carbonate is added, and 4 ~ 8 times of mixed liquor quality of auxiliary material is added, is passed through
Nitrogen protection is stirred, and must stir mixture a, takes stirring mixture a 80 ~ 100:3 in mass ratio ~ 9 that cyclotrisilazane is added
It is stirred, is cooled to room temperature to get liquid silastic.
7. heavy-duty battery sealant according to claim 6, which is characterized in that the auxiliary material are as follows: take prestox
Cyclotetrasiloxane 5 ~ 10:1 in mass ratio ~ 3 is added bis- (3- aminopropyls) -1,1,3,3- tetramethyl disiloxane mix to get.
8. heavy-duty battery sealant according to claim 1, which is characterized in that the tackifying resin are as follows: take terpene phenolic
Urea formaldehyde, coumarone-indene resin, any one in dcpd resin to get.
9. heavy-duty battery sealant according to claim 1, which is characterized in that the preparation method of the crosslinking additives
Are as follows: according to the mass fraction, take 5 ~ 10 parts of potassium acrylates, 0.5 ~ 1.5 part of tetrabutylammonium chloride, 1 ~ 3 part of 4,4'- di-2-ethylhexylphosphine oxide (2,
6- DI-tert-butylphenol compounds), 3 ~ 5 parts of methyltrimethoxysilane, 50 ~ 70 parts of toluene be stirred, filter, smoke filtrate decompression taken to steam
It evaporates to get crosslinking additives.
10. a kind of preparation method of the heavy-duty battery sealant as described in claim 1 ~ 9 any one, which is characterized in that
The preparation method includes the following steps:
A. the crosslinking additives 3 ~ 6:1 in mass ratio ~ addition of 3:10 ~ 20 dimethyldimethoxysil,ne, ethyl alcohol is taken to be stirred, then
The hydrochloric acid of crosslinking additives quality 0.5 ~ 1%, heat preservation is added dropwise, rotary evaporation collects rotary evaporation residue, takes rotary evaporation surplus
Ether is added in excess 2 ~ 5:10 in mass ratio ~ 15, stands, and collects upper liquid drying, obtains dried object a；
B. according to the mass fraction, 5 ~ 10 parts of nucleation heat-resisting additives, 20 ~ 40 parts of graphene oxides, 100 ~ 150 parts of liquid silicon rubbers are taken
Glue, 30 ~ 40 parts of tackifying resins are stirred, and obtain matrix object, take matrix object 10 ~ 30:1 in mass ratio ~ 3 that dried object a stirring is added
Mixing is to get heavy-duty battery sealant.
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| CN101213251A (en) * | 2005-06-30 | 2008-07-02 | 三井化学株式会社 | Rubber composition and use thereof |
| CN106753217A (en) * | 2017-01-18 | 2017-05-31 | 山东大学 | A kind of preparation method of Novel hot vulcanized liquid silicon rubber |
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