CN109609081A - A kind of adhesive for polyurethane for power battery PACK structural bond - Google Patents
A kind of adhesive for polyurethane for power battery PACK structural bond Download PDFInfo
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- CN109609081A CN109609081A CN201811507941.9A CN201811507941A CN109609081A CN 109609081 A CN109609081 A CN 109609081A CN 201811507941 A CN201811507941 A CN 201811507941A CN 109609081 A CN109609081 A CN 109609081A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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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
- C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
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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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The present invention relates to a kind of adhesive for polyurethane for power battery PACK structural bond, the volume ratio of component A and B component is 1:1；By weight, component A includes: 5-20 parts of epoxy resin modification polyalcohol, 0-5 parts of 3-10 parts of 20-35 parts of 0-0.05 parts of 0-3 parts of 10-25 parts of 15-30 parts of polyalcohol, biopolyol, crosslinking agent, catalyst, fire retardant, molecular sieve, the thixotropic agent containing phenyl ring；B component includes: 0-5 parts of 3-10 parts of 0.1-0.3 parts of 18-30 parts of 0-20 parts of 50-70 parts of base polyurethane prepolymer for use as, isocyanates, fire retardant, adhesion promoter, molecular sieve, the thixotropic agent of terminal isocyanate group；Adhesive for polyurethane prepared by the present invention has excellent adhesion energy to the metal materials such as the plastic materials such as PI, PET, the PC not being surface-treated and aluminium, steel and its alloy, has excellent ageing-resistant performance and lower modulus.
Description
Technical field
The present invention relates to adhesive technology field, especially a kind of polyurethane adhesive for power battery PACK structural bond
Glutinous agent and preparation method thereof.
Background technique
Data show that new-energy automobile production and marketing in 2017 close to 800,000, respectively reaches 79.4 ten thousand and 77.7 ten thousand,
Increase by 53.8% and 53.3% respectively on year-on-year basis.New energy policy bonus drives battery industry " blowout ", and 2012 to 2017 terms
Between, domestic power battery enterprise grows rapidly, and installation amount increases 55 times between 5 years, it is contemplated that arrives the year two thousand twenty only China's lithium battery
Production capacity is up to annual 137GWh.The fast-developing development and perfection for promoting related industry of industry, it is viscous in battery PACK structure
In terms of connecing with glue, because power battery PACK mould group Facing material includes the various function materials such as PI, PET, PC, aluminium alloy, it is desirable that
Just there is preferable bonding to the non-specially treated of various materials, while requiring have higher fire-retardant, volume resistivity, resistance to ag(e)ing,
Meet the working condition of power battery high-frequency vibration, adapts to automobile extremely cold area, the use in high fever area etc., while having higher
Environmental requirement, meet the requirement of RoHS Directive, REACH regulation.
Although epoxy resin adhesive has preferable bonding to metal in the prior art, to the bonding of PI, PET material
It is less desirable, while that there are hardness is higher for epoxy resin, it is lower to cooling thermal impact and high-frequency vibration condition tolerance.The second generation
Acrylate adhesive cannot concurrently reach requirement there are both adhesive property and toughness, and ageing properties are poor, storage stability
The problem of difference.Two-component polyurethane adhesive sticks that the agent storage period is long, colloid hardness is adjustable, safety and environmental protection, volume resistivity height etc. are excellent
Gesture becomes first choice.But there is the disadvantages of poor to various material adhesive properties, loss of properties on aging in conventional urethane adhesive.
There is no under the conditions of the non-surface treated of the metal materials such as the plastic materials such as PI, PET, PC and aluminium, steel and its alloy to having at present
There are excellent adhesive property, the excellent adhesive for polyurethane of ageing properties.
It develops in summary a kind of golden to the plastic materials such as PI, PET, PC for not being surface-treated and aluminium, steel and its alloy etc.
Category material, which has excellent adhesion to compare favourably with epoxy resin adhesive adhesive strength simultaneously, has excellent aging
The power battery PACK structural bond of energy is very promising with adhesive for polyurethane.
Summary of the invention
To solve the deficiencies in the prior art, the present invention provides a kind of polyurethane adhesive for power battery PACK structural bond
Glutinous agent, the adhesive have the metal materials such as the plastic materials such as PI, PET, the PC not being surface-treated and aluminium, steel and its alloy excellent
Different adhesive property, while there is low modulus, high tenacity, high flame-retardant property, it is ensured that power battery is in high-frequency vibration, because of the winter
Use state under high temperature difference operating condition caused by the factors such as summer, region, battery-heating.
It is achieved particular by following technical scheme:
A kind of adhesive for polyurethane for power battery PACK structural bond is made of two kinds of components of A, B；By weight,
Wherein component A is made of following material: 5-20 parts of epoxy resin modification polyalcohol, 15-30 parts of the polyalcohol containing phenyl ring, biology base
10-25 parts of polyalcohol, 0-3 parts of crosslinking agent, 0-0.05 parts of catalyst, 20-35 parts of fire retardant, 3-10 parts of molecular sieve, thixotropic agent 0-5
Part；B component is made of following material: 0-20 parts of 50-70 parts of base polyurethane prepolymer for use as, the isocyanates of terminal isocyanate group, fire-retardant
18-30 parts of agent, 0.1-0.3 parts of adhesion promoter, 3-10 parts of molecular sieve, 0-5 parts of thixotropic agent.
The epoxy resin modification polyalcohol is prepared by epoxy resin and polyalcohol, isocyanates blending and modifying；The ring
Oxygen resin is the mixing of one or both of bisphenolA-glycidol ether epoxy resin or Bisphenol F diglycidyl ether；It is described more
First alcohol is one of the polyoxypropyleneglycol of molecular weight 400-2000, polypropylene oxide triol or a variety of；The isocyanide
Acid esters is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene dimethylene diisocyanate, liquefied mdi, polymerization
One of MDI or a variety of.
The base polyurethane prepolymer for use as of the terminal isocyanate group is that the dihydric alcohol of molecular weight 1000-3000 is reacted with isocyanates
It generates；The dihydric alcohol be one of castor oil modified dihydric alcohol that polyoxypropyleneglycol, U.S. Vertellus are produced or
It is a variety of.The isocyanates is that isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne two
One of isocyanates, liquefied mdi, polymeric MDI are a variety of.
The volume ratio of the component A and B component is 1:1.
The polyalcohol containing phenyl ring is that the bisphenol A polyether glycol of A Kema production, Hua Da chemistry or magnificent peak new material are raw
One of phthalic anhydride polyester diol of production is a variety of.
The biopolyol is one of castor oil, rilanit special, soybean oil, palm oil or arbitrary proportion
It is a variety of.
The crosslinking agent is hydroxyl value 300-500mgKOH/g, the polyether polyol of degree of functionality 4-6, preferably, selecting sub-
The YD-635 of eastern chemical industry；The catalyst is bismuth neodecanoate, lauric acid bismuth, isooctyl acid bismuth, bismuth naphthenate, zinc neodecanoate, different pungent
One of sour zinc, zinc naphthenate or arbitrary proportion it is a variety of；The fire retardant is nitrogen phosphorus series non-halogen fire retardant, hydroxide
One of aluminium, magnesium hydroxide are a variety of, preferably, nitrogen phosphorus series non-halogen fire retardant is dongle chemical industry Doher8313.
The thixotropic agent is fumed silica.
The adhesion promoter is two kinds of one of BYK4500 and BYK4510 or arbitrary proportion.
A kind of preparation method of the epoxy resin polyalcohol of the adhesive for polyurethane for power battery PACK structural bond,
Include the following steps:
Epoxy resin is mixed with isocyanates equimolar ratio, order by merging is that isocyanates is added in epoxy resin, is added
Stir process in the process, mixing speed 200-300r/min, it is 200-220 DEG C that adjustment temperature is kept stirring after addition,
Be cooled to 40-50 DEG C after it reacts 0.5-2h, be added equimolar polyalcohol, adjustment temperature is 70-80 DEG C, be kept stirring to
It is cooled to room temperature after reacting 1.5-3h up to epoxy resin modification polyalcohol；
A kind of base polyurethane prepolymer for use as of the terminal isocyanate group of the adhesive for polyurethane for power battery PACK structural bond
Preparation method includes the following steps:
Dihydric alcohol is heated to 100-115 DEG C, is evacuated to -0.098MPa, this process stir process, mixing speed is
300-500r/min is cooled to 40-55 DEG C after being kept stirring dehydration 1.5-2.5h, isocyanates, control theory NCO content is added
For 8-18%, adjustment temperature is cooled to room temperature after being kept stirring reaction 1.5-3h to 70-80 DEG C after the no longer upper punching of reaction temperature
Up to the base polyurethane prepolymer for use as of terminal isocyanate group;
A kind of adhesive for polyurethane preparation method for power battery PACK structural bond: in proportion respectively by A, B
The various raw materials of component are uniformly mixed up to A, B component.
The adhesive for polyurethane of power battery PACK structural bond of the present invention, by introduce epoxy resin with it is polynary
Alcohol is hybridized to multidimensional network structure, improves mechanical performance and ageing properties；Select the polyalcohol containing phenyl ring resistance in raising adhesive
Also there is certain effect to the bonding of metal and PET to raising while hot；It is certain that the selection of biopolyol assigns glue
Hydrophobicity, improve its stability under high humidity environment；Dihydric alcohol used by the base polyurethane prepolymer for use as of terminal isocyanate group
With longer and smooth molecular chain structure, make it possible the low modulus of colloid.
Compared with prior art, the beneficial effects of the present invention are:
1, there is excellent glue to the metal materials such as the plastic materials such as PI, PET, the PC not being surface-treated and aluminium, steel and its alloy
Performance is connect, PI, PET adhesive shear strength > 5MPa are bonded PC adhesive shear strength > 8MPa to untreated aluminium alloy
Shear strength > 10MPa；
2, with excellent ageing-resistant performance, after double 85 aging 1000h, shear strength decays < 20%；
3, there is lower modulus, 25 DEG C of calculating modulus < 500MPa are relatively suitable for the environment of power battery high-frequency vibration.
Specific embodiment
Embodiment 1
(1) prepared by epoxy resin polyalcohol: by 30kg Bisphenol F diglycidyl ether epoxy resin and 5.5kg diphenyl methane two
Isocyanates mixing, order by merging are that isocyanates is added in epoxy resin, and uses mixing speed for 300r/min progress
Stir process, adjustment temperature are 210 DEG C, cool the temperature to 45 DEG C after it reacts 1h, and the polyoxygenated that molecular weight is 1000 is added
Propylene triol 50kg is kept stirring and slowly adjusts temperature to 70 DEG C, is cooled to room temperature after reaction 2h more up to epoxy resin
First alcohol, for use；
(2) prepared by terminal isocyanate group base polyurethane prepolymer for use as: taking the polyoxypropyleneglycol heat temperature raising of 100kg molecular weight 2000
To 110 DEG C and it is evacuated to -0.098MPa, this process stir process, mixing speed 450r/min, after being kept stirring dehydration 2h
45 DEG C are cooled to, 120kg liquefied mdi is proportionally added into, adjustment temperature is kept stirring to 70 DEG C after the no longer upper punching of reaction temperature
The base polyurethane prepolymer for use as up to terminal isocyanate group is cooled to room temperature after reaction 2h, for use；
(3) prepared by component A: extracting epoxy resin polyalcohol 15kg, benzoic anhydride polyester polyol 20kg, castor oil 5kg, castor oil modified
Polyalcohol 15kg, 4.6 degree of functionality rigid-foam polyether polyol 0.5kg, nitrogen phosphorus halogen-free flame retardants 25kg, aluminium hydroxide 8kg, gas phase two
Silica 1kg, molecular sieve 4.5kg, bismuth neodecanoate 0.05kg high speed dispersion stir evenly, revolving speed 1200r/min, are after stirring 2h
Obtain component A；
(4) prepared by B component: taking terminal isocyanate group base polyurethane prepolymer for use as 65kg, polymeric MDI 10kg, nitrogen phosphorus halogen-free flame retardants
20kg, molecular sieve 5kg, fumed silica 0.5kg, adhesion promoter BYK4500 0.1kg high speed dispersion stir evenly, and turn
Up to B component after fast 1200r/min, stirring 2h.
Embodiment 2
(1) prepared by epoxy resin polyalcohol: 30kg bisphenolA-glycidol ether epoxy resin and 5kg diphenyl methane two is different
Cyanate mixing, order by merging are that isocyanates is added in epoxy resin, and mixing speed is used to be stirred for 300r/min
Processing is mixed, adjustment temperature is 210 DEG C, cools the temperature to 45 DEG C after it reacts 1h, and the polyoxygenated third that molecular weight is 1000 is added
Alkene triol 50kg is kept stirring and slowly adjusts temperature to 70 DEG C, is cooled to room temperature after reaction 2h polynary up to epoxy resin
Alcohol, for use；
(2) prepared by terminal isocyanate group base polyurethane prepolymer for use as: taking the castor oil modified dihydric alcohol of 100kg molecular weight 3000 to heat and rises
Temperature is to 110 DEG C and is evacuated to -0.098MPa, this process stir process, mixing speed 450r/min, is kept stirring dehydration 2h
After be cooled to 45 DEG C, be proportionally added into 110kg liquefied mdi, adjustment temperature keeps stirring to 70 DEG C after the no longer upper punching of reaction temperature
The base polyurethane prepolymer for use as being cooled to room temperature after reacting 2h up to terminal isocyanate group is mixed, for use；
(3) prepared by component A: extracting epoxy resin polyalcohol 8kg, benzoic anhydride polyester polyol 25kg, castor oil 5kg, castor oil modified
Polyalcohol 24kg, 4.6 degree of functionality rigid-foam polyether polyol 0.4kg, nitrogen phosphorus halogen-free flame retardants 25kg, aluminium hydroxide 8kg, molecular sieve
5kg, fumed silica 1.5kg, bismuth neodecanoate 0.05kg high speed dispersion stir evenly, revolving speed 1200r/min, are after stirring 2h
Obtain component A；
(4) prepared by B component: taking terminal isocyanate group base polyurethane prepolymer for use as 65kg, polymeric MDI 10kg, nitrogen phosphorus halogen-free flame retardants
20kg, molecular sieve 5kg, fumed silica 0.5kg, adhesion promoter BYK4510 0.1kg high speed dispersion stir evenly, and turn
Up to B component after fast 1200r/min, stirring 2h.
Embodiment 3
(1) prepared by epoxy resin polyalcohol: 30kg Bisphenol F diglycidyl ether epoxy resin and 6kg liquefied mdi being mixed, mixed
Conjunction sequence is that isocyanates is added in epoxy resin, and mixing speed is used to be stirred for 300r/min, adjustment temperature
Degree is 210 DEG C, and 45 DEG C are cooled the temperature to after it reacts 1h, and addition molecular weight is 1000 castor oil modified polyalcohol 50kg, is protected
It holds and stirs and slowly adjust temperature to 70 DEG C, be cooled to room temperature up to epoxy resin polyalcohol, for use after reacting 2h；
(2) prepared by terminal isocyanate group base polyurethane prepolymer for use as: taking the castor oil modified dihydric alcohol of 100kg molecular weight 2000 to heat and rises
Temperature is to 110 DEG C and is evacuated to -0.098MPa, this process stir process, mixing speed 450r/min, is kept stirring dehydration 2h
After be cooled to 45 DEG C, be proportionally added into 120kg liquefied mdi, adjustment temperature keeps stirring to 70 DEG C after the no longer upper punching of reaction temperature
The base polyurethane prepolymer for use as being cooled to room temperature after reacting 2h up to terminal isocyanate group is mixed, for use；
(3) prepared by component A: extracting epoxy resin polyalcohol 20kg, bisphenol A polyether polyalcohol 18kg, castor oil 3kg, castor oil change
Property polyalcohol 23kg, nitrogen phosphorus halogen-free flame retardants 25kg, aluminium hydroxide 8kg, molecular sieve 5kg, fumed silica 1.5kg, laurel
Sour bismuth 0.05kg high speed dispersion stirs evenly, revolving speed 1200r/min, up to component A after stirring 2h；
(4) prepared by B component: taking terminal isocyanate group base polyurethane prepolymer for use as 70kg, nitrogen phosphorus halogen-free flame retardants 25kg, gas phase titanium dioxide
Silicon 0.5kg, adhesion promoter BYK4500 0.1kg high speed dispersion stir evenly, revolving speed 1200r/min, up to B after stirring 2h
Component.
Embodiment 4
(1) prepared by epoxy resin polyalcohol: 30kg bisphenolA-glycidol ether epoxy resin and 6kg liquefied mdi being mixed, mixed
Conjunction sequence is that isocyanates is added in epoxy resin, and mixing speed is used to be stirred for 300r/min, adjustment temperature
Degree is 210 DEG C, cools the temperature to 45 DEG C after it reacts 1h, and the polyoxypropyleneglycol 40kg that molecular weight is 800 is added, and is kept
It stirs and slowly adjusts temperature to 70 DEG C, be cooled to room temperature up to epoxy resin polyalcohol, for use after reacting 2h；
(2) prepared by terminal isocyanate group base polyurethane prepolymer for use as: taking the castor oil modified dihydric alcohol of 100kg molecular weight 2000 to heat and rises
Temperature is to 110 DEG C and is evacuated to -0.098MPa, this process stir process, mixing speed 450r/min, is kept stirring dehydration 2h
After be cooled to 45 DEG C, be proportionally added into 120kg liquefied mdi, adjustment temperature keeps stirring to 70 DEG C after the no longer upper punching of reaction temperature
The base polyurethane prepolymer for use as being cooled to room temperature after reacting 2h up to terminal isocyanate group is mixed, for use；
(3) prepared by component A: extracting epoxy resin polyalcohol 20kg, benzoic anhydride polyester polyol 18kg, castor oil 3kg, castor oil modified
Polyalcohol 23kg, nitrogen phosphorus halogen-free flame retardants 25kg, aluminium hydroxide 8kg, fumed silica 1.5kg, lauric acid bismuth 0.05kg high
Speed dispersion stirs evenly, revolving speed 1200r/min, up to component A after stirring 2h；
(4) prepared by B component: taking terminal isocyanate group base polyurethane prepolymer for use as 70kg, nitrogen phosphorus halogen-free flame retardants 25kg, gas phase titanium dioxide
Silicon 0.5kg, adhesion promoter BYK4500 0.1kg high speed dispersion stir evenly, revolving speed 1200r/min, up to B after stirring 2h
Component.
A kind of adhesive for polyurethane for power battery PACK structural bond made of above embodiments, test its-
Shear strength after 30 DEG C, 25 DEG C, 45 DEG C and double 85 aging 1000h, the modulus at 25 DEG C, volume resistivity and fire-retardant
Property.Shear strength test exemplar does not do any surface treatment.
Shear strength of the present invention is tested according to GB/T 7124-2008, and modulus is tested using dynamic thermomechanical analysis, body
Product resistivity is tested according to GBT1410-2006, and anti-flammability presses UL94 standard testing.Test result is as shown in table 1.
Table 1
A kind of anti-flammability (U polyurethane gluing for power battery PACK structural bond of the invention as can be seen from the table
Agent has excellent fever adhesive property to the plastic materials such as PI, PET, PC and aluminium alloy in -30 DEG C of -45 DEG C of temperature ranges, together
When there is low modulus, high tenacity, high resistivity and high flame-retardant property, it is ensured that power battery in high-frequency vibration, Yin Dongxia,
Use state under high temperature difference operating condition caused by the factors such as domain, battery-heating.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of adhesive for polyurethane for power battery PACK structural bond, which is characterized in that by two kinds of component groups of A, B
At the volume ratio of component A and B component is 1:1；By weight, wherein component A is made of following material: epoxy resin modification
5-20 parts of polyalcohol, 0-3 parts of 10-25 parts of 15-30 parts of polyalcohol, biopolyol, crosslinking agent, catalyst 0- containing phenyl ring
0.05 part, 20-35 parts of fire retardant, 3-10 parts of molecular sieve, 0-5 parts of thixotropic agent；B component is made of following material: isocyanate terminated
0.1-0.3 parts of 18-30 parts of 0-20 parts of 50-70 parts of base polyurethane prepolymer for use as, isocyanates, fire retardant, the adhesion promoter of base divide
3-10 parts, 0-5 parts of thixotropic agent of son sieve；
The epoxy resin modification polyalcohol, preparation method include the following steps: epoxy resin and isocyanates equimolar
Than mixing, order by merging is that isocyanates is added in epoxy resin, stir process in adding procedure, mixing speed 200-
300r/min, it is 200-220 DEG C that adjustment temperature is kept stirring after addition, is cooled to 40-50 DEG C after it reacts 0.5-2h,
Equimolar polyalcohol is added, adjustment temperature is 70-80 DEG C, is kept stirring and is cooled to room temperature after it reacts 1.5-3h up to ring
Oxygen resin modified polyalcohol；The epoxy resin is in bisphenolA-glycidol ether epoxy resin or Bisphenol F diglycidyl ether
One or two kinds of mixing；The polyalcohol is the polyoxypropyleneglycol of molecular weight 400-2000, in polypropylene oxide triol
One or two kinds of mixing.
2. adhesive for polyurethane according to claim 1, which is characterized in that the polyurethane prepolymer of the terminal isocyanate group
The preparation method of body includes the following steps: dihydric alcohol being heated to 100-115 DEG C, is evacuated to -0.098MPa, this mistake
Journey stir process, mixing speed 300-500r/min are cooled to 40-55 DEG C after being kept stirring dehydration 1.5-2.5h, are added different
Cyanate, control theory NCO content are 8-18%, and adjustment temperature is kept stirring to 70-80 DEG C after the no longer upper punching of reaction temperature
The base polyurethane prepolymer for use as up to terminal isocyanate group is cooled to room temperature after reaction 1.5-3h;The dihydric alcohol is molecular weight 1000-
3000 polyoxypropyleneglycol, U.S. Vertellus production the mixing of one or both of castor oil modified dihydric alcohol.
3. adhesive for polyurethane according to claim 1, which is characterized in that the polyalcohol containing phenyl ring is raw for A Kema
One of bisphenol A polyether glycol, Hua Da chemistry or phthalic anhydride polyester diol of magnificent peak new material production of production are a variety of；It is described
Isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene dimethylene diisocyanate, liquefied mdi, gathers
Close one of MDI or a variety of.
4. adhesive for polyurethane according to claim 1, which is characterized in that the biopolyol is castor oil, hydrogen
Change one of castor oil, soybean oil, palm oil or a variety of；The crosslinking agent is hydroxyl value 300-500mgKOH/g, degree of functionality 4-6
Polyether polyol；The catalyst is bismuth neodecanoate, lauric acid bismuth, isooctyl acid bismuth, bismuth naphthenate, zinc neodecanoate, isooctyl acid
One of zinc, zinc naphthenate or arbitrary proportion it is a variety of；The fire retardant is nitrogen phosphorus series non-halogen fire retardant, aluminium hydroxide, hydrogen
One of magnesia is a variety of；The thixotropic agent is fumed silica;The adhesion promoter be BYK4500 and
Two kinds of one of BYK4510 or arbitrary proportion.
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| CN201811507941.9A CN109609081A (en) | 2018-12-11 | 2018-12-11 | A kind of adhesive for polyurethane for power battery PACK structural bond |
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| CN201811507941.9A CN109609081A (en) | 2018-12-11 | 2018-12-11 | A kind of adhesive for polyurethane for power battery PACK structural bond |
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| CN110105909A (en) * | 2019-06-04 | 2019-08-09 | 无锡市万力粘合材料股份有限公司 | Lithium ion battery packet is bonded and sealed the preparation method with polyurethane binder |
| CN110343501A (en) * | 2019-08-16 | 2019-10-18 | 同光（江苏）新材料科技有限公司 | A kind of lithium battery polyurethane AB glue |
| CN111303820A (en) * | 2020-03-09 | 2020-06-19 | 杭州之江新材料有限公司 | Double-component polyurethane structural adhesive for bonding power battery and preparation method thereof |
| CN111534268A (en) * | 2020-04-22 | 2020-08-14 | 湖北回天新材料股份有限公司 | Low-viscosity high-thermal-conductivity bi-component polyurethane adhesive and preparation method and application thereof |
| WO2020227964A1 (en) * | 2019-05-15 | 2020-11-19 | Dow Global Technologies Llc | Two-component adhesive compositions, articles prepared with same and preparation methods thereof |
| CN114539964A (en) * | 2022-02-16 | 2022-05-27 | 苏州赛伍应用技术股份有限公司 | Bi-component polyurethane adhesive for bonding power battery structure and preparation method thereof |
| CN115260972A (en) * | 2022-05-31 | 2022-11-01 | 世晨材料技术(上海)有限公司 | Bio-based two-component polyurethane structural adhesive |
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| CN114539964A (en) * | 2022-02-16 | 2022-05-27 | 苏州赛伍应用技术股份有限公司 | Bi-component polyurethane adhesive for bonding power battery structure and preparation method thereof |
| CN115260972A (en) * | 2022-05-31 | 2022-11-01 | 世晨材料技术(上海)有限公司 | Bio-based two-component polyurethane structural adhesive |
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Address after: No.3-3 Kaifeng Road, Yantai Development Zone, Shandong Province Applicant after: Yantai Debang Technology Co.,Ltd. Address before: No.3-3 Kaifeng Road, Yantai Development Zone, Shandong Province Applicant before: DARBOND TECHNOLOGY Co.,Ltd. |
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Application publication date: 20190412 |