CN114045148A - Light-heat dual-curing adhesive and application thereof in blade lithium battery for vehicle - Google Patents
Light-heat dual-curing adhesive and application thereof in blade lithium battery for vehicle Download PDFInfo
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- CN114045148A CN114045148A CN202111457774.3A CN202111457774A CN114045148A CN 114045148 A CN114045148 A CN 114045148A CN 202111457774 A CN202111457774 A CN 202111457774A CN 114045148 A CN114045148 A CN 114045148A
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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
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/2845—Monohydroxy epoxy 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
- H01M50/227—Organic material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a light-heat dual-curing heat-conducting adhesive and a preparation method and application thereof, wherein the heat-conducting adhesive comprises silicone oil modified polyurethane epoxy acrylate, heat-conducting filler and other auxiliaries, and a sample prepared from the heat-conducting adhesive composition is kept still for 1000 hours in a high-temperature and high-humidity box with the temperature of 105 ℃ and the humidity of 90 ℃ under the synergistic effect of the silicone oil modified polyurethane epoxy acrylate and the polyurethane epoxy acrylate, the tensile shear strength is not less than 7Mpa, and the heat conductivity coefficient is not less than 4W/m.K. The heat-conducting adhesive disclosed by the invention can be used for a vehicle blade lithium battery, and solves the problems of weak bonding strength and thermal runaway of the vehicle blade lithium battery in a high-temperature high-humidity environment at present.
Description
Technical Field
The invention belongs to the technical field of adhesives, particularly relates to a light-heat dual-curing adhesive, and further relates to application of the light-heat dual-curing adhesive in a blade lithium battery for a vehicle.
Background
At present, the energy problem and the environmental pollution problem are continuously aggravated, and the development of new energy electric automobiles is an important strategy for meeting the national requirements of energy conservation, emission reduction and low-carbon economy. In a new energy electric automobile, the key factor determining the endurance, power and safety of the electric automobile is the performance of an automobile power battery.
Currently, mainstream automobile power batteries comprise ternary lithium batteries and lithium iron phosphate batteries. The ternary lithium battery has the characteristics of high energy density, good low-temperature performance, high reliability, long service life, longer battery life and the like, but the manufacturing cost is higher; the lithium iron phosphate battery has the advantages of high temperature resistance, low cost, convenience for mass production of automobiles, easiness in recovery of the battery, higher safety than ternary lithium, and lower cruising performance than the ternary lithium battery.
A blade lithium battery produced in volume in the year 2020 by BYD is a novel lithium iron phosphate battery, the energy density of the lithium iron phosphate battery reaches the equivalent level of a ternary lithium battery, and the cost of the lithium iron phosphate battery is reduced by 30 percent compared with the ternary lithium battery. However, in order to increase the driving range, the electric vehicle needs to arrange as many cells as possible in a certain space, so the space of the "blade lithium battery" on the vehicle is very limited. "blade lithium batteries" generate a large amount of heat during vehicle operation and accumulate in a relatively confined space over time. Because the cells in the 'blade lithium battery' are densely stacked, the heat dissipation of the middle area is relatively difficult to a certain extent, the temperature inconsistency among the cells is aggravated, and the charge-discharge efficiency of the battery is reduced and the power of the battery is influenced; in severe cases, thermal runaway can occur, which can cause safety accidents such as smoking and fire, and affect the safety and service life of the electric automobile.
Therefore, to the above problems, a heat conducting adhesive capable of conducting heat generated during the operation of the battery cells in the "blade lithium battery" away in time is urgently needed to ensure the balance of temperatures between the battery cells and between the battery packs, reduce the influence of thermal runaway, and ensure the safety of the battery and the safety of the electric automobile.
The heat-conducting adhesive matrix commonly used in the prior art comprises an epoxy resin structural adhesive and an acrylic structural adhesive, wherein the epoxy resin adhesive adopts a thermosetting mechanism, the acrylic structural adhesive adopts a photocuring mechanism, the efficiency of the epoxy resin adhesive is low, and the curing effect of the acrylic structural adhesive is influenced because the acrylic structural adhesive is not cured completely by light irradiation. In addition, when the blade lithium battery runs in an electric automobile, the blade lithium battery is in a high-temperature high-humidity vibrating environment, and the structural strength of the conventional heat conducting adhesive cannot meet the bonding strength and heat conducting requirements of the application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a photo-thermal dual-curing heat-conducting adhesive and a preparation method thereof, and aims to solve the technical problems of thermal runaway of a blade lithium battery for a vehicle and weak bonding strength in a high-temperature and high-humidity environment. The photo-thermal dual-curing adhesive has both photo-curing group carbon-carbon double bonds and thermosetting group epoxy groups, can be rapidly cured under ultraviolet irradiation through photo-thermal dual curing, can be cured in a deep layer by continuous thermosetting after the adhesive has initial viscosity, and further improves the bonding strength.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the light-heat dual-curing heat-conducting adhesive composition comprises the following components in percentage by mass:
a sample prepared from the heat-conducting adhesive composition is placed in a high-temperature and high-humidity box with the temperature of 105 ℃ and the humidity of 90 ℃ for 1000 hours, the tensile shear strength is more than or equal to 7Mpa, and the heat conductivity coefficient is more than or equal to 4W/m.K.
The silicone oil modified polyurethane epoxy acrylate is prepared from hydroxyl silicone oil, diisocyanate, hydroxyl (methyl) acrylate and epoxy propanol in the presence of a catalyst.
The polyurethane epoxy acrylate is prepared from polyethylene glycol, diisocyanate, hydroxy (meth) acrylate and epoxy propanol in the presence of a catalyst.
The hydroxyalkyl silicone oil is selected from one or more of the following substances: hydroxyethyl silicone oil, hydroxymethyl silicone oil, hydroxypropyl silicone oil and hydroxybutyl silicone oil.
The molecular weight of the polyethylene glycol is 200-400.
The diisocyanate is selected from one or more of the following: isophorone diisocyanate (IPDI), naphthalene 1, 5-diisocyanate (NDI), methylene dicyclohexyl isocyanate, methylene diphenyl diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, p-phenylene diisocyanate, 3' -dimethyldiphenyl-4, 4' -diisocyanate (DDDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), Norbornane Diisocyanate (NDI), and 4,4' -dibenzyl diisocyanate (DBDI), and combinations thereof.
The hydroxyl (meth) acrylate is selected from one or more of the following: hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate.
The catalyst may be any catalyst used for the reaction of isocyanates with hydroxyl groups. Some examples include amine catalysts such as 2,2' -dimorpholinodiethyl ether and triethylenediamine and organometallic catalysts such as dibutyltin dilaurate, dibutyltin dioctoate.
The catalyst is preferably present in an amount of 0.005 to 3.5% by weight, based on the amount of hydroxyalkyl silicone oil or polyethylene glycol.
The molar ratio of the hydroxyl silicone oil/polyethylene glycol, diisocyanate, hydroxyl (meth) acrylate and epoxypropanol is 1:2:1: 1.
The cross-linking agent is trimethylolpropane triacrylate.
The photoinitiator is selected from one or more of the following: benzyl ketals, hydroxyketones, amine ketones and acyl phosphine oxides such as 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4, 6-triphenylbenzoyl) -phosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, benzoin dimethyl ketal dimethoxyacetophenone, α -hydroxybenzylphenyl ketone, 1-hydroxy-1-methylethylphenyl ketone, oligo-2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone, benzophenone; methyl o-benzylbenzoate; methyl benzoylformate, 2-diethoxyacetophenone, 2-di-sec-butoxyacetophenone, p-phenylbenzophenone, 2-isopropylthioxanthone, 2-methylanthrone, 2-ethylanthrone, 2-chloroanthrone, 1, 2-benzanthrone, benzoyl ether, benzoin methyl ether; benzoin isopropyl ether, alpha-phenylbenzoin, thioxanthone, diethyl thioxanthone, 1, 5-naphthalenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-dimethylaminobenzoate. These photoinitiators may be used alone or in combination with one another.
In a preferred embodiment, the photoinitiator is bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide or Irgacure 819.
The thermal curing agent is selected from one or more of the following substances: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, aliphatic modified amine, aromatic amine, phthalic anhydride, and dicyandiamide.
The heat-conducting filler is selected from one or more of the following substances: aluminum nitride, boron nitride, silicon carbide, magnesium oxide, aluminum oxide, fibrous carbon powder, flaky carbon powder, and graphene.
The heat-conducting filler is treated by a silane coupling agent.
The second purpose of the invention is to provide a preparation method of the photo-thermal dual-curing heat-conducting adhesive, which comprises the following steps:
s1, preparation of silicone oil modified polyurethane epoxy acrylate:
adding hydroxypropyl silicone oil into a container, vacuum dehydrating at 100-130 ℃, cooling to 70-90 ℃, adding diisocyanate and a catalyst, and reacting for 2-6h at 70-90 ℃; adding hydroxyl methacrylate and epoxy propanol, and reacting at 50-80 deg.C for 2-5h to obtain silicone oil modified polyurethane epoxy acrylate;
s2, preparation of polyurethane epoxy acrylate:
adding polyethylene glycol into a container, vacuum dehydrating at 100-130 ℃, cooling to 70-90 ℃, adding diisocyanate and a catalyst, and reacting for 2-6h at 70-90 ℃; then adding methacrylic acid hydroxyl ester and epoxy propanol, and reacting for 2-5h at 50-80 ℃ to obtain polyurethane epoxy acrylate;
and S3, stirring and mixing the raw materials except the heat-conducting filler uniformly in a container according to the formula, adding the heat-conducting filler, and stirring and mixing uniformly to obtain the light-heat dual-curing adhesive.
The invention also provides an application of the photo-thermal dual curing adhesive in a blade lithium battery for a vehicle, and particularly relates to an application of the photo-thermal dual curing adhesive in a heat-conducting adhesive medium between a battery core and a cover plate or a bottom plate in the blade lithium battery for the vehicle.
Compared with the prior art, the invention has the following advantages:
(1) the invention creatively selects the silicone oil modified polyurethane epoxy acrylate and the polyurethane epoxy acrylate as the main resin part of the photo-thermal dual-curing adhesive, on one hand, epoxy provides a thermosetting group, and acrylate provides a photo-curing group, and on the other hand, the addition of silicone oil brings about the improvement of the overall bonding strength of the adhesive.
(2) The inventor creatively discovers that the silicone oil modified polyurethane epoxy acrylate and the polyurethane epoxy acrylate generate a synergistic effect in an adhesive system, so that the adhesive strength of the adhesive is improved in a high-temperature and high-humidity environment.
(3) The inventor creatively discovers that a certain amount of heat-conducting filler is introduced into a light-heat dual-curing adhesive system, so that the heat-conducting property of the adhesive is improved while the adhesive property is not influenced, and the thermal runaway problem of the automotive blade lithium battery is well solved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Preparation example 1
Preparation of silicone oil modified polyurethane epoxy acrylate Si-APUE-1:
adding 0.01mol of hydroxypropyl silicone oil into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, carrying out vacuum dehydration at 120 ℃ for 2h, reducing the temperature to 80 ℃, adding a mixed solution of 0.02mol of isophorone diisocyanate and 0.03 wt% (mass fraction of hydroxypropyl silicone oil) of dibutyltin dilaurate, and reacting at 80 ℃ for 4 h; then 0.01mol of hydroxyethyl methacrylate and 0.01mol of epoxy propanol are added to react for 3h at 60 ℃ to obtain the silicone oil modified polyurethane epoxy acrylate Si-APUE-1.
Preparation example 2
Preparation of silicone oil modified polyurethane epoxy acrylate Si-APUE-2:
adding 0.01mol of hydroxyethyl silicone oil into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, dehydrating for 2 hours at 120 ℃ in vacuum, reducing the temperature to 80 ℃, adding a mixed solution of 0.02mol of methylene diphenyl diisocyanate and 0.03 wt% (mass fraction of hydroxyethyl silicone oil) of dibutyltin dilaurate, and reacting for 4 hours at 80 ℃; then 0.01mol of hydroxypropyl (methyl) acrylate and 0.01mol of epoxy propanol are added to react for 3h at 60 ℃ to obtain the silicone oil modified polyurethane epoxy acrylate Si-APUE-2.
Preparation example 3
Preparation of silicone oil modified polyurethane epoxy acrylate Si-APUE-3:
adding 0.01mol of hydroxybutyl silicone oil into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, dehydrating for 2 hours in vacuum at 120 ℃, then reducing the temperature to 80 ℃, adding a mixed solution of 0.02mol of norbornane diisocyanate and 0.03 wt% (mass fraction of hydroxybutyl silicone oil) of dibutyltin dilaurate, and reacting for 4 hours at 80 ℃; then 0.01mol of hydroxybutyl (methyl) acrylate and 0.01mol of epoxy propanol are added to react for 3 hours at the temperature of 60 ℃ to obtain the silicone oil modified polyurethane epoxy acrylate Si-APUE-3.
Preparation example 4
Preparation of polyurethane epoxy acrylate APUE-1:
adding 0.01mol of polyethylene glycol 200 into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, carrying out vacuum dehydration at 120 ℃ for 2h, reducing the temperature to 80 ℃, adding a mixed solution of 0.02mol of isophorone diisocyanate and 0.03 wt% (mass fraction of polyethylene glycol 200) of dibutyltin dilaurate, and reacting at 80 ℃ for 4 h; then 0.01mol of hydroxyethyl methacrylate and 0.01mol of epoxy propanol are added to react for 3h at 60 ℃ to obtain the polyurethane epoxy acrylate APUE-1.
Preparation example 5
Preparation of polyurethane epoxy acrylate APUE-2:
adding 0.01mol of polyethylene glycol 300 into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, carrying out vacuum dehydration at 120 ℃ for 2h, reducing the temperature to 80 ℃, adding a mixed solution of 0.02mol of methylene diphenyl diisocyanate and 0.03 wt% (mass fraction of polyethylene glycol 300) of dibutyltin dilaurate, and reacting at 80 ℃ for 4 h; then 0.01mol of hydroxypropyl (methyl) acrylate and 0.01mol of epoxy propanol are added to react for 3 hours at 60 ℃ to obtain the polyurethane epoxy acrylate APUE-2.
Preparation example 6
Preparation of polyurethane epoxy acrylate APUE-3:
adding 0.01mol of polyethylene glycol 400 into a three-neck flask provided with a stirrer, a thermometer and a nitrogen introducing device, carrying out vacuum dehydration at 120 ℃ for 2h, reducing the temperature to 80 ℃, adding a mixed solution of 0.02mol of norbornane diisocyanate and 0.03 wt% (mass fraction of polyethylene glycol 400) of dibutyltin dilaurate, and reacting at 80 ℃ for 4 h; then 0.01mol of hydroxybutyl (meth) acrylate and 0.01mol of epoxypropanol are added and reacted for 3 hours at 60 ℃ to obtain the polyurethane epoxy acrylate APUE-3.
Example 1
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-1 20％
APUE-1 30％
10 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
30% KH550 treated silicon nitride;
and secondly, stirring and mixing Si-APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 2
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-1 15％
APUE-1 30％
trimethylolpropane triacrylate 20%
Irgacure 819 1％
Ethylenediamine 9%
25% KH550 treated silicon nitride;
and secondly, stirring and mixing Si-APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 3
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-1 10％
APUE-1 30％
30 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
KH550 treated silicon nitride 20%;
and secondly, stirring and mixing Si-APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 4
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-2 20％
APUE-2 30％
10 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
30% KH550 treated silicon nitride;
and secondly, stirring and mixing Si-APUE-2, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 5
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-2 15％
APUE-2 30％
trimethylolpropane triacrylate 20%
Irgacure 819 1％
Ethylenediamine 9%
25% of silicon nitride treated with KH 550.
And secondly, stirring and mixing Si-APUE-2, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 6
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-2 10％
APUE-2 30％
30 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
KH550 treated silicon nitride 20%.
And secondly, stirring and mixing Si-APUE-2, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 7
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-3 20％
APUE-3 30％
10 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
30% KH550 treated silicon nitride;
and secondly, stirring and mixing Si-APUE-3, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Example 8
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-1 20％
APUE-1 30％
10 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
30% KH550 treated silicon nitride;
and secondly, stirring and mixing Si-APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon carbide, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Comparative example 1
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-1 50％
10 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
30% of silicon nitride treated with KH 550.
And secondly, stirring and mixing Si-APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the photo-thermal dual-curing adhesive.
Comparative example 2
Preparing a light-heat dual curing adhesive with heat conductivity:
firstly, preparing the following raw materials in percentage by mass:
APUE-1 50％
10 percent of trimethylolpropane triacrylate
Irgacure 819 1％
Ethylenediamine 9%
30% of silicon nitride treated with KH 550.
And secondly, stirring and mixing APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine uniformly in a container according to the formula, adding silicon nitride, and stirring and mixing uniformly to obtain the light-heat dual-curing adhesive.
Comparative example 3
Preparing the photo-thermal dual curing adhesive:
firstly, preparing the following raw materials in percentage by mass:
Si-APUE-1 30％
APUE-1 40％
trimethylolpropane triacrylate 20%
Irgacure 819 1％
Ethylenediamine 9%
And secondly, stirring and uniformly mixing Si-APUE-1, trimethylolpropane triacrylate, Irgacure 819 and ethylenediamine in a container according to the formula to obtain the photo-thermal dual-curing adhesive.
Sample preparation and performance testing:
preparation of tensile shear property test sample: the photo-thermal dual curing adhesives of examples 1 to 8 and comparative examples 1 to 3 were coated on transparent PET, each PET was 100mm (length)/25 mm (width)/1.5 mm (thickness), each adhered test piece was glued over its entire width, the length of the glue was 12.5mm, the typical thickness of the glue was 0.2mm, and the two PET test pieces were adhered together, ensuring accurate alignment of the two adhered test pieces and as uniform as possible the thickness of the glue layer.
Curing the PET bonding sheet coated with the adhesive in a mode of combining ultraviolet light and heating, primarily curing the PET bonding sheet for 10 seconds under an ultraviolet light source with the wavelength of 350-400nm, and then curing and molding the PET bonding sheet in an environment with the temperature of 85 ℃ for 20 min; and then placing the PET bonding sheet in a high-temperature high-humidity box with the temperature of 105 ℃ and the humidity of 90 ℃, standing for 1000h, and taking out to be tested.
Preparation of a heat conduction performance test sample: the photo-thermal dual curing adhesives of examples 1 to 8 and comparative examples 1 to 3 were placed in a mold cavity having a diameter of 2cm and a height of 1cm to make the thickness of the sample as uniform as possible without bubbles.
Curing the sample in the mold by combining ultraviolet light and heating, primarily curing the sample for 10s under an ultraviolet light source with the wavelength of 350-400nm, and then curing, molding and demolding the sample in an environment with the temperature of 85 ℃ for 20 min; and then placing the sample in a high-temperature high-humidity box with the temperature of 105 ℃ and the humidity of 90 ℃, standing for 1000h, and taking out the sample to be tested.
And (3) performance testing:
tensile shear properties and thermal conductivity were tested according to GB/T7124-.
TABLE 1
Comparing examples 1,3,7-8 and comparative examples 1-2 in table 1, it can be seen that the silicone oil modified polyurethane epoxy acrylate and the polyurethane epoxy acrylate have a synergistic effect, and the combination of the silicone oil modified polyurethane epoxy acrylate and the polyurethane epoxy acrylate improves the adhesive property of the adhesive, which is reflected by the improvement of the tensile shear strength.
Comparing examples 1-3 and 4-6 in table 1, it can be seen that the adhesive performance of the adhesive is improved with the increase of the content of the silicone oil modified polyurethane epoxy acrylate in the adhesive, which indicates that the introduction of the silicon-oxygen bond in the adhesive molecular network brings about the improvement of the network adhesive force, which is reflected in the improvement of the tensile shear strength.
Comparing examples 1-3,4-6 and comparative example 3 in table 1, it can be seen that as the content of the heat conductive filler in the adhesive is increased, the heat conductive property of the adhesive is increased, which is reflected by the increase of the heat conductivity coefficient.
Claims (7)
1. The light-heat dual-curing heat-conducting adhesive composition is characterized by comprising the following components in percentage by mass:
a sample prepared from the heat-conducting adhesive composition is placed in a high-temperature and high-humidity box with the temperature of 105 ℃ and the humidity of 90 ℃ for 1000 hours, the tensile shear strength is more than or equal to 7Mpa, and the heat conductivity coefficient is more than or equal to 4W/m.K.
2. The light-heat dual-curing heat-conducting adhesive composition as claimed in claim 1, wherein the silicone oil-modified polyurethane epoxy acrylate is prepared from hydroxy alkyl silicone oil, diisocyanate, hydroxy (meth) acrylate and epoxy propanol in the presence of a catalyst;
the polyurethane epoxy acrylate is prepared from polyethylene glycol, diisocyanate, hydroxy (meth) acrylate and epoxy propanol in the presence of a catalyst.
3. The photo-thermal dual-curing thermal conductive adhesive composition of claim 2, wherein the hydroxy-hydrocarbon silicone oil is selected from one or more of the following substances: hydroxyethyl silicone oil, hydroxymethyl silicone oil, hydroxypropyl silicone oil, hydroxybutyl silicone oil;
the molecular weight of the polyethylene glycol is 200-400;
the diisocyanate is selected from one or more of the following: isophorone diisocyanate (IPDI), naphthalene 1, 5-diisocyanate (NDI), methylene dicyclohexyl isocyanate, methylene diphenyl diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, p-phenylene diisocyanate, 3' -dimethyldiphenyl-4, 4' -diisocyanate (DDDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI), Norbornane Diisocyanate (NDI), and 4,4' -dibenzyl diisocyanate (DBDI), and combinations thereof;
the hydroxyl (meth) acrylate is selected from one or more of the following: hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate;
the catalyst is selected from one or more of the following: 2,2' -dimorpholinodiethyl ether or triethylenediamine, and the organic metal catalyst is dibutyltin dilaurate or dibutyltin dioctoate.
4. The photo-thermal dual-curing thermal conductive adhesive composition according to claim 3, wherein the hydroxyl silicone oil/polyethylene glycol, diisocyanate, hydroxyl (meth) acrylate and epoxypropanol are in a molar ratio of 1:2:1: 1;
the catalyst is preferably present in an amount of 0.005 to 3.5 wt.%, based on the total weight of the composition.
5. The photo-thermal dual-curing thermal conductive adhesive composition according to any one of claims 1 to 4,
the cross-linking agent is trimethylolpropane triacrylate;
the photoinitiator is selected from one or more of the following: benzyl ketals, hydroxyketones, amine ketones and acyl phosphine oxides such as 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2,4, 6-triphenylbenzoyl) -phosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -butan-1-one, benzoin dimethyl ketal dimethoxyacetophenone, α -hydroxybenzylphenyl ketone, 1-hydroxy-1-methylethylphenyl ketone, oligo-2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone, benzophenone; methyl o-benzylbenzoate; methyl benzoylformate, 2-diethoxyacetophenone, 2-di-sec-butoxyacetophenone, p-phenylbenzophenone, 2-isopropylthioxanthone, 2-methylanthrone, 2-ethylanthrone, 2-chloroanthrone, 1, 2-benzanthrone, benzoyl ether, benzoin methyl ether; benzoin isopropyl ether, alpha-phenylbenzoin, thioxanthone, diethyl thioxanthone, 1, 5-naphthalenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-dimethylaminobenzoate;
the thermal curing agent is selected from one or more of the following substances: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, aliphatic modified amine, aromatic amine, phthalic anhydride, dicyandiamide;
the heat-conducting filler is selected from one or more of the following substances: aluminum nitride, boron nitride, silicon carbide, magnesium oxide, aluminum oxide, fibrous carbon powder, flaky carbon powder, and graphene; the heat-conducting filler is treated by a silane coupling agent.
6. A preparation method of the photo-thermal dual-curing heat-conducting adhesive as claimed in any one of claims 1 to 5, comprising the following steps:
s1, preparation of silicone oil modified polyurethane epoxy acrylate:
adding hydroxypropyl silicone oil into a container, vacuum dehydrating at 100-130 ℃, cooling to 70-90 ℃, adding diisocyanate and a catalyst, and reacting for 2-6h at 70-90 ℃; adding hydroxyl methacrylate and epoxy propanol, and reacting at 50-80 deg.C for 2-5h to obtain silicone oil modified polyurethane epoxy acrylate;
s2, preparation of polyurethane epoxy acrylate:
adding polyethylene glycol into a container, vacuum dehydrating at 100-130 ℃, cooling to 70-90 ℃, adding diisocyanate and a catalyst, and reacting for 2-6h at 70-90 ℃; then adding methacrylic acid hydroxyl ester and epoxy propanol, and reacting for 2-5h at 50-80 ℃ to obtain polyurethane epoxy acrylate;
and S3, stirring and mixing the raw materials except the heat-conducting filler uniformly in a container according to the formula, adding the heat-conducting filler, and stirring and mixing uniformly to obtain the light-heat dual-curing adhesive.
7. The application of the photo-thermal dual-curing heat-conducting adhesive as claimed in any one of claims 1 to 5 in a blade lithium battery for a vehicle, in particular as a heat-conducting adhesive medium between a battery cell and a cover plate or a bottom plate in the blade lithium battery.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907538A (en) * | 2022-06-27 | 2022-08-16 | 韦尔通(厦门)科技股份有限公司 | Ultraviolet curing resin, ultraviolet curing adhesive and preparation method thereof |
| CN115197670A (en) * | 2022-08-29 | 2022-10-18 | 烟台市福山义昌精细化工厂 | Special sealant for petroleum casing screw threads and preparation method thereof |
| CN115368819A (en) * | 2022-07-08 | 2022-11-22 | 深圳市派恩新材料技术有限公司 | Fluorine-containing coating and preparation method and use method thereof |
| CN115572528A (en) * | 2022-11-15 | 2023-01-06 | 佛山市高明区首邦化工有限公司 | Anticorrosive paint for furniture and preparation method and application thereof |
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| CN110467901A (en) * | 2018-05-10 | 2019-11-19 | 上海本诺电子材料有限公司 | OLED heats dual UV curable paint organic silicon modified epoxy acrylate glue and preparation method with UV |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110467901A (en) * | 2018-05-10 | 2019-11-19 | 上海本诺电子材料有限公司 | OLED heats dual UV curable paint organic silicon modified epoxy acrylate glue and preparation method with UV |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114907538A (en) * | 2022-06-27 | 2022-08-16 | 韦尔通(厦门)科技股份有限公司 | Ultraviolet curing resin, ultraviolet curing adhesive and preparation method thereof |
| CN114907538B (en) * | 2022-06-27 | 2023-07-14 | 韦尔通科技股份有限公司 | Ultraviolet light curing resin, ultraviolet light curing adhesive and preparation method thereof |
| CN115368819A (en) * | 2022-07-08 | 2022-11-22 | 深圳市派恩新材料技术有限公司 | Fluorine-containing coating and preparation method and use method thereof |
| CN115197670A (en) * | 2022-08-29 | 2022-10-18 | 烟台市福山义昌精细化工厂 | Special sealant for petroleum casing screw threads and preparation method thereof |
| CN115572528A (en) * | 2022-11-15 | 2023-01-06 | 佛山市高明区首邦化工有限公司 | Anticorrosive paint for furniture and preparation method and application thereof |
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