CN109337630B

CN109337630B - Preparation method of double-component room-temperature fast-curing anti-seismic heat-conducting structure adhesive

Info

Publication number: CN109337630B
Application number: CN201811227378.XA
Authority: CN
Inventors: 陈建浩; 陈钢; 韩驰旻
Original assignee: Guangzhou Yinhan Energy Technology Co ltd
Current assignee: Guangzhou Yinhan Energy Technology Co ltd
Priority date: 2018-10-22
Filing date: 2018-10-22
Publication date: 2022-12-13
Anticipated expiration: 2038-10-22
Also published as: CN109337630A

Abstract

The invention discloses a double-component room temperature fast curing anti-seismic heat-conducting structural adhesive which comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 50-100 parts of silane terminated polyether resin, 0-50 parts of plasticizer, 300-600 parts of heat conducting material, 20-200 parts of flame retardant material, 5-60 parts of epoxy resin curing agent, 0-10 parts of coupling agent and 0-10 parts of antioxidant, wherein the component B comprises the following raw materials in parts by weight: 20-100 parts of epoxy resin, 20-50 parts of plasticizer, 300-600 parts of heat conducting material, 20-200 parts of flame retardant material, 0-10 parts of coupling agent, 0-10 parts of water removing agent, 0-20 parts of thixotropic agent and 0-10 parts of catalyst. The double-component room-temperature fast-curing anti-seismic heat-conducting structural adhesive can be applied to heat-conducting bonding between a new energy automobile power battery module and a water-cooling system, so that the effective release of heat generated in the use process of a power battery is met, and the power battery is protected from overheating loss.

Description

Preparation method of double-component room-temperature fast-curing anti-seismic heat-conducting structure adhesive

Technical Field

The invention belongs to the technical field of new energy automobile power battery modules, and particularly relates to a double-component room-temperature fast-curing anti-seismic heat-conducting structure adhesive and a preparation method thereof.

Background

With the development and the upgrade of new energy automobile technology, the requirements on the energy density and the battery capacity of a power battery are higher and higher, the energy density of a single power battery cell is correspondingly improved, the heat productivity of a power battery module is higher and higher during working, and the power battery is damaged by high temperature for a long time, so that the driving endurance mileage of the new energy automobile is influenced. At present, novel new energy automobile power battery modules can be equipped with a water-cooling active cooling system for solving the problems.

Regard as new energy automobile power battery module and water-cooling system's heat-conduction with heat conduction silica gel or heat conduction silica gel gasket and link, heat conduction silica gel is high with heat conduction silica gel gasket heat conductivity, and the compliance is high, but body intensity is low, probably leads to the colloid to damage when the car shakes for a long time or violent collision strikes and makes heat conduction link inefficacy to make the battery heat save the harm battery.

The patent named "two-component adhesive for assembling power lithium battery modules" (application publication No. CN 106367013A) discloses a two-component epoxy resin flame-retardant heat-conducting structural adhesive applied to the assembly of lithium battery modules. But the curing hardness is larger, the tensile shear strength and the tensile strength are not reflected, and the brittle fracture characteristic of the epoxy resin body has the risk of fracture failure of the bonding surface in the long-term vibration fatigue environment of the automobile.

Meanwhile, the automobile manufacturing industry is one of the industries with the highest degree of automation, and the automatic production has high requirements on the production speed and the production rhythm. The electric core of the new energy automobile power battery module is large in quantity, the stacking three-dimensional structure of the electric core is complex, and the requirement on the bonding speed of the adhesive is very high for the design scheme of the electric core module bonded by the adhesive. And the battery core is sensitive to high temperature, and the rapid bonding of the adhesive can not be realized through high-temperature baking. Therefore, the adhesive which is rapidly cured at room temperature is particularly important for a bonding scheme of a new energy automobile power battery module. The epoxy resin adhesive, the polyurethane adhesive and the acrylic acid adhesive which are rapidly cured at room temperature at present can release a large amount of heat in the curing process, so that the local heating temperature of the power battery in the dispensing process is too high, and the power battery can be damaged.

A patent (patent No. CN 104559901B) named as 'a two-component adhesive and a preparation method and application thereof' discloses that the two-component polyurethane flame-retardant heat-conducting adhesive is applied to bonding of a cell and a cell film. But the curing condition requires 45 ℃ 3hrs +25 ℃ 72hrs, and additional heating and baking conditions are needed to achieve curing and bonding. Meanwhile, the curing time is long, the wiring requirement on an automatic production line is long, and the beat and the speed of the highly automatic production of the automobile are influenced.

In conclusion, although the heat-conducting flame-retardant structural adhesive is applied to the new energy automobile power battery industry, the application does not comprehensively consider all properties.

Disclosure of Invention

The invention aims to provide a preparation method of a double-component room-temperature fast-curing anti-seismic heat-conducting structural adhesive, which aims to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a double-component room temperature fast curing anti-seismic heat conduction structure adhesive comprises a component A and a component B, wherein the component A is composed of the following raw materials in parts by weight: 50-100 parts of silane terminated polyether resin, 0-50 parts of plasticizer, 300-600 parts of heat conducting material, 20-200 parts of flame retardant material, 5-60 parts of epoxy resin curing agent, 0-10 parts of coupling agent and 0-10 parts of antioxidant, wherein the component B comprises the following raw materials in parts by weight: 20-100 parts of epoxy resin, 20-50 parts of plasticizer, 300-600 parts of heat conducting material, 20-200 parts of flame retardant material, 0-10 parts of coupling agent, 0-10 parts of water removing agent, 0-20 parts of thixotropic agent and 0-10 parts of catalyst.

Preferably, the silane-terminated polyether resin is any one or a mixture of several of dimethoxysilane-terminated polyether, trimethoxysilane-terminated polyether, triethoxysilane-terminated polyether and dimethoxysilane one-side-terminated polyether, wherein a plurality of silane-terminated polyethers are mixed to obtain ideal properties such as tensile strength, tensile deformation rate, curing speed, adhesive strength, and the like, and commercially available products such as Japanese bell-shaped S303H, S203H, S327, SAX400, SAX350, SAX260, SAT145, SAT010, SAX750, SAX725, SAX720, SAX510, SAX520, SAX530, SAX580, RS-5902; ESSX5830E, ESS8888E, ESS2410E, ESS2420E, ESS3430E, ESS3630E from Asahi glass, japan, and the like.

Preferably, the plasticizer is any one or a mixture of diisodecyl phthalate, diisononyl phthalate, 3000 molecular weight polyether triol and 2000 molecular weight polyether diol.

Preferably, the heat conduction material is any one or a combination of a plurality of materials selected from alpha-aluminum oxide, zinc oxide, magnesium oxide, boron nitride and aluminum nitride, wherein the particle size of the heat conduction material is 0.1-150 micrometers, the particle size shape comprises irregular shape, spherical shape, sphere-like shape, needle shape and sheet shape, the more the heat conduction material is added, the higher the heat conduction performance is, the lower the corresponding elongation at break is, and the higher the viscosity is, so that the heat conduction material is not suitable for automatic use.

Preferably, the flame retardant material is an additive type flame retardant comprising any one or a mixture of more of aluminum hydroxide, magnesium hydroxide, organic montmorillonite, ammonium polyphosphate, aluminum hypophosphite, diphenyl phosphate, melamine, pentaerythritol, dimethyl methylphosphonate, diethyl ethylphosphate, chlorinated paraffin, antimony trioxide and decabromodiphenylethane, and commercially available products such as Exolite AP422, exolite AP462, exolite AP482, exolite OP935, exolite OP1230, exolite 1240 and the like, of Clariant, germany.

Preferably, the epoxy resin curing agent comprises any one or a mixture of triethylene tetramine, N-aminoethyl piperazine, isophorone diamine, 2,4, 6-tris (dimethylaminomethyl) phenol and 2-ethyl-4-methylimidazole.

Preferably, the coupling agent is any one or a mixture of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-gamma-aminopropyltriethoxysilane and N-gamma-aminopropyltrimethoxysilane, the antioxidant is any one or a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, and the commercially available coupling agents such as Irganox 245, irganox 1010 from BASF, AT-10, AT-626, PW9225, PW9228 from Yabao, and the like.

Preferably, the epoxy resin is any one or a mixture of more of E54 type bisphenol A diglycidyl ether, E51 type bisphenol A diglycidyl ether, E44 type bisphenol A diglycidyl ether, E41 type bisphenol A diglycidyl ether and cardanol modified glycidyl ether, and is commercially available as cadrley NC-514, NC-541S and the like, and the water scavenger is any one or a mixture of more of vinyltriethoxysilane, vinyltrimethoxysilane, monocyclic oxazolidine and bicyclic oxazolidine.

Preferably, the thixotropic agent is any one or more of fumed silica, nano calcium carbonate, polyamide wax and modified castor oil, and the catalyst is any one or more of dibutyltin bis (acetylacetonate), 1, 3-tetrabutyl-1, 3-didodecyloxy distannoxane, dibutyltin dilaurate, organotin of stannous octoate and chelated tin catalyst.

A preparation method of a double-component room temperature fast curing anti-seismic heat-conducting structural adhesive comprises the following steps:

s1, preparing a component A, adding silane-terminated polyether resin into a planetary stirrer, adding a plasticizer, adding a heat conduction material, an antioxidant and a flame-retardant material during stirring, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing at high speed for 120 minutes, cooling to a temperature of less than 60 ℃ under a vacuum state, adding an epoxy curing agent, stirring for 10 minutes under a vacuum of-95 kpa, adding a coupling agent, stirring for 5 minutes, vacuumizing to-95 kpa, and stirring for 30 minutes until the mixture is uniformly stirred to obtain the component A;

s2, preparing a component B, namely adding epoxy resin into a planetary stirrer, adding a plasticizer during stirring, adding a heat conduction material and a flame retardant material, adding a half amount of a water removing agent, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing for 120 minutes at high speed at high temperature, keeping the temperature under a vacuum state, cooling to less than 50 ℃, adding the remaining half amount of the water removing agent, stirring for 10 minutes under vacuum-90 kpa, adding a coupling agent, stirring for 10 minutes under vacuum-95 kpa, adding a catalyst, stirring for 10 minutes under vacuum-95 kpa, finally adding a thixotropic agent, and stirring for 20 minutes under vacuum-95 kpa to obtain the component B;

and S3, uniformly mixing the prepared component A and the component B according to the mass ratio of 2.

The invention has the technical effects and advantages that: the double-component room temperature fast curing anti-seismic heat conduction structure adhesive is prepared by independently preparing the component A and the component B, and adopting the mixed use of a heat conduction material, a plasticizer, a flame retardant material, an epoxy resin curing agent and the like to prepare the adhesive, so that the room temperature fast curing, heat conduction, structure bonding, anti-seismic impact resistance, flame retardance and weather resistance of a new energy automobile power battery module are improved, meanwhile, the curing agent is matched with the heat conduction material and a coupling agent for use, the curing time of the curing agent is shortened, and finally, the component A and the component B are mixed for use, so that the double-component room temperature fast curing anti-seismic heat conduction structure adhesive can be applied to the heat conduction bonding of the new energy automobile power battery module and a water cooling system, the effective release of heat generated in the using process of a power battery is met, and the power battery is protected from overheating loss.

Detailed Description

For further understanding of the present invention, the following detailed description will be made of a two-component room temperature fast curing vibration-resistant heat-conductive adhesive provided by the present invention through specific examples, and the scope of the present invention is not limited by the following examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

DINP described in the above table is diisononyl phthalate, PPG3050D is 3000 molecular weight polyether triol, DMP-30 is 2,4, 6-tris (dimethylaminomethyl) phenol, KH 540 is gamma-aminopropyltrimethoxysilane, KH550 is gamma-aminopropyltriethoxysilane, KH 560 is 3-glycidoxypropyltrimethoxysilane, KH 792 is N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, and A-171 is vinyltrimethoxysilane.

Example 1

s1, preparing a component A, namely adding 80 parts of SAX400 and 20 parts of ESSX5830E into a planetary stirrer, then adding 150 parts of alumina, 20 parts of antimony trioxide and 1 part of Irganox 245, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, performing high-temperature high-speed dispersion for 120 minutes, cooling to a temperature lower than 60 ℃ under a vacuum state, adding 8 parts of triethylene tetramine, stirring for 10 minutes under a vacuum condition of-95 kpa, adding 1 part of KH 792, stirring for 5 minutes, vacuumizing to-95 kpa, and stirring for 30 minutes until the mixture is uniformly stirred to obtain the component A;

s2, preparing a component B, namely adding 50 parts of E51 bisphenol A glycidyl ether into a planetary stirrer, adding 45 parts of chlorinated paraffin during stirring, adding 150 parts of alumina, 40 parts of antimony trioxide and 1 part of A-171, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing for 120 minutes at high temperature and high speed, cooling to a temperature lower than 50 ℃ under a vacuum state, adding 1 part of A-171, stirring for 10 minutes under vacuum-95 kpa, adding 3 parts of KH 560, stirring for 10 minutes under vacuum-95 kpa, adding 4 parts of U-220H, stirring for 10 minutes under vacuum-95 kpa, adding 17 parts of nano calcium carbonate, and stirring for 10 minutes under vacuum-95 kpa to obtain the component B;

Example 2

s1, preparing a component A, adding 70 parts of S303H and 30 parts of SAX580 into a planetary stirrer, adding 30 parts of PPG3050D in the stirring process, then adding 200 parts of alumina, 100 parts of organic bentonite and 1 part of Irganox 245, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing at high temperature and high speed for 120 minutes, cooling to a temperature of less than 60 ℃ under a vacuum state, adding 15 parts of isophorone diamine, stirring for 10 minutes under vacuum of-95 kpa, adding 1 part of KH550, stirring for 5 minutes, vacuumizing to-95 kpa, and stirring for 30 minutes until the mixture is uniformly stirred to obtain the component A;

s2, preparing a component B, namely adding 50 parts of E44 bisphenol A glycidyl ether into a planetary stirrer, adding 50 parts of PPG3050D in the stirring process, then adding 200 parts of alumina and 100 parts of organic bentonite, adding 1 part of A-171, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, performing high-temperature high-speed dispersion for 120 minutes, cooling to a temperature lower than 50 ℃ under a vacuum state, adding 1 part of A-171, stirring for 10 minutes under vacuum-95 kpa, adding 2 parts of KH 540, stirring for 10 minutes under vacuum-95 kpa, adding 4 parts of U-130, stirring for 10 minutes under vacuum-95 kpa, adding 2 parts of fumed silica, and stirring for 10 minutes under vacuum-95 kpa to obtain the component B;

Example 3

s1, preparing a component A, adding 95 parts of S303H and 5 parts of SAX400 into a planetary stirrer, adding 27 parts of diisononyl phthalate in the stirring process, then adding 455 parts of alumina, 70 parts of organic bentonite, 13 parts of ExolitAP422 and 1 part of PW9225, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing at high temperature and high speed for 120 minutes, cooling to a temperature of less than 60 ℃ under a vacuum state, adding 5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, stirring for 10 minutes under vacuum of-95 kpa, adding 1 part of KH550, stirring for 5 minutes, vacuumizing to-95 kpa, and stirring for 30 minutes until the mixture is uniformly stirred to obtain the component A;

s2, preparing a component B, namely adding 25 parts of NC-514 into a planetary stirrer, adding 38 parts of diisononyl phthalate in the stirring process, adding 200 parts of alumina, 50 parts of organic bentonite and 17 parts of ExolitAP422, adding 1 part of A-171, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing for 120 minutes at high temperature and high speed, cooling to a temperature lower than 50 ℃ under a vacuum state, adding 1 part of A-171, stirring for 10 minutes at vacuum-95 kpa, adding 3 parts of KH 560, stirring for 10 minutes at vacuum-95 kpa, adding 3 parts of U-220H, and stirring for 20 minutes at vacuum-95 kpa to obtain the component B;

Example 4

s1, preparing a component A, namely adding 60 parts of SAX400, 40 parts of ESSX5830E and 10 parts of SAT010 into a planetary stirrer, then adding 540 parts of alumina, 20 parts of antimony trioxide and 1 part of PW9225, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing for 120 minutes at high temperature and high speed, cooling to a temperature lower than 60 ℃ under a vacuum state, adding 10 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, stirring for 10 minutes under vacuum-95 kpa, adding 1 part of KH 792, stirring for 5 minutes, vacuumizing to-95 kpa, and stirring for 30 minutes until the mixture is uniform to obtain the component A;

s2, preparing a component B, namely adding 30 parts of E44 bisphenol A glycidyl ether and 25 parts of E51 bisphenol A glycidyl ether into a planetary stirrer, adding 40 parts of chlorinated paraffin during stirring, then adding 540 parts of alumina, 20 parts of antimony trioxide and 1 part of A-171, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing at high temperature and high speed for 120 minutes, cooling to a temperature of less than 50 ℃ under a vacuum state, adding 1 part of A-171, stirring for 10 minutes under vacuum-95 kpa, adding 4 parts of KH 560, stirring for 10 minutes under vacuum-95 kpa, adding 4 parts of U-220H, stirring for 10 minutes under vacuum-95 kpa, adding 5 parts of fumed silica, and stirring for 10 minutes under vacuum-95 kpa;

In particular, the method comprises the following steps of,

the tensile shear strength in the above table was tested in accordance with GBT 7124-2008 "determination of tensile shear strength of adhesives (rigid material vs rigid material)";

the tensile strength and the elongation at break are tested according to GBT 528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber;

thermal conductivity was determined according to ASTM _ D _5470-06 Standard Test Method for Thermal Transmission Properties of Thermal Conductive Electrical Insulation Materials;

the hardness was measured according to GBT531.1-2008 "test method for indentation hardness of vulcanized rubber or thermoplastic rubber" part 1 Shore Durometer method ".

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims

1. A double-component room temperature fast curing anti-seismic heat-conducting structural adhesive comprises a component A and a component B, wherein the component A is composed of the following raw materials in parts by weight: 50-100 parts of silane terminated polyether resin, 0-50 parts of plasticizer, 300-600 parts of heat conducting material, 20-200 parts of flame retardant material, 5-60 parts of epoxy resin curing agent, 0-10 parts of coupling agent and 0-10 parts of antioxidant, wherein the component B comprises the following raw materials in parts by weight: 20-100 parts of epoxy resin, 20-50 parts of plasticizer, 300-600 parts of heat conducting material, 20-200 parts of flame retardant material, 0-10 parts of coupling agent, 0-10 parts of water removing agent, 0-20 parts of thixotropic agent and 0-10 parts of catalyst; the silane terminated polyether resin is a mixture of more than two of dimethoxy silane terminated polyether, trimethoxy silane terminated polyether and triethoxy silane terminated polyether; the plasticizer is any one or a mixture of diisodecyl phthalate, diisononyl phthalate, polyether triol with the molecular weight of 3000 and polyether diol with the molecular weight of 2000; the heat conducting material is any one or combination of more of alpha-alumina, zinc oxide, magnesium oxide, boron nitride and aluminum nitride, wherein the particle size of the heat conducting material is 0.1-150 microns, and the particle size shape comprises irregular shape, spherical shape, quasi-spherical shape, needle shape and sheet shape; the flame retardant material is an additive flame retardant and comprises any one or a mixture of more of aluminum hydroxide, magnesium hydroxide, organic montmorillonite, ammonium polyphosphate, aluminum hypophosphite, diphenyl phosphate, melamine, pentaerythritol, dimethyl methylphosphonate, diethyl ethylphosphate, chlorinated paraffin, antimony trioxide and decabromodiphenylethane; the epoxy resin curing agent comprises one or a mixture of more of triethylene tetramine, N-aminoethyl piperazine, isophorone diamine, 2,4, 6-tri (dimethylamino methyl) phenol and 2-ethyl-4-methylimidazole; the coupling agent is any one or a mixture of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and 3-glycidyl ether oxypropyltrimethoxysilane; the epoxy resin is any one or mixture of more of E54 type bisphenol A diglycidyl ether, E51 type bisphenol A diglycidyl ether, E44 type bisphenol A diglycidyl ether, E41 type bisphenol A diglycidyl ether and cardanol modified glycidyl ether;

the mass ratio of the component A to the component B is 2.

2. The two-component room temperature fast curing anti-seismic heat-conducting structural adhesive according to claim 1, characterized in that: the antioxidant is any one or a mixture of more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.

3. The two-component room temperature fast curing anti-seismic heat-conducting structural adhesive according to claim 1, characterized in that: the water removing agent is any one or a mixture of more of vinyltriethoxysilane, vinyltrimethoxysilane, monocyclic oxazolidine and bicyclic oxazolidine.

4. The two-component room temperature fast curing anti-seismic heat-conducting structural adhesive according to claim 1, characterized in that: the thixotropic agent is any one or mixture of more of fumed silica, nano calcium carbonate, polyamide wax and modified castor oil, and the catalyst is any one or mixture of dibutyltin bis (acetylacetonate), 1, 3-tetrabutyl-1, 3-didodecyloxy distannoxane, dibutyltin dilaurate, organotin of stannous octoate and chelated tin catalysts.

5. A preparation method of the room temperature fast curing anti-seismic heat-conducting structural adhesive as claimed in any one of claims 1 to 4 is characterized in that: the method comprises the following steps:

s1, preparing a component A, adding silane-terminated polyether resin into a planetary stirrer, adding a plasticizer, adding a heat conduction material, an antioxidant and a flame retardant material in the stirring process, stirring for 20 minutes at room temperature, vacuumizing to-95 kpa, heating to 110 ℃, dispersing for 120 minutes at high speed, keeping the temperature to be less than 60 ℃ in a vacuum state, adding an epoxy resin curing agent, stirring for 10 minutes at vacuum-95 kpa, adding a coupling agent, stirring for 5 minutes, vacuumizing to-95 kpa, and stirring for 30 minutes until the mixture is uniformly stirred to obtain the component A;