CN117363308A - Low-density double-component polyurethane heat-conducting structural adhesive for power battery and preparation method thereof - Google Patents
Low-density double-component polyurethane heat-conducting structural adhesive for power battery and preparation method thereof Download PDFInfo
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- CN117363308A CN117363308A CN202311417045.4A CN202311417045A CN117363308A CN 117363308 A CN117363308 A CN 117363308A CN 202311417045 A CN202311417045 A CN 202311417045A CN 117363308 A CN117363308 A CN 117363308A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 52
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title description 16
- 239000011521 glass Substances 0.000 claims abstract description 67
- 239000011324 bead Substances 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000004359 castor oil Substances 0.000 claims abstract description 53
- 235000019438 castor oil Nutrition 0.000 claims abstract description 53
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 44
- 239000006229 carbon black Substances 0.000 claims abstract description 40
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 230000002745 absorbent Effects 0.000 claims abstract description 14
- 239000002250 absorbent Substances 0.000 claims abstract description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 21
- 235000003332 Ilex aquifolium Nutrition 0.000 claims description 16
- 235000002296 Ilex sandwicensis Nutrition 0.000 claims description 16
- 235000002294 Ilex volkensiana Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical group CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 11
- 239000006096 absorbing agent Substances 0.000 claims description 11
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000002411 adverse Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 239000003292 glue Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 241001018563 Nekemias grossedentata Species 0.000 description 3
- 241000219099 Parthenocissus quinquefolia Species 0.000 description 3
- 235000009388 Parthenocissus quinquefolia Nutrition 0.000 description 3
- 244000290333 Vanilla fragrans Species 0.000 description 3
- 235000009499 Vanilla fragrans Nutrition 0.000 description 3
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 small molecule isocyanate Chemical class 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a low-density double-component polyurethane heat-conducting structural adhesive for a power battery, which is prepared from the following components in percentage by volume (0.8-1.2): the component A and the component B of the component 1; the component A is prepared from the following raw materials: 5-15 parts by weight of castor oil; 5-10 parts by weight of modified castor oil; 1-10 parts by weight of a chain extender; 65-75 parts by weight of heat conducting powder; 1-3 parts by weight of glass beads; 0.5 to 3 parts by weight of white carbon black thixotropic agent; 0.5 to 3 parts by weight of adhesion promoter; 0.1 to 1 weight portion of metal catalyst; 0.5 to 1 weight portion of yellow color paste; the component B is prepared from the following raw materials: 10-30 parts by weight of diisocyanate; 5-20 parts by weight of polyether glycol; 65-75 parts by weight of heat conducting powder; 1-3 parts by weight of glass beads; 0.5 to 3 parts by weight of white carbon black thixotropic agent; 0.5 to 3 parts by weight of water absorbent; 0.5 to 1 weight portion of blue color paste. On the basis of solving the problem of high density of the existing double-component polyurethane heat-conducting structural adhesive, the product does not have adverse effects on heat-conducting performance and the like.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesives, in particular to a low-density double-component polyurethane heat-conducting structural adhesive for a power battery and a preparation method thereof.
Background
In the field of power battery PACK package, the double-component polyurethane heat conduction structural adhesive plays an important role in recent years, and the double-component polyurethane heat conduction structural adhesive has the functions of heat conduction and structural adhesion, so that the adhesive consumption in a single battery PACK is large. It is because the amount of the heat conductive structural adhesive used in a single battery pack is large, and thus, in order to achieve weight reduction in a downstream battery/automobile factory, it is desirable that the heat conductive structural adhesive be able to reduce the density while ensuring the heat conductivity. For example, the thermal conductivity of the two-component polyurethane thermal conductive structural adhesives currently used most widely in the market is approximately 1.2W/m.k, and the product density in the market of this type is in the range of 1.8g/cm 3 ～2.0g/cm 3 If the density can be adjusted from 1.8g/cm 3 Reduced to 1.6g/cm 3 The weight of the glue can be reduced by 12%.
At present, in order to reduce the density of the product, the prior art mainly starts from the aspect of heat conducting powder, and still takes a 1.2W/m.k product as an example, in order to achieve the heat conductivity coefficient of 1.2W/m.k, the addition amount of the heat conducting powder in the two-component polyurethane adhesive needs to reach 70 percent. Therefore, the most direct method is to reduce the addition amount of the filler, and the density of the glue can be reduced by adopting the heat-conducting filler (such as boron nitride and the like) with higher heat conductivity coefficient and/or lower density. However, the terminal price of the current glue for the power battery is obviously reduced, and if high-heat-conductivity and/or low-density fillers such as boron nitride are adopted, the cost is obviously increased, so that the glue is unacceptable to downstream customers; therefore, the low-density/lightweight two-component polyurethane heat-conducting structural adhesive for the power battery is provided.
Disclosure of Invention
In view of the above, the invention aims to provide a low-density double-component polyurethane heat-conducting structural adhesive for a power battery and a preparation method thereof, which solve the problem that the density of the existing double-component polyurethane heat-conducting structural adhesive is large.
The invention provides a low-density double-component polyurethane heat-conducting structural adhesive for a power battery, which is prepared from the following components in percentage by volume (0.8-1.2): the component A and the component B of the component 1; the component A is prepared from the following raw materials:
5-15 parts by weight of castor oil;
5-10 parts by weight of modified castor oil;
1-10 parts by weight of a chain extender;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of adhesion promoter;
0.1 to 1 weight portion of metal catalyst;
0.5 to 1 weight portion of yellow color paste;
the component B is prepared from the following raw materials:
10-30 parts by weight of diisocyanate;
5-20 parts by weight of polyether glycol;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of water absorbent;
0.5 to 1 weight portion of blue color paste.
Preferably, the modified castor oil is selected from the group consisting of an Italian AC-006 modified castor oil and/or an Italian AC-009 modified castor oil.
Preferably, the chain extender is selected from 2-ethyl-1, 3-hexanediol and/or 2-butyl-2-ethyl-1, 3-propanediol.
Preferably, the heat conducting powder is selected from Jin Ge JAZ-312 heat conducting powder and/or Jin Ge JAZ-144 heat conducting powder;
the glass beads are selected from holly HS28 glass beads and/or holly HK38 glass beads.
Preferably, the white carbon thixotropic agent is selected from CABOT TS720 white carbon and/or winning R202 white carbon.
Preferably, the adhesion promoter is selected from the group consisting of the Pick BYK-4510 adhesion promoter and/or the Pick BYK-4511 adhesion promoter.
Preferably, the metal catalyst is a Vanilla Coscat-83 organobismuth catalyst.
Preferably, the diisocyanate is selected from one or more of the group consisting of Van der Waals diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, carbodiimide-uretonimine modified 4,4' -diphenylmethane diisocyanate;
the polyether glycol is selected from Wanhua C2020 polyether glycol and/or Dongda DL2000 polyether glycol.
Preferably, the water absorbing agent is a Borchers TI water absorbing agent.
The invention also provides a preparation method of the low-density double-component polyurethane heat-conducting structural adhesive for the power battery, which comprises the following steps:
a) Heating castor oil, modified castor oil, a chain extender, heat conducting powder, glass beads and a white carbon black thixotropic agent to 110-130 ℃ under stirring at 150-250 rpm, vacuumizing to below-0.09 MPa, dehydrating for 1.5-2.5 h, cooling to below 50 ℃, adding an adhesion promoter, a metal catalyst and yellow color paste, vacuumizing to below-0.09 MPa, and continuing stirring at 80-120 rpm for 0.5-1 h to obtain a component A;
b) Firstly, drying and dehydrating the heat conducting powder, the glass beads and the white carbon black thixotropic agent at 80-120 ℃ for 20-30 hours for later use; stirring diisocyanate and polyether glycol at 80-120 rpm at 20-30 ℃ and vacuumizing to below-0.09 MPa for reaction for 1-3 h, adding heat conducting powder, glass beads and white carbon black thixotropic agent which are dried in advance, adding water absorbing agent and blue color paste, stirring at 180-220 rpm at 20-30 ℃ and vacuumizing to below-0.09 MPa for reaction for 0.5-1.5 h to obtain a component B;
c) Uniformly mixing the component A and the component B to obtain the low-density double-component polyurethane heat-conducting structural adhesive for the power battery;
the steps a) and b) are not limited in order.
The invention provides a low-density double-component polyurethane heat-conducting structural adhesive for a power battery, which is prepared from the following components in percentage by volume (0.8-1.2): the component A and the component B of the component 1; the component A is prepared from the following raw materials: 5-15 parts by weight of castor oil; 5-10 parts by weight of modified castor oil; 1-10 parts by weight of a chain extender; 65-75 parts by weight of heat conducting powder; 1-3 parts by weight of glass beads; 0.5 to 3 parts by weight of white carbon black thixotropic agent; 0.5 to 3 parts by weight of adhesion promoter; 0.1 to 1 weight portion of metal catalyst; 0.5 to 1 weight portion of yellow color paste; the component B is prepared from the following raw materials: 10-30 parts by weight of diisocyanate; 5-20 parts by weight of polyether glycol; 65-75 parts by weight of heat conducting powder; 1-3 parts by weight of glass beads; 0.5 to 3 parts by weight of white carbon black thixotropic agent; 0.5 to 3 parts by weight of water absorbent; 0.5 to 1 weight portion of blue color paste. Compared with the prior art, the low-density double-component polyurethane heat-conducting structural adhesive for the power battery provided by the invention adopts specific components with specific contents to realize better interaction as a whole, and does not adversely affect heat-conducting performance and the like on the basis of solving the problem of higher density of the existing double-component polyurethane heat-conducting structural adhesive.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, easily available raw materials, low cost and wide industrial application prospect.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a low-density double-component polyurethane heat-conducting structural adhesive for a power battery, which is prepared from the following components in percentage by volume (0.8-1.2): the component A and the component B of the component 1; the component A is prepared from the following raw materials:
5-15 parts by weight of castor oil;
5-10 parts by weight of modified castor oil;
1-10 parts by weight of a chain extender;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of adhesion promoter;
0.1 to 1 weight portion of metal catalyst;
0.5 to 1 weight portion of yellow color paste;
the component B is prepared from the following raw materials:
10-30 parts by weight of diisocyanate;
5-20 parts by weight of polyether glycol;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of water absorbent;
0.5 to 1 weight portion of blue color paste.
According to the invention, the traditional aluminum hydroxide and aluminum oxide system is adopted in the selection of the heat conducting powder, so that the cost of the product is not obviously increased, and the purpose of reducing the density is realized by adopting glass beads in order to realize the final purpose of reducing the density; of course, the selection of the glass beads has obvious defects that the addition of the glass beads can obviously reduce the density but also reduce the heat conductivity coefficient of the glue at the same time because the interior of the glass beads is provided with air; therefore, the invention needs a balance in the adjustment of the formula, and the amount of the glass beads needs to be precisely controlled.
In the invention, the low-density double-component polyurethane heat-conducting structural adhesive for the power battery comprises the following components in volume ratio (0.8-1.2): 1 and a component B, preferably 1:1.
in the invention, the component A is prepared from the following raw materials:
5-15 parts by weight of castor oil;
5-10 parts by weight of modified castor oil;
1-10 parts by weight of a chain extender;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of adhesion promoter;
0.1 to 1 weight portion of metal catalyst;
0.5 to 1 weight portion of yellow color paste;
the preparation method is preferably prepared from the following raw materials:
8-11 parts of castor oil;
8 parts by weight of modified castor oil;
5 parts by weight of a chain extender;
71.5 to 73 parts by weight of heat conducting powder;
1.5 to 3 parts by weight of glass beads;
1.5 parts by weight of a white carbon black thixotropic agent;
1 part by weight of an adhesion promoter;
0.1 parts by weight of a metal catalyst;
0.5 parts of yellow color paste.
In the present invention, the castor oil is unmodified castor oil, and is commercially available from common castor oil materials known to those skilled in the art.
In the present invention, the modified castor oil is preferably selected from the group consisting of Eartan AC-006 modified castor oil and/or Eartan AC-009 modified castor oil, more preferably Eartan AC-006 modified castor oil or Eartan AC-009 modified castor oil. The source of the modified castor oil is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the chain extender is preferably selected from 2-ethyl-1, 3-hexanediol (EHD) and/or 2-butyl-2-ethyl-1, 3-propanediol (BEPD), more preferably 2-ethyl-1, 3-hexanediol or 2-butyl-2-ethyl-1, 3-propanediol. The source of the chain extender is not particularly limited and commercially available products known to those skilled in the art may be used.
In the invention, the heat conducting powder is preferably selected from Jin Ge JAZ-312 heat conducting powder and/or Jin Ge JAZ-144 heat conducting powder, more preferably Jin Ge JAZ-312 heat conducting powder or Jin Ge JAZ-144 heat conducting powder. The source of the heat conductive powder is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the glass beads are preferably selected from holly HS28 glass beads and/or holly HK38 glass beads, more preferably holly HS28 glass beads or holly HK38 glass beads. The source of the glass beads is not particularly limited, and commercially available products known to those skilled in the art may be used. The density of the double-component polyurethane heat-conducting structural adhesive is reduced through the glass beads, and the negative influence of the glass beads on heat conduction is further compensated by improving the content of the heat-conducting powder in the formula.
In the invention, the white carbon thixotropic agent is preferably selected from CABOT TS720 white carbon and/or winning R202 white carbon, more preferably CABOT TS720 white carbon or winning R202 white carbon; the adhesion promoter is preferably selected from the group consisting of a Pick BYK-4510 adhesion promoter and/or a Pick BYK-4511 adhesion promoter, more preferably a Pick BYK-4510 adhesion promoter or a Pick BYK-4511 adhesion promoter; the metal catalyst is preferably a Vanilla Coscat-83 organobismuth catalyst. The sources of the white carbon thixotropic agent, the adhesion promoter, the metal catalyst and the yellow pigment paste are not particularly limited, and commercially available products known to those skilled in the art can be used.
In the invention, the component B is prepared from the following raw materials:
10-30 parts by weight of diisocyanate;
5-20 parts by weight of polyether glycol;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of water absorbent;
0.5 to 1 weight portion of blue color paste;
the preparation method is preferably prepared from the following raw materials:
19.5 to 22 parts by weight of diisocyanate;
9-10 parts by weight of polyether glycol;
65-67 parts by weight of heat conducting powder;
1.5 to 3 parts by weight of glass beads;
0.5 parts by weight of a white carbon black thixotropic agent;
0.5 to weight portions of water absorbent;
and 0.5 parts of blue color paste.
In the present invention, the diisocyanate is preferably selected from one or more of the group consisting of a trilobate diphenylmethane diisocyanate (MDI-100), a liquefied diphenylmethane diisocyanate (MDI-50), a carbodiimide-uretonimine modified 4,4 '-diphenylmethane diisocyanate (CDMDI-100L), more preferably a trilobate diphenylmethane diisocyanate (MDI-100), a liquefied diphenylmethane diisocyanate (MDI-50) and a carbodiimide-uretonimine modified 4,4' -diphenylmethane diisocyanate (CDMDI-100L); the polyether diol is preferably selected from the group consisting of Wanhua C2020 polyether diol and/or Dongda DL2000 polyether diol, more preferably the polyether diol is preferably selected from the group consisting of Wanhua C2020 polyether diol and Dongda DL2000 polyether diol. The sources of the diisocyanate and polyether diol are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the heat conductive powder, glass beads and white carbon black thixotropic agent are the same as those in the above technical solution, and will not be described herein again.
In the present invention, the water absorbing agent is preferably a Borchers TI water absorbing agent. The source of the water absorbing agent and the blue color paste is not particularly limited, and commercially available products known to those skilled in the art can be used.
The low-density double-component polyurethane heat-conducting structural adhesive for the power battery provided by the invention adopts specific components with specific contents, realizes better interaction as a whole, solves the problem that the existing double-component polyurethane adhesive is difficult to disassemble after being solidified, and has high strength.
The invention also provides a preparation method of the low-density double-component polyurethane heat-conducting structural adhesive for the power battery, which comprises the following steps:
a) Heating castor oil, modified castor oil, a chain extender, heat conducting powder, glass beads and a white carbon black thixotropic agent to 110-130 ℃ under stirring at 150-250 rpm, vacuumizing to below-0.09 MPa, dehydrating for 1.5-2.5 h, cooling to below 50 ℃, adding an adhesion promoter, a metal catalyst and yellow color paste, vacuumizing to below-0.09 MPa, and continuing stirring at 80-120 rpm for 0.5-1 h to obtain a component A;
b) Firstly, drying and dehydrating the heat conducting powder, the glass beads and the white carbon black thixotropic agent at 80-120 ℃ for 20-30 hours for later use; stirring diisocyanate and polyether glycol at 80-120 rpm at 20-30 ℃ and vacuumizing to below-0.09 MPa for reaction for 1-3 h, adding heat conducting powder, glass beads and white carbon black thixotropic agent which are dried in advance, adding water absorbing agent and blue color paste, stirring at 180-220 rpm at 20-30 ℃ and vacuumizing to below-0.09 MPa for reaction for 0.5-1.5 h to obtain a component B;
c) Uniformly mixing the component A and the component B to obtain the low-density double-component polyurethane heat-conducting structural adhesive for the power battery;
the steps a) and b) are not limited in order.
The preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, easily available raw materials, low cost and wide industrial application prospect.
Compared with the prior art, the invention does not adopt expensive boron nitride and other heat conducting powder, and still adopts an economic aluminum hydroxide and aluminum oxide heat conducting powder system, and the balance of density and heat conductivity coefficient is adjusted by matching with glass beads, so that the density reduction purpose of the double-component polyurethane heat conducting structural adhesive is realized. Experimental results TableOn the basis of ensuring that the heat conductivity coefficient reaches 1.2W/m.k, the density of the double-component polyurethane heat-conducting structural adhesive provided by the invention can be as low as 1.55g/cm 3 ～1.65g/cm 3 The heat conductivity coefficient is stabilized at 1.20W/m.k-1.25W/m.k, meanwhile, the body tensile strength of the glue is 7 MPa-9 MPa, the tensile shear strength is 7 MPa-9 MPa, and the elongation at break is 10% -40%.
The invention provides a low-density double-component polyurethane heat-conducting structural adhesive for a power battery, which is prepared from the following components in percentage by volume (0.8-1.2): the component A and the component B of the component 1; the component A is prepared from the following raw materials: 5-15 parts by weight of castor oil; 5-10 parts by weight of modified castor oil; 1-10 parts by weight of a chain extender; 65-75 parts by weight of heat conducting powder; 1-3 parts by weight of glass beads; 0.5 to 3 parts by weight of white carbon black thixotropic agent; 0.5 to 3 parts by weight of adhesion promoter; 0.1 to 1 weight portion of metal catalyst; 0.5 to 1 weight portion of yellow color paste; the component B is prepared from the following raw materials: 10-30 parts by weight of diisocyanate; 5-20 parts by weight of polyether glycol; 65-75 parts by weight of heat conducting powder; 1-3 parts by weight of glass beads; 0.5 to 3 parts by weight of white carbon black thixotropic agent; 0.5 to 3 parts by weight of water absorbent; 0.5 to 1 weight portion of blue color paste. Compared with the prior art, the low-density double-component polyurethane heat-conducting structural adhesive for the power battery provided by the invention adopts specific components with specific contents to realize better interaction as a whole, and does not adversely affect heat-conducting performance and the like on the basis of solving the problem of higher density of the existing double-component polyurethane heat-conducting structural adhesive.
In addition, the preparation method provided by the invention has the advantages of simple process, mild and easily controlled conditions, easily available raw materials, low cost and wide industrial application prospect.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available; comprising the following steps:
(modified) castor oil: castor oil, italian ampelopsis root AC-006 modified castor oil and Italian ampelopsis root AC-009 modified castor oil;
chain extender: 2-ethyl-1, 3-hexanediol (EHD), 2-butyl-2-ethyl-1, 3-propanediol (BEPD);
a diisocyanate: van der Waals diphenylmethane diisocyanate (MDI-100), liquefied diphenylmethane diisocyanate MDI-50, carbodiimide-uretonimine modified 4,4' -diphenylmethane diisocyanate (CDMDI-100L);
polyether glycol: wanhua C2020, dongda DL2000;
and (3) heat conducting powder: jin Ge JAZ-312 and Jin Ge JAZ-144;
glass beads: holly HS28 and HK38;
white carbon black thixotropic agent: CABOT TS720 and win R202;
adhesion promoters: pick BYK-4510 and Pick BYK-4511;
metal catalyst: van der Waals Coscat-83 organobismuth catalyst;
water absorbing agent: borchers TI (monofunctional small molecule isocyanate);
color paste: baomeishi blue color paste and yellow color paste.
The preparation method of the following examples of the invention comprises the following steps:
(1) And (3) a component A:
heating castor oil, modified castor oil, a chain extender, heat conducting powder, glass beads and a white carbon black thixotropic agent to 120 ℃ under stirring at 200rpm, vacuumizing to below-0.09 MPa, dehydrating for 2 hours, cooling to below 50 ℃, adding an adhesion promoter, a metal catalyst and yellow color paste, vacuumizing to below-0.09 MPa, and continuing stirring at 100rpm for 0.8 hours to obtain a component A.
(2) And the component B comprises the following components:
firstly, drying and dehydrating heat conduction powder, glass beads and a white carbon black thixotropic agent in a drying room at 100 ℃ for 24 hours for later use; and (3) stirring diisocyanate and polyether glycol at normal temperature of 100rpm, vacuumizing to below-0.09 MPa, reacting for 2 hours, then adding heat conducting powder, glass beads and white carbon black thixotropic agent which are dried in advance, adding water absorbent and blue color paste, stirring at normal temperature of 200rpm, vacuumizing to below-0.09 MPa, and reacting for 1 hour to obtain the component B.
(3) The A component and the B component are mixed according to the volume ratio of 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Example 1
And (3) a component A: 11 parts of castor oil, 8 parts of Embectomy AC-006 modified castor oil, 5 parts of 2-ethyl-1, 3-hexanediol, 71.5 parts of Jin Ge JAZ-312 heat conducting powder, 1.5 parts of holly HS28 glass beads, 1.5 parts of CABOT TS720 white carbon black thixotropic agent, 1 part of Pick BYK-4510 adhesion promoter, 0.1 part of Van-terus Coscat-83 metal catalyst and 0.5 part of Baomei yellow color paste.
And the component B comprises the following components: 22 parts of Wanhua MDI-100 diphenylmethane diisocyanate, 10 parts of Wanhua C2020 polyether glycol, 65 parts of Jin Ge JAZ-312 heat conducting powder, 1.5 parts of holly HS28 glass beads, 0.5 part of CABOOT TS720 white carbon black thixotropic agent, 0.5 part of Borchers TI water absorbent and 0.5 part of Baomei blue color paste.
The double-component polyurethane structural adhesive is prepared according to the preparation method.
Example 2
And (3) a component A: 9 parts of castor oil, 8 parts of Italian ampelopsis grossedentata AC-009 modified castor oil, 5 parts of 2-ethyl-1, 3-hexanediol, 73 parts of Jin Ge JAZ-144 heat conduction powder, 2 parts of holly HS28 glass beads, 1.5 parts of CABOT TS720 white carbon black thixotropic agent, 1 part of Pick BYK-4510 adhesion promoter, 0.1 part of Van-terlus Coscat-83 metal catalyst and 0.5 part of Baomeishi yellow color paste.
And the component B comprises the following components: 19.5 parts of Wanhua MDI-50 liquefied diphenylmethane diisocyanate, 10 parts of Dongda DL2000 polyether glycol, 67 parts of Jin Ge JAZ-144 heat conducting powder, 2 parts of Santa Clay HS28 glass beads, 0.5 part of CABOOT TS720 white carbon black thixotropic agent, 0.5 part of Borchers TI water absorbent and 0.5 part of Baomeishi blue color paste.
The double-component polyurethane structural adhesive is prepared according to the preparation method.
Example 3
And (3) a component A: 8 parts of castor oil, 8 parts of Italian ampelopsis grossedentata AC-009 modified castor oil, 5 parts of 2-butyl-2-ethyl-1, 3-propanediol, 73 parts of Jin Ge JAZ-144 heat conducting powder, 3 parts of holly Rate HK38 glass microsphere, 1.5 parts of Yingzhuang R202 white carbon black thixotropic agent, 1 part of Pick BYK-4511 adhesion promoter, 0.1 part of Van-T Coscat-83 metal catalyst and 0.5 part of Baomei yellow color paste.
And the component B comprises the following components: 19.5 parts of Wanhua MDI-100L liquefied diphenylmethane diisocyanate, 9 parts of Dongda DL2000 polyether glycol, 67 parts of JAZ-144 heat conducting powder, 3 parts of holly HK38 glass beads, 0.5 part of Yingchuang R202 white carbon black thixotropic agent, 0.5 part of Borchers TI water absorbent and 0.5 part of Baomeishi blue color paste.
The double-component polyurethane structural adhesive is prepared according to the preparation method.
Comparative example 1
And (3) a component A: 14 parts of castor oil, 10 parts of Italian ampelopsis AC-009 modified castor oil, 5 parts of 2-ethyl-1, 3-hexanediol, 68 parts of Jin Ge JAZ-312 heat conducting powder, 1.5 parts of CABOT TS720 white carbon black thixotropic agent, 1 part of Pick BYK-4510 adhesion promoter, 0.1 part of Vanilla Coscat-83 metal catalyst and 0.5 part of Baomeishi yellow color paste.
And the component B comprises the following components: 23.5 parts of Wanhua MDI-100 diphenylmethane diisocyanate, 10 parts of Wanhua C2020 polyether glycol, 65 parts of Jin Ge JAZ-312 heat conducting powder, 0.5 part of CABOT TS720 white carbon black thixotropic agent, 0.5 part of Borchers TI water absorbent and 0.5 part of Baomeishi blue color paste.
The double-component polyurethane structural adhesive is prepared according to the preparation method.
Comparative example 2
And (3) a component A: 12.5 parts of castor oil, 10 parts of Italian ampelopsis grossedentata AC-006 modified castor oil, 5 parts of 2-ethyl-1, 3-hexanediol, 68 parts of Jin Ge JAZ-312 heat conducting powder, 1.5 parts of holly HS28 glass beads, 1.5 parts of CABOT TS720 white carbon black thixotropic agent, 1 part of Pick BYK-4510 adhesion promoter, 0.1 part of Van der Coscat-83 metal catalyst and 0.5 part of Baomei yellow color paste.
And the component B comprises the following components: 22 parts of Wanhua MDI-100L liquefied diphenylmethane diisocyanate, 10 parts of Dongda DL2000 polyether glycol, 65 parts of Jin Ge JAZ-312 heat conducting powder, 1.5 parts of holly HS28 glass beads, 0.5 part of CABOOT TS720 white carbon black thixotropic agent, 0.5 part of Borchers TI water absorbent and 0.5 part of Baomeishi blue color paste.
The formulation table is presented in table 1 below.
Table 1 typical comparative experiments
In the above test, comparative example 1 can be understood as a formulation of a conventional product, that is, the requirement of heat conductivity is satisfied by adding heat conductive powder, and no glass beads are additionally added to reduce the density; in comparative example 2, the density is reduced by directly adding glass beads on the basis of comparative example 1, and the loss of the heat conductivity coefficient is compensated by not correspondingly increasing the content of the heat conducting powder; in the embodiments 1 to 3, the density is reduced by adding glass beads, and the loss of the heat conductivity coefficient is compensated by increasing the content of the heat conducting powder, so that the balance of heat conduction and density is finally realized; the specific difference is represented by the difference of glass beads, because glass beads of different true densities are inconsistent in the degree of density reduction, and when glass beads of higher true densities are used (example 3), the amount of glass beads added is correspondingly increased.
The properties of the two-component polyurethane structural adhesives were tested according to the following test criteria.
Thermal conductivity coefficient: ASTM D5470-17,Standard Test Method for Thermal Transmission Properties of Thermally Conductive Electrical Insulation Materials;
density after curing: GB/T533-2008, measuring the density of vulcanized rubber or thermoplastic rubber;
tensile strength and elongation at break of body: GB/T528-2009, measurement of tensile stress strain properties of vulcanized rubber or thermoplastic rubber;
tensile shear strength: GB/T7124-2008, determination of tensile shear strength of adhesive (rigid material versus rigid material).
The test results are shown in Table 2 below.
Table 2 test results
From the results, comparative example 1 was used as a base formulation having a thermal conductivity of about 1.25W/m.k and a density of 1.81g/cm 3 About, comparative example 2 added glass beads, but no corresponding increase in the content of thermally conductive filler, it can be seen that the density can be significantly reduced to 1.58g/cm 3 But the heat conductivity coefficient is reduced to 1.12W/m.k, so that the market demand can not be met; while examples 1 to 3 reduce the density by adding glass beads, and at the same time, properly raise the content of the heat conductive powder to compensate for the loss of the heat conductive coefficient, a balance can be finally achieved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A low-density double-component polyurethane heat-conducting structural adhesive for a power battery is prepared from the following components in percentage by volume (0.8-1.2): the component A and the component B of the component 1; the component A is prepared from the following raw materials:
5-15 parts by weight of castor oil;
5-10 parts by weight of modified castor oil;
1-10 parts by weight of a chain extender;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of adhesion promoter;
0.1 to 1 weight portion of metal catalyst;
0.5 to 1 weight portion of yellow color paste;
the component B is prepared from the following raw materials:
10-30 parts by weight of diisocyanate;
5-20 parts by weight of polyether glycol;
65-75 parts by weight of heat conducting powder;
1-3 parts by weight of glass beads;
0.5 to 3 parts by weight of white carbon black thixotropic agent;
0.5 to 3 parts by weight of water absorbent;
0.5 to 1 weight portion of blue color paste.
2. The low-density two-component polyurethane heat conducting structural adhesive for a power battery according to claim 1, wherein the modified castor oil is selected from the group consisting of an ibandrus AC-006 modified castor oil and/or an ibandrus AC-009 modified castor oil.
3. The low-density two-component polyurethane heat conducting structural adhesive for a power battery according to claim 1, wherein the chain extender is selected from 2-ethyl-1, 3-hexanediol and/or 2-butyl-2-ethyl-1, 3-propanediol.
4. The low-density two-component polyurethane heat conducting structural adhesive for a power battery according to claim 1, wherein the heat conducting powder is selected from Jin Ge JAZ-312 heat conducting powder and/or Jin Ge JAZ-144 heat conducting powder;
the glass beads are selected from holly HS28 glass beads and/or holly HK38 glass beads.
5. The low-density two-component polyurethane heat-conducting structural adhesive for a power battery according to claim 1, wherein the white carbon thixotropic agent is selected from CABOT TS720 white carbon and/or winning R202 white carbon.
6. The low-density two-component polyurethane heat conductive structural adhesive for a power battery according to claim 1, wherein the adhesion promoter is selected from the group consisting of the pick BYK-4510 adhesion promoter and/or the pick BYK-4511 adhesion promoter.
7. The low-density two-component polyurethane heat-conducting structural adhesive for a power battery according to claim 1, wherein the metal catalyst is a vanterus Coscat-83 organobismuth catalyst.
8. The low-density two-component polyurethane heat-conducting structural adhesive for a power battery according to claim 1, wherein the diisocyanate is one or more selected from the group consisting of a trilobate diphenylmethane diisocyanate, a liquefied diphenylmethane diisocyanate, and a carbodiimide-uretonimine modified 4,4' -diphenylmethane diisocyanate;
the polyether glycol is selected from Wanhua C2020 polyether glycol and/or Dongda DL2000 polyether glycol.
9. The low-density two-component polyurethane heat conductive structural adhesive for a power cell of claim 1, wherein the water absorbing agent is Borchers TI water absorbing agent.
10. A method for preparing the low-density two-component polyurethane heat-conducting structural adhesive for the power battery according to any one of claims 1 to 9, which comprises the following steps:
a) Heating castor oil, modified castor oil, a chain extender, heat conducting powder, glass beads and a white carbon black thixotropic agent to 110-130 ℃ under stirring at 150-250 rpm, vacuumizing to below-0.09 MPa, dehydrating for 1.5-2.5 h, cooling to below 50 ℃, adding an adhesion promoter, a metal catalyst and yellow color paste, vacuumizing to below-0.09 MPa, and continuing stirring at 80-120 rpm for 0.5-1 h to obtain a component A;
b) Firstly, drying and dehydrating the heat conducting powder, the glass beads and the white carbon black thixotropic agent at 80-120 ℃ for 20-30 hours for later use; stirring diisocyanate and polyether glycol at 80-120 rpm at 20-30 ℃ and vacuumizing to below-0.09 MPa for reaction for 1-3 h, adding heat conducting powder, glass beads and white carbon black thixotropic agent which are dried in advance, adding water absorbing agent and blue color paste, stirring at 180-220 rpm at 20-30 ℃ and vacuumizing to below-0.09 MPa for reaction for 0.5-1.5 h to obtain a component B;
c) Uniformly mixing the component A and the component B to obtain the low-density double-component polyurethane heat-conducting structural adhesive for the power battery;
the steps a) and b) are not limited in order.
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