CN115404035B - Polyurethane adhesive with high heat conduction and weather resistance for automobile lithium battery and preparation method thereof - Google Patents
Polyurethane adhesive with high heat conduction and weather resistance for automobile lithium battery and preparation method thereof Download PDFInfo
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- CN115404035B CN115404035B CN202211022914.9A CN202211022914A CN115404035B CN 115404035 B CN115404035 B CN 115404035B CN 202211022914 A CN202211022914 A CN 202211022914A CN 115404035 B CN115404035 B CN 115404035B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 239000000853 adhesive Substances 0.000 title claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims abstract description 36
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004432 silane-modified polyurethane Substances 0.000 claims abstract description 22
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 4
- -1 amine compound Chemical class 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- DQSYGNJXYMAPMV-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3,5-ditert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 DQSYGNJXYMAPMV-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application relates to a high-heat-conductivity weather-resistance polyurethane adhesive for an automobile lithium battery and a preparation method thereof, wherein the polyurethane adhesive comprises the following components in parts by weight: 70-100 parts of silane modified polyurethane prepolymer, 40-60 parts of plasticizer, 30-100 parts of filler, 1-3 parts of aminated graphene oxide, 1-3 parts of tackifier, 1-2 parts of antioxidant and 0.5-1 part of catalyst, wherein the filler is a compound of aluminum oxide treated by a silane coupling agent and aluminum hypophosphite treated by the silane coupling agent. According to the polyurethane adhesive with high heat conduction and weather resistance for the automobile lithium battery, disclosed by the application, the heat conduction of the adhesive is greatly increased by adding the aluminum oxide treated by the silane coupling agent and the aluminum hypophosphite compound treated by the silane coupling agent, and the synergistic effect of the silane modified polyurethane prepolymer and the aminated graphene oxide is improved, so that the heat conduction is improved, and the weather resistance of the adhesive is further improved.
Description
Technical Field
The application belongs to the technical field of adhesives, and particularly relates to a polyurethane adhesive with high heat conduction and weather resistance for an automobile lithium battery and a preparation method thereof.
Background
The new energy electric automobile is a main direction of development of the future automobile industry, the traditional oil motor cars such as cars and buses are gradually replaced by the new energy automobile, and the power batteries such as lithium batteries become main energy sources of the new energy automobile.
The adhesive is one of the core factors for realizing stable, efficient, durable and safe operation of the electric drive system. The adhesive mainly has four functions of providing protection effect for the power battery, providing safe and reliable lightweight design, heat management and helping the power battery to cope with more complex use environments on the power battery, so that the application of the adhesive is wider and wider, but the performance requirement on the adhesive is higher and higher.
Polyurethane adhesives are one of the bonding materials widely used at present, and have better toughness, room temperature curability and better adhesion to plastic parts than epoxy resin adhesives; because of high bonding strength, good impact resistance and chemical resistance, the polyurethane adhesive has wide range of bonding materials, has been widely applied in automobile manufacturing, and becomes one of main adhesive types for automobiles.
However, the polyurethane adhesive conventionally used for bonding power battery parts is poor in heat conductivity and weather resistance, and is difficult to adapt to battery operation environments of high-frequency vibration jolt, high-low temperature and high-humidity heat.
Therefore, there is a need for a polyurethane adhesive with high thermal conductivity and weather resistance for lithium batteries of automobiles.
Disclosure of Invention
The application aims to provide a polyurethane adhesive with high heat conduction and weather resistance for an automobile lithium battery, which has the advantages of excellent heat conduction, good weather resistance and long service life.
The application solves the problems by adopting the following technical scheme: the polyurethane adhesive with high heat conduction and weather resistance for the automobile lithium battery comprises the following components in parts by weight:
70-100 parts of silane modified polyurethane prepolymer
40-60 parts of plasticizer
30-100 parts of filler
1-3 parts of amination graphene oxide
1-3 parts of tackifier
Antioxidant 1-2 parts
0.5-1 part of catalyst
Wherein the filler is a compound of aluminum oxide treated by a silane coupling agent and aluminum hypophosphite treated by the silane coupling agent.
Preferably, the plasticizer is at least one of dibutyl phthalate, diethyl phthalate, didecyl phthalate and dioctyl phthalate.
Preferably, the mass ratio of the aluminum oxide treated by the silane coupling agent to the aluminum hypophosphite treated by the silane coupling agent is 1-2:1-2.
Preferably, the silane coupling agent-treated alumina is prepared by the following preparation method: adding aluminum oxide into an ethanol solution of a silane coupling agent with the mass concentration of 0.5% -10%, stirring for 30-60 min at 30-50 ℃, centrifuging for 30-45 min at 5000-10000r/min, and drying the obtained solid after centrifuging to obtain the aluminum oxide treated by the silane coupling agent; the aluminum hypophosphite treated by the silane coupling agent is prepared by the following preparation method: adding aluminum hypophosphite into an ethanol solution of a silane coupling agent with the mass concentration of 0.5% -10%, stirring for 30-60 min at the temperature of 30-50 ℃, centrifuging for 30-45 min at the speed of 5000-10000r/min, and drying the obtained solid after centrifuging to obtain the aluminum hypophosphite treated by the silane coupling agent.
Preferably, the aminated graphene oxide is prepared by the following steps: dispersing graphene oxide in deionized water to prepare graphene oxide colloid suspension; according to (6-8 g): 100mL of the solution is prepared by dissolving an amine compound in absolute ethyl alcohol, and stirring until the amine compound is fully dissolved to obtain a solution; adding the solution into the graphene oxide colloid suspension, uniformly stirring to obtain an aminated graphene oxide dispersion solution, and carrying out vacuum suction filtration, washing and freeze drying on the aminated graphene oxide dispersion solution to obtain the aminated graphene oxide.
Preferably, the tackifier is at least one of aminopropyl trimethoxysilane, aminopropyl triethoxysilane, aminopropyl methyldimethoxy silane and glycidoxypropyl trimethoxysilane.
Preferably, the antioxidant is at least one of 2, 6-di-tert-butyl-4-methylphenol and bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide.
Preferably, the catalyst is at least one of dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctanoate and stannous octoate.
The application further aims to provide a preparation method of the polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile, which comprises the following steps:
(1) Adding the silane modified polyurethane prepolymer, the plasticizer and the aminated graphene oxide into a stirrer, and stirring and mixing under a vacuum condition;
(2) Adding filler into the mixture stirred and mixed in the step (1), and stirring and mixing under vacuum condition;
(3) Adding tackifier, antioxidant and catalyst into the stirred and mixed mixture obtained in the step (2), and stirring and mixing under vacuum condition.
Compared with the prior art, the application has the advantages that:
(1) According to the application, the silane modified polyurethane prepolymer and the aminated graphene oxide are adopted, and have a synergistic effect, so that the heat conductivity is improved, and the weather resistance of the adhesive is further improved.
(2) The application adopts the aluminum oxide treated by the silane coupling agent and the compound of the aluminum hypophosphite treated by the silane coupling agent as the filler, so that the heat conduction performance of the polyurethane adhesive is greatly improved, and the aluminum oxide and the aluminum hypophosphite treated by the silane coupling agent have good compatibility with other components.
Detailed Description
The present application is described in further detail below with reference to examples.
Example 1
The polyurethane adhesive with high heat conduction and weather resistance for the automobile lithium battery comprises the following components in parts by weight:
80 parts of silane modified polyurethane prepolymer
Plasticizer dibutyl phthalate 50 parts
60 parts of filler
2 parts of amination graphene oxide
Tackifier aminopropyl trimethoxy silane 2 parts
Antioxidant 2, 6-di-tert-butyl-4-methylphenol 1 part
Catalyst dibutyltin dilaurate 0.7 part
Wherein the silane modified polyurethane prepolymer is silane modified polyurethane prepolymer with the brand of SPUR 1015LM produced by Michaelis high new material group.
The filler is aluminum oxide treated by a silane coupling agent and aluminum hypophosphite compound treated by the silane coupling agent in a mass ratio of 1:1; the aluminum oxide treated by the silane coupling agent is prepared by the following preparation method: according to 5g: adding alumina into a silane coupling agent KH550 ethanol solution with the mass concentration of 5% according to the proportion of 100mL, stirring for 60min at 30 ℃, centrifuging for 30min at 10000r/min, and drying the solid obtained after centrifugation to obtain the alumina treated by the silane coupling agent; the aluminum hypophosphite treated by the silane coupling agent is prepared by the following preparation method: according to 5g:100mL of aluminum hypophosphite is added into a silane coupling agent KH550 ethanol solution with the mass concentration of 5%, after stirring for 60min at 30 ℃,10000r/min is centrifuged for 30min, and the solid obtained after centrifugation is dried, thus obtaining the aluminum hypophosphite treated by the silane coupling agent.
The aminated graphene oxide is prepared by the following steps: 3g of graphene oxide is dispersed in 100mL of deionized water to prepare a graphene oxide colloid suspension; according to 6g: dissolving diethylenetriamine in absolute ethanol according to the proportion of 100mL, and stirring until the diethylenetriamine is fully dissolved to obtain a solution; adding the solution into the graphene oxide colloid suspension, uniformly stirring to obtain an aminated graphene oxide dispersion solution, and carrying out vacuum suction filtration, washing and freeze drying on the aminated graphene oxide dispersion solution to obtain the aminated graphene oxide.
A preparation method of a polyurethane adhesive with high heat conduction and weather resistance for an automobile lithium battery comprises the following steps:
(1) Adding the silane modified polyurethane prepolymer, the plasticizer and the aminated graphene oxide into a stirrer, stirring and mixing for 30min at the temperature of 50 ℃ and the vacuum degree of 0.06 MPa;
(2) Adding filler into the mixture stirred and mixed in the step (1), and stirring and mixing for 30min at the temperature of 30 ℃ and the vacuum degree of 0.06 MPa;
(3) Adding tackifier, antioxidant and catalyst into the stirred and mixed mixture obtained in the step (2), and stirring and mixing for 20min at the temperature of 30 ℃ and the vacuum degree of 0.06 MPa.
Example 2
The polyurethane adhesive with high heat conduction and weather resistance for the automobile lithium battery comprises the following components in parts by weight:
100 parts of silane modified polyurethane prepolymer
50 parts of dioctyl phthalate plasticizer
80 parts of filler
3 parts of aminated graphene oxide
3 parts of tackifier glycidoxypropyl trimethoxy silane
2 parts of antioxidant bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide
Catalyst dibutyl tin dioctanoate 1 part
Wherein the silane modified polyurethane prepolymer is silane modified polyurethane prepolymer with the brand of SPUR 1050MM produced by Mai high new material group.
The filler is aluminum oxide treated by a silane coupling agent and aluminum hypophosphite compound treated by the silane coupling agent in a mass ratio of 1:2; the aluminum oxide treated by the silane coupling agent is prepared by the following preparation method: according to 5g: adding alumina into a silane coupling agent KH550 ethanol solution with the mass concentration of 5% according to the proportion of 100mL, stirring for 60min at 30 ℃, centrifuging for 30min at 10000r/min, and drying the solid obtained after centrifugation to obtain the alumina treated by the silane coupling agent; the aluminum hypophosphite treated by the silane coupling agent is prepared by the following preparation method: according to 5g:100mL of aluminum hypophosphite is added into a silane coupling agent KH550 ethanol solution with the mass concentration of 5%, after stirring for 60min at 30 ℃,10000r/min is centrifuged for 30min, and the solid obtained after centrifugation is dried, thus obtaining the aluminum hypophosphite treated by the silane coupling agent.
The aminated graphene oxide is prepared by the following steps: 3g of graphene oxide is dispersed in 100mL of deionized water to prepare a graphene oxide colloid suspension; according to 6g: dissolving diethylenetriamine in absolute ethanol according to the proportion of 100mL, and stirring until the diethylenetriamine is fully dissolved to obtain a solution; adding the solution into the graphene oxide colloid suspension, uniformly stirring to obtain an aminated graphene oxide dispersion solution, and carrying out vacuum suction filtration, washing and freeze drying on the aminated graphene oxide dispersion solution to obtain the aminated graphene oxide.
A preparation method of a polyurethane adhesive with high heat conduction and weather resistance for an automobile lithium battery comprises the following steps:
(1) Adding the silane modified polyurethane prepolymer, the plasticizer and the aminated graphene oxide into a stirrer, stirring and mixing for 30min at the temperature of 50 ℃ and the vacuum degree of 0.06 MPa;
(2) Adding filler into the mixture stirred and mixed in the step (1), and stirring and mixing for 30min at the temperature of 30 ℃ and the vacuum degree of 0.06 MPa;
(3) Adding tackifier, antioxidant and catalyst into the stirred and mixed mixture obtained in the step (2), and stirring and mixing for 20min at the temperature of 30 ℃ and the vacuum degree of 0.06 MPa.
Example 3
70 parts of silane modified polyurethane prepolymer
40 parts of plasticizer diethyl phthalate
40 parts of filler
1 part of amination graphene oxide
Tackifier aminopropyl triethoxysilane 1 part
Antioxidant 2, 6-di-tert-butyl-4-methylphenol 1 part
Catalyst stannous octoate 0.5 parts
Wherein the silane modified polyurethane prepolymer is silane modified polyurethane prepolymer with the brand of SPUR 1015LM produced by Michaelis high new material group.
The filler is aluminum oxide treated by a silane coupling agent and aluminum hypophosphite compound treated by the silane coupling agent in a mass ratio of 2:1; the aluminum oxide treated by the silane coupling agent is prepared by the following preparation method: according to 5g: adding alumina into a silane coupling agent KH550 ethanol solution with the mass concentration of 5% according to the proportion of 100mL, stirring for 60min at 30 ℃, centrifuging for 30min at 10000r/min, and drying the solid obtained after centrifugation to obtain the alumina treated by the silane coupling agent; the aluminum hypophosphite treated by the silane coupling agent is prepared by the following preparation method: according to 5g:100mL of aluminum hypophosphite is added into a silane coupling agent KH550 ethanol solution with the mass concentration of 5%, after stirring for 60min at 30 ℃,10000r/min is centrifuged for 30min, and the solid obtained after centrifugation is dried, thus obtaining the aluminum hypophosphite treated by the silane coupling agent.
The aminated graphene oxide is prepared by the following steps: 3g of graphene oxide is dispersed in 100mL of deionized water to prepare a graphene oxide colloid suspension; according to 6g: dissolving diethylenetriamine in absolute ethanol according to the proportion of 100mL, and stirring until the diethylenetriamine is fully dissolved to obtain a solution; adding the solution into the graphene oxide colloid suspension, uniformly stirring to obtain an aminated graphene oxide dispersion solution, and carrying out vacuum suction filtration, washing and freeze drying on the aminated graphene oxide dispersion solution to obtain the aminated graphene oxide.
A preparation method of a polyurethane adhesive with high heat conduction and weather resistance for an automobile lithium battery comprises the following steps:
(1) Adding the silane modified polyurethane prepolymer, the plasticizer and the aminated graphene oxide into a stirrer, stirring and mixing for 30min at the temperature of 50 ℃ and the vacuum degree of 0.06 MPa;
(2) Adding filler into the mixture stirred and mixed in the step (1), and stirring and mixing for 30min at the temperature of 30 ℃ and the vacuum degree of 0.06 MPa;
(3) Adding tackifier, antioxidant and catalyst into the stirred and mixed mixture obtained in the step (2), and stirring and mixing for 20min at the temperature of 30 ℃ and the vacuum degree of 0.06 MPa.
The polyurethane adhesives prepared in the above examples and comparative examples were tested for adhesive properties without any treatment, and then tested for properties after being left at 120℃for 24 hours and irradiated with UV300 for 24 hours, and when tested for properties, the tensile strength and elongation at break were measured according to GB/T528, and the thermal conductivity was measured as follows: 200ml of test sample was placed in a 250ml glass beaker using a TPS 2500S model thermal conductivity tester from Hotdisk, sweden under a standard environment at 25℃and the test probe was placed in the sample and read after the data had stabilized.
Comparative example 1
The only difference from example 1 is that: the silane coupling agent treated alumina was not added.
Comparative example 2
The only difference from example 1 is that: aluminum hypophosphite treated without the addition of a silane coupling agent.
Comparative example 3
The only difference from example 1 is that: no silane coupling agent was added.
Comparative example 4
The only difference from example 1 is that: silane coupling agent treated alumina: the mass ratio of the aluminum hypophosphite treated by the silane coupling agent is 3:1.
Comparative example 5
The only difference from example 1 is that: no aminated graphene oxide was added.
Table 1 results of test of properties of polyurethane adhesive with high thermal conductivity and weather resistance for lithium batteries of automobiles
As can be seen from the performance test results in example 1 and comparative examples 1-2, the heat conductive properties of aluminum hypophosphite treated with only the silane coupling agent, and aluminum hypophosphite treated with both the silane coupling agent, aluminum hypophosphite treated with the silane coupling agent, and aluminum hypophosphite treated with both the silane coupling agent were significantly greater than the desired heat conductive effects (the sum of the effects of aluminum hypophosphite treated with only the silane coupling agent, aluminum oxide treated with only the silane coupling agent), the aluminum hypophosphite treated with the silane coupling agent, aluminum oxide treated with only the silane coupling agent of the present application had a synergistic effect, not a simple additive effect; as can be seen from example 1 and comparative example 3, the aluminum hypophosphite and aluminum oxide treated with the silane coupling agent have better compatibility, so that the prepared polyurethane adhesive has better weather resistance and thermal conductivity; as can be seen from example 1 and comparative example 4, the properties were more excellent only with the mass ratio of the alumina treated with the silane coupling agent of the present application to the aluminum hypophosphite treated with the silane coupling agent; from the performance test results of example 1 and comparative example 5, it can be seen that the addition of the aminated graphene oxide not only improves the thermal conductivity, but also further improves the weather resistance of the adhesive.
In addition to the above embodiments, the present application also includes other embodiments, and all technical solutions that are formed by equivalent transformation or equivalent substitution should fall within the protection scope of the claims of the present application.
Claims (8)
1. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile is characterized in that: comprises the following components in parts by weight:
70-100 parts of silane modified polyurethane prepolymer
40-60 parts of plasticizer
30-100 parts of filler
1-3 parts of amination graphene oxide
1-3 parts of tackifier
Antioxidant 1-2 parts
0.5-1 part of catalyst
The filler is a compound of aluminum oxide treated by a silane coupling agent and aluminum hypophosphite treated by the silane coupling agent, and the mass ratio of the aluminum oxide treated by the silane coupling agent to the aluminum hypophosphite treated by the silane coupling agent is 1-2:1-2.
2. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to claim 1, wherein the polyurethane adhesive is characterized in that: the plasticizer is at least one of dibutyl phthalate, diethyl phthalate, didecyl phthalate and dioctyl phthalate.
3. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to claim 1, wherein the polyurethane adhesive is characterized in that: the aluminum oxide treated by the silane coupling agent is prepared by the following preparation method: adding aluminum oxide into an ethanol solution of a silane coupling agent with the mass concentration of 0.5% -10%, stirring for 30-60 min at 30-50 ℃, centrifuging for 30-45 min at 5000-10000r/min, and drying the obtained solid after centrifuging to obtain the aluminum oxide treated by the silane coupling agent; the aluminum hypophosphite treated by the silane coupling agent is prepared by the following preparation method: adding aluminum hypophosphite into an ethanol solution of a silane coupling agent with the mass concentration of 0.5% -10%, stirring for 30-60 min at the temperature of 30-50 ℃, centrifuging for 30-45 min at the speed of 5000-10000r/min, and drying the obtained solid after centrifuging to obtain the aluminum hypophosphite treated by the silane coupling agent.
4. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to claim 1, wherein the polyurethane adhesive is characterized in that: the aminated graphene oxide is prepared by the following steps: dispersing graphene oxide in deionized water to prepare graphene oxide colloid suspension; according to (6-8 g): 100mL of the solution is prepared by dissolving an amine compound in absolute ethyl alcohol, and stirring until the amine compound is fully dissolved to obtain a solution; adding the solution into the graphene oxide colloid suspension, uniformly stirring to obtain an aminated graphene oxide dispersion solution, and carrying out vacuum suction filtration, washing and freeze drying on the aminated graphene oxide dispersion solution to obtain the aminated graphene oxide.
5. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to claim 1, wherein the polyurethane adhesive is characterized in that: the tackifier is at least one of aminopropyl trimethoxy silane, aminopropyl triethoxy silane, aminopropyl methyl dimethoxy silane and glycidoxy propyl trimethoxy silane.
6. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to claim 1, wherein the polyurethane adhesive is characterized in that: the antioxidant is at least one of 2, 6-di-tert-butyl-4-methylphenol and bis (3, 5-di-tert-butyl-4-hydroxyphenyl) sulfide.
7. The polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to claim 1, wherein the polyurethane adhesive is characterized in that: the catalyst is at least one of dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dioctanoate and stannous octoate.
8. A method for preparing the polyurethane adhesive with high heat conduction and weather resistance for the lithium battery of the automobile according to any one of claims 1 to 7, which is characterized in that: the method comprises the following steps:
(1) Adding the silane modified polyurethane prepolymer, the plasticizer and the aminated graphene oxide into a stirrer, and stirring and mixing under a vacuum condition;
(2) Adding filler into the mixture stirred and mixed in the step (1), and stirring and mixing under vacuum condition;
(3) Adding tackifier, antioxidant and catalyst into the stirred and mixed mixture obtained in the step (2), and stirring and mixing under vacuum condition.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211022914.9A CN115404035B (en) | 2022-08-25 | 2022-08-25 | Polyurethane adhesive with high heat conduction and weather resistance for automobile lithium battery and preparation method thereof |
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| CN202211022914.9A CN115404035B (en) | 2022-08-25 | 2022-08-25 | Polyurethane adhesive with high heat conduction and weather resistance for automobile lithium battery and preparation method thereof |
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| CN115404035B true CN115404035B (en) | 2023-11-28 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337630A (en) * | 2018-10-22 | 2019-02-15 | 广州市垠瀚能源科技有限公司 | A kind of two-component room temperature fast-curing antidetonation conductive structure adhesive preparation method |
| CN111961254A (en) * | 2020-08-27 | 2020-11-20 | 湖北航天化学技术研究所 | Preparation method of modified aluminum hypophosphite flame retardant |
| WO2021128102A1 (en) * | 2019-12-25 | 2021-07-01 | 宁波禾隆新材料股份有限公司 | Flame-retardant wood-plastic surface layer composite, and method for preparing wood-plastic composite material having flame-retardant wood-plastic surface composite |
| CN113621173A (en) * | 2021-08-20 | 2021-11-09 | 湖北航天化学技术研究所 | Composite flame retardant, additive type single-component flame-retardant waterborne polyurethane and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337630A (en) * | 2018-10-22 | 2019-02-15 | 广州市垠瀚能源科技有限公司 | A kind of two-component room temperature fast-curing antidetonation conductive structure adhesive preparation method |
| WO2021128102A1 (en) * | 2019-12-25 | 2021-07-01 | 宁波禾隆新材料股份有限公司 | Flame-retardant wood-plastic surface layer composite, and method for preparing wood-plastic composite material having flame-retardant wood-plastic surface composite |
| CN111961254A (en) * | 2020-08-27 | 2020-11-20 | 湖北航天化学技术研究所 | Preparation method of modified aluminum hypophosphite flame retardant |
| CN113621173A (en) * | 2021-08-20 | 2021-11-09 | 湖北航天化学技术研究所 | Composite flame retardant, additive type single-component flame-retardant waterborne polyurethane and preparation method thereof |
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