CN116731659A - Double-component polyurethane structural adhesive and preparation method thereof - Google Patents
Double-component polyurethane structural adhesive and preparation method thereof Download PDFInfo
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- CN116731659A CN116731659A CN202310774894.9A CN202310774894A CN116731659A CN 116731659 A CN116731659 A CN 116731659A CN 202310774894 A CN202310774894 A CN 202310774894A CN 116731659 A CN116731659 A CN 116731659A
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- aluminum hydroxide
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 68
- 239000000853 adhesive Substances 0.000 title claims abstract description 67
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 95
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 22
- 239000004359 castor oil Substances 0.000 claims abstract description 22
- 235000019438 castor oil Nutrition 0.000 claims abstract description 22
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002516 radical scavenger Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 23
- 238000011049 filling Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims 4
- 238000004062 sedimentation Methods 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000010008 shearing Methods 0.000 description 9
- XAGFODPZIPBFFR-NJFSPNSNSA-N Aluminium-29 Chemical group [29Al] XAGFODPZIPBFFR-NJFSPNSNSA-N 0.000 description 8
- 239000005062 Polybutadiene Substances 0.000 description 8
- 229920002857 polybutadiene Polymers 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 phosphate ester Chemical class 0.000 description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- DTSDCAXPMITGKB-UHFFFAOYSA-N aniline;triethoxy(propyl)silane Chemical compound NC1=CC=CC=C1.CCC[Si](OCC)(OCC)OCC DTSDCAXPMITGKB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 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 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 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
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to a double-component polyurethane structural adhesive and a preparation method thereof. Wherein, the bi-component polyurethane structural adhesive comprises the following components in volume ratio of 1:1 and a component A and a component B which are mixed and used, wherein the component A comprises the following components in parts by weight: 5 to 15 parts of castor oil modified polyol, 80 to 90 parts of modified aluminum hydroxide, 1 to 3 parts of water scavenger, 1 to 5 parts of gas-phase white carbon black and 1 to 3 parts of catalyst; the component B comprises the following components in parts by weight: 2 to 8 parts of hydroxyl-terminated polybutadiene polyol, 5 to 11 parts of diisocyanate, 80 to 90 parts of modified aluminum hydroxide, 1 to 5 parts of gas-phase white carbon black and 0.1 to 0.8 part of water scavenger. The double-component polyurethane structural adhesive has the advantages of low density, high heat conduction, low viscosity, high bonding strength, flame retardance and difficult precipitation and sedimentation.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a double-component polyurethane structural adhesive and a preparation method thereof.
Background
At present, most of the power batteries of the new energy automobiles are lithium ion batteries, and the lithium ion batteries in the automobile battery packs can generate heat in the charging and discharging processes. In order to transfer the heat generated by the battery to the cooling system of the battery pack, a thermally conductive structural adhesive material is required. The battery pack has a compact battery assembly structure, small gaps between batteries, and the heat-conducting structure adhesive material is required to have excellent fluidity before solidification, so that the gaps of the batteries are filled. In addition, the battery pack is inevitably subjected to vibration during running of the automobile, and thus the heat conductive structure adhesive material is required to have excellent adhesive properties and shock absorption. The main heat-conducting structure bonding material in the market at present is a double-component polyurethane heat-conducting structure adhesive, and the polyurethane adhesive with the heat conductivity coefficient of 1-2W/(m.K) is the most widely used in consideration of the principle of light weight. Polyurethane heat conduction structural adhesive with the viscosity of more than 2W/(m.K) in the market is sticky, is unfavorable for flowing and wetting gaps of the battery cells, has high density, and is unfavorable for the lightweight of the battery pack.
In the related art, one scheme is to use spherical alumina to match part of aluminum hydroxide as a filler, and although the effects of low viscosity, flame retardance and high adhesion can be achieved, the density of the alumina is higher and is between 3.6 and 3.9g/mL, so that the density of the adhesive is also increased, and the thermal conductivity coefficient of the polyurethane structural adhesive manufactured by the method is 2W/(m.K), and the density of the polyurethane structural adhesive is generally between 2.5 and 2.6 g/mL. Another solution is to use a liquid flame retardant of global alumina in combination with a phosphate ester, which, like the previous solution, has a higher density and the phosphate ester flame retardant has a plasticizing effect, resulting in a decrease in the adhesive strength of the glue. In addition, aluminum hydroxide is used together with a plasticizer, so that the adhesive strength is reduced, but the plasticizer is not added, the colloid is particularly thick due to the strong polarity of the aluminum hydroxide, and the effect of low viscosity cannot be achieved, and the heat conductivity coefficient of the polyurethane structural adhesive manufactured by the scheme is 2W/(m.K), and the density of the polyurethane structural adhesive is generally between 2.1 and 3.0 g/mL. Still another solution is disclosed in patent CN114316880a, in which aluminum hydroxide, aluminum oxide and glass beads are mixed together to effectively reduce the density, but the disadvantage is that too much glass beads can cause rapid viscosity rise and decrease in adhesion strength, and the compatibility of the beads with polyurethane system is poor, the beads can be separated out and float on the surface, which is unfavorable for long-term storage stability of the product, and the hollow property of the beads can reduce the thermal conductivity, so that the beads of the solution can only be applied in polyurethane system with low thermal conductivity, such as 0.8W/(m·k).
In view of the above, providing a new two-component polyurethane structural adhesive and a preparation method thereof are technical problems to be solved in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the bi-component polyurethane structural adhesive and the preparation method thereof, which have the advantages of low density, high heat conduction, low viscosity, high bonding strength, flame retardance and difficult precipitation and sedimentation.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a two-component polyurethane structural adhesive, which comprises an A component and a B component, wherein the volume ratio of the A component to the B component is 1:1, mixing and using;
the component A comprises the following components in parts by weight: 5 to 15 parts of castor oil modified polyol, 80 to 90 parts of modified aluminum hydroxide, 1 to 3 parts of water scavenger, 1 to 5 parts of gas-phase white carbon black and 1 to 3 parts of catalyst;
the component B comprises the following components in parts by weight: 2 to 8 parts of hydroxyl-terminated polybutadiene polyol, 5 to 11 parts of diisocyanate, 80 to 90 parts of modified aluminum hydroxide, 1 to 5 parts of gas-phase white carbon black and 0.1 to 0.8 part of water scavenger.
According to one embodiment of the invention, the castor oil modified polyol has a hydroxyl number of 170 to 315mg KOH/g.
According to one embodiment of the invention, the modified aluminum hydroxide has a particle size of 5 to 40. Mu.m.
According to one embodiment of the invention, the particle size of the modified aluminum hydroxide comprises one or more of 5 μm, 10 μm, 20 μm and 40 μm.
According to one embodiment of the invention, the modified aluminum hydroxide is prepared by adopting a silane coupling agent to modify aluminum hydroxide, and the weight part ratio of the aluminum hydroxide to the silane coupling agent is 100:1.
according to one embodiment of the invention, the specific surface area of the fumed silica comprises 150m 2 /g、180m 2 /g and 200m 2 One or more of/g.
According to one embodiment of the invention, the water scavenger comprises one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, and a p-toluenesulfonyl isocyanate.
According to one embodiment of the present invention, the hydroxyl-terminated polybutadiene polyol comprises one or more of a 2000 molecular weight secondary hydroxyl-terminated polybutadiene, a 3000 molecular weight secondary hydroxyl-terminated polybutadiene, a 2000 molecular weight primary hydroxyl-terminated polybutadiene, and a 3000 molecular weight primary hydroxyl-terminated polybutadiene.
The invention also provides a preparation method of the double-component polyurethane structural adhesive, which comprises the following steps:
step S1: preparing a component A: adding 5-15 parts of castor oil modified polyol and 80-90 parts of modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 30-40 ℃, adding 1-3 parts of a water scavenger, 1-5 parts of gas-phase white carbon black and 1-3 parts of a catalyst, stirring for 1-1.5 hours, and sealing and filling nitrogen for preservation to obtain a component A;
step S2: and (3) preparing a component B: adding 2-8 parts of hydroxyl-terminated polybutadiene polyol and 80-90 parts of modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, cooling to 50-60 ℃ after vacuum dehydration for 1-2 hours, adding 5-11 parts of diisocyanate, reacting for 2-3 hours at the temperature of 80-85 ℃, cooling to 30-40 ℃, adding 1-5 parts of gas-phase white carbon black and 0.1-0.8 part of water scavenger, stirring for 1-1.5 hours, and sealing and filling nitrogen for preservation to obtain the component B;
step S3: preparing a two-component polyurethane structural adhesive: and mixing the component A and the component B according to a volume ratio of 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
According to one embodiment of the present invention, before the step S1, the method further includes:
preparing modified aluminum hydroxide: adding aluminum hydroxide with the grain diameter of 5-40 mu m into a stirrer, stirring at the speed of 800r/min and heating to 70 ℃; the weight ratio of the aluminum hydroxide to the silane coupling agent is 100:1, adding a silane coupling agent into the aluminum hydroxide in a spraying mode, keeping the rotating speed of 800r/min, and heating to 105 ℃ for reaction for 20 min; maintaining the rotating speed, cooling to room temperature, discharging, sealing and preserving to obtain the modified aluminum hydroxide.
The beneficial effects are that: the volume ratio of the component A to the component B is 1:1, preparing the double-component polyurethane structural adhesive, wherein the component A comprises the following components in parts by weight: 5 to 15 parts of castor oil modified polyol, 80 to 90 parts of modified aluminum hydroxide, 1 to 3 parts of water scavenger, 1 to 5 parts of gas-phase white carbon black and 1 to 3 parts of catalyst; the component B comprises the following components in parts by weight: 2 to 8 parts of hydroxyl-terminated polybutadiene polyol, 5 to 11 parts of diisocyanate, 80 to 90 parts of modified aluminum hydroxide, 1 to 5 parts of gas-phase white carbon black and 0.1 to 0.8 part of water scavenger. The double-component polyurethane structural adhesive can achieve cohesive failure in the bonding failure mode between GB/T7124-2008 (3003 aluminum) which is not treated, has the shearing strength of more than or equal to 9.00MPa, has the shearing strength of more than or equal to 3.00MPa on PET (Polyethylene terephthalate, polyester resin) base materials, has the heat conductivity coefficient of more than 2.00W/(m.K), has the mixing density of less than or equal to 2.00g/mL, and has the advantages of low density, high heat conductivity, low viscosity, high bonding strength, flame retardance and difficult precipitation and sedimentation.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a two-component polyurethane structural adhesive according to an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is described below through specific examples.
The new energy automobile power battery mainly has three structural types of square shell, soft package and cylinder, and a large amount of materials are needed in the battery system to realize the grouping of the electric cells, and the requirements of each material are different and can be basically divided into structural bonding materials, heat conducting materials, insulating materials, heat insulating materials and sealing materials, wherein the structural bonding materials are very key. The structural bonding material is mainly used for bonding the battery cells, the foam, the battery cells, the module shell and the like, and mainly has the effects that the battery cells and the module are integrated, so that the requirements of vibration, impact, falling and the like of the module are met. The bi-component polyurethane structural adhesive provided by the embodiment of the invention has the advantages of low density, high heat conduction, low viscosity, high bonding strength, flame retardance and difficult precipitation and sedimentation, and can be applied to battery assembly, in particular to new energy automobile power battery assembly.
The bi-component polyurethane structural adhesive provided by the embodiment of the invention comprises a component A and a component B, wherein the volume ratio of the component A to the component B is 1:1, mixing and using; wherein the component A comprises the following components in parts by weight: 5 to 15 parts of castor oil modified polyol, 80 to 90 parts of modified aluminum hydroxide, 1 to 3 parts of water scavenger, 1 to 5 parts of gas-phase white carbon black and 1 to 3 parts of catalyst; the component B comprises the following components in parts by weight: 2 to 8 parts of hydroxyl-terminated polybutadiene polyol, 5 to 11 parts of diisocyanate, 80 to 90 parts of modified aluminum hydroxide, 1 to 5 parts of gas-phase white carbon black and 0.1 to 0.8 part of water scavenger.
As an example, the modified aluminum hydroxide is prepared by modifying aluminum hydroxide with a silane coupling agent, and the weight part ratio of aluminum hydroxide to the silane coupling agent is 100:1.
further, the silane coupling agent includes one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, N-beta-aminoethyl-gamma-aminopropyl methyldimethoxysilane, aniline methyltriethoxysilane, aniline propyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane. Beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.
As an example, modified aluminum hydroxide can be produced by charging aluminum hydroxide having a particle diameter of 5 to 40 μm into a stirrer, and heating to 70 ℃ while stirring at a rotation speed of 800 r/min; the weight ratio of the aluminum hydroxide to the silane coupling agent is 100:1, adding a silane coupling agent into a stirrer in a spraying manner, keeping the rotating speed of 800r/min, heating to 105 ℃ and reacting for 20 min; maintaining the rotating speed, cooling to room temperature, discharging, sealing and preserving to obtain the modified aluminum hydroxide with the grain diameter of 5-40 mu m.
As one example, the particle size of the modified aluminum hydroxide includes one or more of 5 μm, 10 μm, 20 μm, and 40 μm.
In the preparation process of the polyurethane heat-conducting material, the smaller the particle size of the filler is, the better the anti-sedimentation performance is, the smaller the loss to equipment is, but the components are easy to become larger in viscosity, difficult to disperse, poor in operability and the like, and the heat-conducting performance is not improved easily only by selecting the filler with small particle size. While coarse-particle size fillers, although having a higher thermal conductivity, are prone to sedimentation and large particles can wear the machine. According to the embodiment of the invention, through mixing and matching of aluminum hydroxide with different particle sizes, the anti-sedimentation effect of the components is better, the filling amount of the filler is reduced, and the heat conductivity coefficient is higher. The aluminum hydroxide with different particle sizes is matched and the silane coupling agent is adopted for surface treatment, so that the surface of the modified aluminum hydroxide is similar to an oil-in-water group, the modified aluminum hydroxide is more easily infiltrated with castor oil modified polyol, the purpose of reducing the viscosity of a system is achieved, the prepared colloid achieves the effects of high heat conductivity coefficient, low density and low viscosity, and the group grafted on the surface of the modified aluminum hydroxide can participate in the reaction, and the adhesive force of the colloid is increased.
As an example, the hydroxyl number of the castor oil modified polyol is 170 to 315mg KOH/g. Preferably, the castor oil modified polyol comprises one or more of a hydroxyl number of 315mg KOH/g, a hydroxyl number of 170mg KOH/g, a hydroxyl number of 215mg KOH/g, a hydroxyl number of 240mg KOH/g, and a hydroxyl number of 260mg KOH/g. More preferably, the hydroxyl number is 315mg KOH/g of modified castor oil. The polyol of the embodiment is selected from castor oil modified polyol with low viscosity, high powder filling amount and aging resistance, and has good adhesion to metal.
As an example, the hydroxyl-terminated polybutadiene polyol includes one or more of a 2000 molecular weight secondary hydroxyl-terminated polybutadiene, a 3000 molecular weight secondary hydroxyl-terminated polybutadiene, a 2000 molecular weight primary hydroxyl-terminated polybutadiene, and a 3000 molecular weight primary hydroxyl-terminated polybutadiene. Preferably a terminal primary hydroxyl polybutadiene of 2000 molecular weight. The bonding of the new energy battery core is also based on PET, and the PET has low polarity, and hydroxyl-terminated polybutadiene with the same low polarity is selected, so that the bonding property to PET is good.
As an example, the specific surface area of the fumed silica comprises 150m 2 /g、180m 2 /g and 200m 2 One or more of/g. Fumed silica having a specific surface area of 150m2/g is preferred. The gas-phase white carbon black can be used for thixotropic treatment of the adhesive to reduce sedimentation and reinforcing to improve bonding performance.
As one example, the water scavenger includes one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, and p-toluenesulfonyl isocyanate. The A component is preferably 3A molecular sieve, and the B component is preferably p-toluenesulfonyl isocyanate.
As one example, the diisocyanate includes one or more of diphenylmethane diisocyanate, carbodiimide-uretonimine modified MDI, polymethylene polyphenyl isocyanate, and dicyclohexylmethane diisocyanate. Dicyclohexylmethane diisocyanate is preferred.
As one example, the catalyst is an organotin catalyst including one or more of dibutyltin dilaurate, stannous octoate, dibutyltin dilaurate and dibutyltin diacetate. Dibutyl tin dilaurate is preferred.
The embodiment of the invention also provides a preparation method of the double-component polyurethane structural adhesive, as shown in fig. 1, comprising the following steps:
step S1: preparing a component A: 5 to 15 parts of castor oil modified polyol and 80 to 90 parts of modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100 to 110 ℃, dehydrated in vacuum for 1 to 2 hours and cooled to 30 to 40 ℃, then added with 1 to 3 parts of water scavenger, 1 to 5 parts of gas-phase white carbon black and 1 to 3 parts of catalyst, stirred for 1 to 1.5 hours and then sealed and filled with nitrogen for preservation as a component A.
In this step, the descriptions of the raw materials are described in detail in the foregoing, and will not be repeated here.
Step S2: and (3) preparing a component B: adding 2-8 parts of hydroxyl-terminated polybutadiene polyol and 80-90 parts of modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, cooling to 50-60 ℃ after vacuum dehydration for 1-2 hours, adding 5-11 parts of diisocyanate, reacting for 2-3 hours at the temperature of 80-85 ℃, cooling to 30-40 ℃, adding 1-5 parts of gas-phase white carbon black and 0.1-0.8 part of water scavenger, stirring for 1-1.5 hours, and sealing and filling nitrogen for preservation to obtain a component B.
In this step, the descriptions of the raw materials are described in detail in the foregoing, and will not be repeated here.
Step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
As an embodiment, before step S1, further includes:
preparing modified aluminum hydroxide: adding aluminum hydroxide with the grain diameter of 5-40 mu m into a stirrer, stirring at the speed of 800r/min and heating to 70 ℃; the weight ratio of the aluminum hydroxide to the silane coupling agent is 100:1, adding a silane coupling agent into aluminum hydroxide in a spraying mode, keeping the rotating speed of 800r/min, heating to 105 ℃ and reacting for 20 min; maintaining the rotating speed, cooling to room temperature, discharging, sealing and preserving to obtain the modified aluminum hydroxide.
In the step, 1000g of 5 mu m aluminum hydroxide, 10 mu m aluminum hydroxide, 20 mu m aluminum hydroxide and 40 mu m aluminum hydroxide are respectively put into each stirrer, the temperature is raised to 70 ℃ while stirring at the rotation speed of 800r/min, 10g of beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane is added into the aluminum hydroxide in a spraying mode, the rotation speed of 800r/min is kept, the temperature is raised to 105 ℃ for reacting for 20min, the rotation speed is kept to be reduced, the temperature is cooled to room temperature, and finally, the materials are discharged and stored in a sealing mode, so that four fillers of 5 mu m modified aluminum hydroxide, 10 mu m modified aluminum hydroxide, 20 mu m modified aluminum hydroxide and 40 mu m modified aluminum hydroxide are respectively obtained.
The viscosity of each component in the bi-component polyurethane structural adhesive prepared by the embodiment of the invention is less than 150000mpa.s (at present, the viscosity of the structural adhesive with the heat conductivity coefficient of a condensate reaching more than 2W/(m.K) is generally more than 150000 mpa.s), cohesive failure can be achieved in the bonding failure mode between GB/T7124-2008 (3003 aluminum) which is not processed, the shearing strength is more than or equal to 9.00MPa, the shearing strength of PET (Polyethylene terephthalate) and polyester resin) base materials is more than or equal to 3.00MPa, the heat conductivity coefficient reaches more than 2.00W/(m.K), and the mixing density is less than or equal to 2.00 g/mL.
Example 1
Step S1: preparing a component A: 10 parts by weight of 315mg KOH/g castor oil modified polyol, 56 parts by weight of 40 mu m modified aluminum hydroxide and 29 parts by weight of 10 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated for 1-2 hours in vacuum and cooled to 30-40 ℃, and then 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m are added 2 Stirring/g gas-phase white carbon black and 1 part by weight of dibutyl tin dilaurate for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component A;
step S2: and (3) preparing a component B: adding 4.5 parts by weight of 2000 molecular weight terminal primary hydroxyl polybutadiene, 56 parts by weight of 40 mu m modified aluminum hydroxide and 29 parts by weight of 10 mu m modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 50-60 ℃, adding 8 parts by weight of dicyclohexylmethane diisocyanate, keeping the temperature at 80-85 ℃ for reacting for 2-3 hours, cooling to 30-40 ℃, and adding 0.5 part by weight of p-toluenesulfonyl isocyanate and 2 parts by weight of 150m 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Example 2
Step S1: preparing a component A: 5 parts by weight of 315mg KOH/g castor oil modified polyol, 66 parts by weight of 40 mu m modified aluminum hydroxide and 24 parts by weight of 10 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated for 1-2 hours in vacuum and cooled to 30-40 ℃, and then 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m are added 2 Stirring/g gas-phase white carbon black and 1 part by weight of dibutyl tin dilaurate for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component A;
step S2: and (3) preparing a component B: will 7 weight portions2000 molecular weight terminal primary hydroxyl polybutadiene, 61 parts by weight of 40 mu m modified aluminum hydroxide and 19 parts by weight of 10 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated in vacuum for 1-2 hours and cooled to 50-60 ℃, 10.5 parts by weight of dicyclohexylmethane diisocyanate is added, the reaction is carried out for 2-3 hours at the temperature of 80-85 ℃, cooled to 30-40 ℃, and 0.5 part by weight of p-toluenesulfonyl isocyanate and 2 parts by weight of 150m are added 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Example 3
Step S1: preparing a component A: 10 parts by weight of 315mg KOH/g castor oil modified polyol, 56 parts by weight of 40 mu m modified aluminum hydroxide and 29 parts by weight of 5 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated for 1-2 hours in vacuum and cooled to 30-40 ℃, and then 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m are added 2 Stirring/g gas-phase white carbon black and 1 part by weight of dibutyl tin dilaurate for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component A;
step S2: and (3) preparing a component B: adding 4.5 parts by weight of 2000 molecular weight terminal primary hydroxyl polybutadiene, 56 parts by weight of 40 mu m modified aluminum hydroxide and 29 parts by weight of 5 mu m modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 50-60 ℃, adding 8 parts by weight of dicyclohexylmethane diisocyanate, keeping the temperature at 80-85 ℃ for reacting for 2-3 hours, cooling to 30-40 ℃, and adding 0.5 part by weight of p-toluenesulfonyl isocyanate and 2 parts by weight of 150m 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Example 4
Step S1: preparation AThe components are as follows: 10 parts by weight of 315mg KOH/g castor oil modified polyol, 56 parts by weight of 30 mu m modified aluminum hydroxide and 29 parts by weight of 5 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated for 1-2 hours in vacuum and cooled to 30-40 ℃, and then 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m are added 2 Stirring/g gas-phase white carbon black and 1 part by weight of dibutyl tin dilaurate for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component A;
step S2: and (3) preparing a component B: adding 4.5 parts by weight of 2000 molecular weight terminal primary hydroxyl polybutadiene, 56 parts by weight of 30 mu m modified aluminum hydroxide and 29 parts by weight of 5 mu m modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 50-60 ℃, adding 8 parts by weight of dicyclohexylmethane diisocyanate, keeping the temperature at 80-85 ℃ for reacting for 2-3 hours, cooling to 30-40 ℃, and adding 0.5 part by weight of p-toluenesulfonyl isocyanate and 2 parts by weight of 150m 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Example 5
Step S1: preparing a component A: 15 parts by weight of 315mg KOH/g castor oil modified polyol, 61 parts by weight of 30 mu m modified aluminum hydroxide and 19 parts by weight of 5 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated for 1-2 hours in vacuum and cooled to 30-40 ℃, and then 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m are added 2 Stirring/g gas-phase white carbon black and 1 part by weight of dibutyl tin dilaurate for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component A;
step S2: and (3) preparing a component B: 2 parts by weight of 2000 molecular weight terminal primary hydroxyl polybutadiene, 66 parts by weight of 30-micron modified aluminum hydroxide and 24 parts by weight of 5-micron modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated in vacuum for 1-2 hours, cooled to 50-60 ℃, added with 5.5 parts by weight of dicyclohexylmethane diisocyanate, and kept warmAfter reacting for 2 to 3 hours at the temperature of 80 to 85 ℃, the temperature is reduced to 30 to 40 ℃, and then 0.5 weight part of p-toluenesulfonyl isocyanate and 2 weight parts of 150m are added 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Comparative example 1
Step S1: preparing a component A: 10 parts by weight of 315mg KOH/g castor oil modified polyol, 56 parts by weight of 40 mu m aluminum hydroxide and 29 parts by weight of 10 mu m aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated in vacuum for 1-2 hours and cooled to 30-40 ℃, and then 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m aluminum hydroxide are added 2 Stirring/g gas-phase white carbon black and 1 part by weight of dibutyl tin dilaurate for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component A;
step S2: and (3) preparing a component B: adding 4.5 parts by weight of 2000 molecular weight terminal primary hydroxyl polybutadiene, 56 parts by weight of 40 mu m aluminum hydroxide and 29 parts by weight of 10 mu m aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 50-60 ℃, adding 8 parts by weight of dicyclohexylmethane diisocyanate, keeping the temperature of 80-85 ℃ for reacting for 2-3 hours, cooling to 30-40 ℃, and adding 0.5 part by weight of p-toluenesulfonyl isocyanate and 2 parts by weight of 150m 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
Comparative example 2
Step S1: preparing a component A: 10 parts by weight of 315mg KOH/g castor oil modified polyol and 85 parts by weight of 30 mu m modified aluminum hydroxide are put into a reaction vessel, stirred and heated to 100-110 ℃, dehydrated in vacuum for 1-2 hours and cooled to 30-40 ℃, and then added with 2 parts by weight of 3A molecular sieve and 2 parts by weight of 150m 2 Gas phase white carbon black/g and 1 part by weight of dibutyl tin dilaurylStirring the laurate for 1 to 1.5 hours, and then sealing and filling nitrogen to store the laurate as a component A;
step S2: and (3) preparing a component B: adding 4.5 parts by weight of 2000 molecular weight terminal primary hydroxyl polybutadiene and 85 parts by weight of 30 mu m modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 50-60 ℃, adding 8 parts by weight of dicyclohexylmethane diisocyanate, keeping the temperature of 80-85 ℃ for reacting for 2-3 hours, cooling to 30-40 ℃, and adding 0.5 part by weight of p-toluenesulfonyl isocyanate and 2 parts by weight of 150m 2 Stirring for 1-1.5 hours, and sealing, filling nitrogen and preserving as a component B;
step S3: preparing a two-component polyurethane structural adhesive: the volume ratio of the component A to the component B is 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
The two-component polyurethane structural adhesives prepared in examples 1 to 5 and comparative examples 1 to 2 were cured at normal temperature of 25℃and humidity of 55RH% for 7 days, and the following performance tests were carried out, and the test results are shown in Table 1.
1. Viscosity test: the viscosities of A, B components were tested according to standard GB/T9751.1-2008 using Bowler-FeiCAP2000+ cone plate viscosimetry, respectively;
2. density testing: using a 6mm thick and 15mm diameter cured block, and testing the cured mixed density by a densitometer;
3. shear strength test: manufacturing a shearing test bar according to the standard GB/T7124-2008, and testing the shearing strength of the GB/T7124-2008 (3003 aluminum) and the shearing strength of the PET material by using a universal tensile machine;
4. thermal conductivity test: manufacturing a heat conduction block according to the standard GB/T29313-2012, and testing the heat conductivity by using HOTDISK;
5. sedimentation performance test: taking 2Kg samples of the experimental example and the comparative example, and checking the precipitation condition of the bottom of the sample glue sample by using a scraper every month, wherein the sample glue sample is soft sedimentation if the scraper tip is provided with a filler soft block but can be stirred, and the sample glue sample is hard sedimentation if the scraper tip is hard and cannot be stirred;
6. flame retardant performance test: manufacturing a flame-retardant strip with the thickness of 3mm according to the UL 94 standard, and testing the flame-retardant performance by using a flame-retardant box;
table 1 shows the results of performance tests of the two-component polyurethane structural adhesives prepared in examples 1-5 and comparative examples 1-2.
As shown in Table 1, the low-density high-heat-conductivity two-component polyurethane structural adhesive prepared by special surface modification of aluminum hydroxide and reasonable proportion of different particle diameters in examples 1-5 has the advantages of low density, high heat conductivity, low viscosity, high adhesive strength, flame retardance and difficult precipitation sedimentation, wherein the viscosity of each component in example 2 is less than 100000mpa.s, cohesive failure can be achieved for untreated GB/T7124-2008 (3003 aluminum material), the shearing strength is more than or equal to 9.00MPa, the shearing strength is more than or equal to 3.00MPa for PET base materials, the heat conductivity coefficient of a solidified product is more than 2.00W/(m.K), and meanwhile, each density is less than or equal to 2.00g/mL, and the low-density high-heat-conductivity high-viscosity high-adhesive-strength flame-retardant high-performance two-component polyurethane structural adhesive can be applied to battery assembly, especially new energy automobile power battery assembly.
The foregoing is only the embodiments of the present invention, and therefore, the patent scope of the invention is not limited thereto, and all equivalent structures or equivalent processes using the descriptions of the present invention and the accompanying drawings, or direct or indirect application in other related technical fields, are included in the scope of the invention.
Claims (10)
1. The double-component polyurethane structural adhesive is characterized by comprising an A component and a B component, wherein the volume ratio of the A component to the B component is 1:1, mixing and using;
the component A comprises the following components in parts by weight: 5 to 15 parts of castor oil modified polyol, 80 to 90 parts of modified aluminum hydroxide, 1 to 3 parts of water scavenger, 1 to 5 parts of gas-phase white carbon black and 1 to 3 parts of catalyst;
the component B comprises the following components in parts by weight: 2 to 8 parts of hydroxyl-terminated polybutadiene polyol, 5 to 11 parts of diisocyanate, 80 to 90 parts of modified aluminum hydroxide, 1 to 5 parts of gas-phase white carbon black and 0.1 to 0.8 part of water scavenger.
2. The two-component polyurethane construction adhesive according to claim 1, wherein the castor oil modified polyol has a hydroxyl number of 170 to 315mg KOH/g.
3. The two-component polyurethane construction glue according to claim 1, wherein the particle size of the modified aluminium hydroxide is 5-40 μm.
4. The two-component polyurethane construction glue of claim 3, wherein the particle size of the modified aluminum hydroxide comprises one or more of 5 μιη, 10 μιη, 20 μιη, and 40 μιη.
5. The two-component polyurethane structural adhesive according to claim 1, wherein the modified aluminum hydroxide is prepared by modifying aluminum hydroxide with a silane coupling agent, and the weight ratio of the aluminum hydroxide to the silane coupling agent is 100:1.
6. the two-component polyurethane structural adhesive according to claim 1, wherein the specific surface area of the fumed silica comprises 150m 2 /g、180m 2 /g and 200m 2 One or more of/g.
7. The two-part polyurethane structural adhesive of claim 1, wherein the water scavenger comprises one or more of a 3A molecular sieve, a 4A molecular sieve, a 5A molecular sieve, and a p-toluenesulfonyl isocyanate.
8. The two-component polyurethane construction adhesive of claim 1, wherein the hydroxyl-terminated polybutadiene polyol comprises one or more of a 2000 molecular weight, a 3000 molecular weight, a 2000 molecular weight, a primary hydroxyl-terminated polybutadiene, and a 3000 molecular weight, primary hydroxyl-terminated polybutadiene.
9. The preparation method of the two-component polyurethane structural adhesive is characterized by comprising the following steps of:
step S1: preparing a component A: adding 5-15 parts of castor oil modified polyol and 80-90 parts of modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, vacuum dehydrating for 1-2 hours, cooling to 30-40 ℃, adding 1-3 parts of a water scavenger, 1-5 parts of gas-phase white carbon black and 1-3 parts of a catalyst, stirring for 1-1.5 hours, and sealing and filling nitrogen for preservation to obtain a component A;
step S2: and (3) preparing a component B: adding 2-8 parts of hydroxyl-terminated polybutadiene polyol and 80-90 parts of modified aluminum hydroxide into a reaction vessel, stirring and heating to 100-110 ℃, cooling to 50-60 ℃ after vacuum dehydration for 1-2 hours, adding 5-11 parts of diisocyanate, reacting for 2-3 hours at the temperature of 80-85 ℃, cooling to 30-40 ℃, adding 1-5 parts of gas-phase white carbon black and 0.1-0.8 part of water scavenger, stirring for 1-1.5 hours, and sealing and filling nitrogen for preservation to obtain the component B;
step S3: preparing a two-component polyurethane structural adhesive: and mixing the component A and the component B according to a volume ratio of 1:1, uniformly mixing to obtain the double-component polyurethane structural adhesive.
10. The method according to claim 9, further comprising, prior to the step S1:
preparing modified aluminum hydroxide: adding aluminum hydroxide with the grain diameter of 5-40 mu m into a stirrer, stirring at the speed of 800r/min and heating to 70 ℃; the weight ratio of the aluminum hydroxide to the silane coupling agent is 100:1, adding a silane coupling agent into the aluminum hydroxide in a spraying mode, keeping the rotating speed of 800r/min, and heating to 105 ℃ for reaction for 20 min; maintaining the rotating speed, cooling to room temperature, discharging, sealing and preserving to obtain the modified aluminum hydroxide.
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