CN116042167A - Carbon dioxide-based bi-component polyurethane heat-conducting adhesive and preparation method thereof - Google Patents
Carbon dioxide-based bi-component polyurethane heat-conducting adhesive and preparation method thereof Download PDFInfo
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- 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
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- C08G18/40—High-molecular-weight compounds
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- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/28—Nitrogen-containing compounds
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Abstract
The invention belongs to the field of polyurethane adhesives, and relates to a carbon dioxide-based bi-component polyurethane heat-conducting adhesive and a preparation method thereof. The carbon dioxide-based double-component polyurethane heat-conducting adhesive comprises a component A and a component B in a volume ratio of (1-2) to 1; the component A comprises an isocyanate double-end-capped polyurethane prepolymer, a first heat-conducting filler and an optional first auxiliary agent, wherein the isocyanate double-end-capped polyurethane prepolymer is prepared by nucleophilic addition reaction of modified carbon dioxide-based polycarbonate dihydric alcohol, castor oil polyol and polyisocyanate optionally in the presence of a first catalyst; the component B comprises polyether polyol, polybutadiene polyol, small molecule polyol, second heat conducting filler, and optional second catalyst and second auxiliary agent. The carbon dioxide-based bi-component polyurethane heat-conducting adhesive provided by the invention has excellent adhesive strength and heat-conducting property.
Description
Technical Field
The invention belongs to the field of polyurethane adhesives, and particularly relates to a carbon dioxide-based bi-component polyurethane heat-conducting adhesive and a preparation method thereof.
Background
The rapid development of the new energy automobile industry makes the power battery PACK put forward a new demand in the adhesive aspect. The surface materials of the power battery PACK module comprise various functional materials such as PET blue film and aluminum alloy, structural adhesive is required to adhere various materials well under the condition that surface treatment is not performed, meanwhile, medium elastic modulus and excellent flame retardance are required, the working condition of high-frequency vibration of the power battery is met, and the power battery PACK module is suitable for use in extremely cold areas and high-heat areas of automobiles. In addition, as the energy density of the power battery is higher, the charge and discharge heat release amount in unit time of the battery is higher, and the requirement on the heat conduction performance of the adhesive is higher.
It is known that the adhesive strength of an adhesive gradually decreases as the heat conductive filler increases and the resin decreases. In the prior art, epoxy glue and acrylic ester glue have extremely high bonding strength, but the problem of low heat conductivity coefficient is common. Although the organosilicon heat-conducting adhesive can achieve higher modulus of heat conductivity coefficient, the bonding strength is very low, and the requirement of structural bonding is difficult to meet.
The double-component polyurethane adhesive has the advantages of long storage period, adjustable modulus and the like, and is gradually valued in the structural bonding of the lithium battery PACK. However, the key raw material in the traditional polyurethane adhesive, namely the polyol polymer, is mostly from limited fossil fuel resources, which limits the green and environment-friendly development of the polyurethane adhesive to a great extent. On the other hand, the adhesive strength of polyurethane adhesives prepared by using conventional polyester polyols and polyether polyols needs to be further improved, and especially the adhesive strength is obviously reduced when the content of the heat conducting filler is higher.
In summary, in order to meet the increasing composite demands of new energy automobiles in the aspects of structural bonding and heat dissipation of lithium batteries PACK, how to prepare a two-component polyurethane adhesive which is green and environment-friendly and has excellent bonding strength and heat conducting property has become a problem to be solved.
Disclosure of Invention
The invention aims at providing a carbon dioxide-based two-component polyurethane heat-conducting adhesive with good adhesive strength and heat-conducting property.
The second aim of the invention is to provide a preparation method of the carbon dioxide-based two-component polyurethane heat-conducting adhesive.
The carbon dioxide-based bi-component polyurethane heat-conducting adhesive provided by the invention comprises a component A and a component B in a volume ratio of (1-2) 1; the component A comprises an isocyanate double-end-capped polyurethane prepolymer, a first heat-conducting filler and an optional first auxiliary agent, wherein the isocyanate double-end-capped polyurethane prepolymer is prepared by nucleophilic addition reaction of modified carbon dioxide-based polycarbonate dihydric alcohol, castor oil polyol and polyisocyanate optionally in the presence of a first catalyst; the component B comprises polyether polyol, polybutadiene polyol, small molecule polyol, a second heat-conducting filler, and optional second catalyst and second auxiliary agent; the modified carbon dioxide-based polycarbonate diol contains a structural unit shown in a formula (I), a structural unit shown in a formula (II) and a structural unit shown in a formula (III) at the same time:
in the formula (III), R 1 、R 2 And R is 3 Each independently is C 1 -C 5 Is a hydrocarbon group.
In one embodiment, the modified carbon dioxide based polycarbonate diol is represented by formula (IV):
in the formula (IV), m and n represent the molar ratio of the corresponding structural units, wherein n is more than or equal to 0.90 and less than or equal to 0.97 (such as 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97 or any value therebetween), and m+n=1. In the formula (IV), the content of the structural unit derived from propylene oxide is represented by n, and the content of the structural unit derived from 1, 2-epoxy-4-vinylcyclohexane is represented by m, so that the molar ratio of the structural units is different, and the formula (IV) is only used to represent the kind and the ratio of each structural unit, and the copolymerization type and the connection relationship between the structural units cannot be represented. The modified carbon dioxide based polycarbonate diol may be a random copolymer or a block copolymer.
In the present invention, C 1 -C 5 Specific examples of alkyl groups of (a) include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl.
The number average molecular weight of the modified carbon dioxide based polycarbonate diol is preferably 1500 to 4000, such as 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000 or any value therebetween.
In a preferred embodiment, the volume ratio of the A and B components is (1-2): 1, such as 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, or any value therebetween.
In a preferred embodiment, the isocyanate-terminated polyurethane prepolymer is present in component a in an amount of from 20 to 60 parts by weight, such as 20, 25, 30, 35, 40, 45, 50, 55, 60 parts by weight and any value therebetween; the first thermally conductive filler is present in an amount of 45 to 85 parts by weight, such as 45, 50, 55, 60, 65, 70, 75, 80, 85 parts by weight or any value therebetween; the first auxiliary agent is contained in an amount of 0.1 to 5 parts by weight, such as 0.1, 0.5, 1,2, 3,4, 5 parts by weight or any value therebetween.
In a preferred embodiment, the polyether polyol is present in component B in an amount of 10 to 30 parts by weight, such as 10, 12, 15, 18, 20, 22, 25, 28, 30 parts by weight or any value therebetween; the polybutadiene polyol is present in an amount of 10 to 20 parts by weight, such as 10, 12, 15, 18, 20 parts by weight or any value therebetween; the content of the small molecular polyol is 1-5 parts by weight, such as 1,2, 3,4, 5 parts by weight or any value between them; the second heat conductive filler is contained in an amount of 50 to 80 parts by weight, such as 50, 55, 60, 65, 70, 75, 80 parts by weight or any value therebetween; the second catalyst is present in an amount of 0 to 1 part by weight, such as 0, 0.2, 0.4, 0.6, 0.8, 1 part by weight or any value therebetween; the second auxiliary agent is contained in an amount of 0.1 to 5 parts by weight, such as 0.1, 0.5, 1,2, 3,4, 5 parts by weight or any value therebetween.
The modified carbon dioxide-based polycarbonate diol can be obtained commercially or prepared according to various existing methods. In a preferred embodiment, the modified carbon dioxide based polycarbonate diol is prepared according to the following method:
s1, placing a third catalyst into a high-pressure reaction kettle, vacuumizing the high-pressure reaction kettle for at least 2 hours at 50-80 ℃ and filling CO 2 Treatment in CO 2 Adding propylene oxide and 1, 2-epoxy-4-vinylcyclohexane into a high-pressure reaction kettle under the protection of (1), stirring, and passing CO 2 The pressure regulator introduces CO into the kettle 2 The high-pressure reaction kettle is placed in a constant temperature bath for copolymerization reaction for 4 to 8 hours under the condition of 28.5 to 32.0atm, and after the reaction is finished, the high-pressure reaction kettle is cooled to the temperature below 20 ℃ to slowly release the residual CO 2 Obtaining carbon dioxide-based polycarbonate diol;
s2, adding carbon dioxide-based polycarbonate dihydric alcohol, 3-mercaptopropyl trialkoxysilane, a free radical photoinitiator and an organic solvent into a reaction kettle, stirring until the solid is completely dissolved, and then carrying out reaction under ultraviolet irradiation to obtain a mercapto alkene reaction product;
s3, concentrating the sulfhydryl alkene reaction product, slowly adding the concentrated product into a non-solvent to precipitate a polymer, filtering and drying to obtain the modified carbon dioxide-based polycarbonate diol.
In a preferred embodiment, the molar ratio of the amount of the third catalyst to the total amount of propylene oxide and 1, 2-epoxy-4-vinylcyclohexane is 1 (2000-7000), such as 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500, 1:5000, 1:5500, 1:6000, 1:6500, 1:7000 or any value in between.
In a preferred embodiment, the molar ratio of 1, 2-epoxy-4-vinylcyclohexane to propylene oxide is 1 (13-55), such as 1:13, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, or any value therebetween.
In a preferred embodiment, the third catalyst is selected from one or more of zinc carboxylate catalytic systems, zinc phenoxide catalytic systems, beta-diimine zinc catalytic systems, pyridine-zinc catalytic systems, porphyrin-based catalytic systems, salenMX-based catalytic systems, rare earth catalytic systems, double metal cyanide catalytic systems, and supported catalytic systems.
The free radical photoinitiator can be various existing compounds capable of absorbing ultraviolet light energy to generate free radicals so as to trigger mercapto and alkenyl to perform mercapto-ene click reaction. In a preferred embodiment of the present invention, the free radical photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylbenzophenone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl) butanone 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-hexanone, bis 2, 6-difluoro-3-pyrrolidocenetitanium, methyl benzoate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl o-benzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone, and 2-ethyl anthraquinone.
In a preferred embodiment, the modified carbon dioxide-based polycarbonate diol is used in an amount of 10 to 30 parts by weight, such as 10, 12, 18, 20, 22, 25, 28, 30 parts by weight or any value therebetween, in the preparation of the isocyanate-terminated polyurethane prepolymer; the castor oil polyol is used in an amount of 5 to 10 parts by weight, such as 5, 6, 7, 8, 9, 10 parts by weight or any value therebetween; the polyisocyanate is used in an amount of 5 to 15 parts by weight, such as 5, 8, 10, 12, 15 parts by weight or any value therebetween; the first catalyst is used in an amount of 0 to 1 part by weight, such as 0, 0.2, 0.4, 0.6, 0.8, 1 part by weight or any value therebetween.
The polyisocyanate is a compound with two or more isocyanate groups at the molecular chain terminal, and can be specifically aromatic isocyanate and/or aliphatic isocyanate, and specific examples thereof include but are not limited to: toluene-2, 4-diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, lysine diisocyanate, liquefied diphenylmethane diisocyanate, low-viscosity HDI trimer, and polymethylene polyphenyl polyisocyanates.
In a preferred embodiment, the polyether polyol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol, polytetrahydrofuran glycol, and co-diols thereof.
In a preferred embodiment, the polyether polyol has a number average molecular mass of 400 to 1000, such as 400, 500, 600, 700, 800, 900, 1000 or any value therebetween.
In a preferred embodiment, the polybutadiene polyol is selected from one or more of a hydroxyl-terminated polybutadiene polyol, a hydrogenated hydroxyl-terminated polybutadiene polyol, and a hydroxyl-terminated polybutadiene-acrylonitrile polyol.
In a preferred embodiment, the polybutadiene polyol has a number average molecular mass of 1000 to 3000, such as 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000 or any value therebetween.
In a preferred embodiment, the small molecule polyol is selected from one or more of propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, and triethanolamine.
In a preferred embodiment, the first catalyst and the second catalyst are each independently selected from one or more of dibutyltin dilaurate, 2-dimorpholinodiethyl ether, organobismuth catalysts, and stannous octoate.
In a preferred embodiment, the first and second heat conductive fillers both contain heat conductive filler i and heat conductive filler ii; the heat conducting filler I is composed of a particle size D 50 Spherical alumina of 3-8 μm and particle diameter D 50 A mixture of spherical alumina 10-30 μm in a mass ratio of (0.5-2.0): 1; the second heat conducting filler is selected from one or more of magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, graphene, carbon nano tube, carbon fiber powder, aluminum hydroxide and magnesium hydroxide. Wherein the particle diameter D 50 Spherical alumina of 3-8 μm and particle diameter D 50 The mass ratio of the spherical alumina of 10-30 μm is (0.5-2.0): 1, and can be specifically 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1 or any value between the two.
In a preferred embodiment, the first and second adjuvants are each independently selected from one or more of an interfacial treatment agent, an antifoaming agent, a thixotropic agent, a stabilizer, a water scavenger, a diluent, a toughening agent, an anti-aging agent, a pigment, and a filler. Specific examples of the interface treatment agent include, but are not limited to: one or more of gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, aminomethyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane and gamma-ureidopropyl triethoxysilane. Specific examples of the antifoaming agent include, but are not limited to: one or more of polymeric defoamers, silicone defoamers, and mineral oil defoamers. In addition, the thixotropic agent, the stabilizer, the water scavenger, the diluent, the toughening agent, the anti-aging agent, the pigment and the filler may be selected as conventional in the art, and will be known to those skilled in the art, and will not be described herein.
The preparation method of the carbon dioxide-based bi-component polyurethane heat-conducting adhesive provided by the invention comprises the following steps:
and (3) preparation of the component A: adding modified carbon dioxide-based polycarbonate dihydric alcohol and castor oil polyhydric alcohol into a reaction kettle, heating to 110-130 ℃, stirring and mixing uniformly under the condition that the vacuum degree is lower than-0.085 MPa, dehydrating for 1-2 hours, cooling to room temperature, introducing dry nitrogen to restore normal pressure, adding polyisocyanate and a first catalyst, heating and stirring, heating to 70-80 ℃, continuing to react for 3-5 hours under the protection of nitrogen, adding a first heat-conducting filler and optionally a first auxiliary agent, vacuumizing, stirring and mixing uniformly to obtain a component A;
and (3) preparation of a component B: and uniformly stirring and mixing polyether polyol, polybutadiene polyol, micromolecular polyol, a second heat-conducting filler, an optional second catalyst and a second auxiliary agent, heating to 110-130 ℃, dehydrating under the condition that the vacuum degree is lower than-0.085 MPa, cooling to room temperature, and introducing dry nitrogen to restore normal pressure to obtain the component B.
The key point of the invention is that the modified carbon dioxide-based polycarbonate diol which is provided with a structural unit derived from propylene oxide, a flexible sulfur-containing group and a trialkoxysilane structural unit is introduced on the basis of the traditional polyurethane adhesive, and the special structure not only can obviously improve the bonding strength of the polyurethane adhesive, but also can bridge with the heat-conducting filler through coupling reaction, so that the heat-conducting filler can be better dispersed, and meanwhile, the anti-sedimentation performance of the heat-conducting adhesive is improved, and the heat-conducting performance of the obtained polyurethane adhesive is very excellent. In addition, the modified carbon dioxide-based polycarbonate diol adopts carbon dioxide as a raw material, and the corresponding polyurethane adhesive has the advantages of environmental protection, low cost and the like, is beneficial to realizing carbon emission reduction, accords with the sustainable development concept, and accords with economic and social benefits.
Detailed Description
The present invention will be described in detail by examples.
In the following preparation examples, propylene oxide was selected from P109309 of Shanghai aladine Biochemical technologies Co., ltd; 1, 2-epoxy-4-vinylcyclohexane is selected from Celloxide 2000 of Japanese cellophane; the photoinitiator DMPA was selected from 01049771 from Shanghai Taitan technologies Co.
In the following examples and comparative examples, the castor oil polyol is selected from the group consisting of the illicium japonicum oil, under the trade name URIC AC008; polyether polyol is purchased from national chemical company and has the brand of GY420; polybutadiene polyol was purchased from Nippon Caesalpinia under the trade designation G-2000; the small molecule polyol is 1, 4-butanediol, available from a040124 of Annaiji chemistry; the polyisocyanate is polymethylene polyphenyl polyisocyanate, and is selected from PM-2025 of Wanhua chemical company; the first catalyst and the second catalyst are both 2, 2-dimorpholinodiethyl ether and are selected from B802012 of Shanghai Michelia Biochemical technology Co., ltd; the interface treating agent is gamma-aminopropyl trimethoxysilane, and is selected from KBM-903 of Japanese Xinyue company; the defoamer was purchased from the Pick company under the brand BYK535; the thixotropic agent is fumed silica available from cabot corporation under the trade designation TS720; the first heat-conducting filler is spherical alumina, D 50 Particle diameters of 5 μm and 20 μm, respectively; the second heat conduction filler is spherical aluminum nitride, D 50 The particle size was 35. Mu.m.
In the following examples and comparative examples, the amounts of the respective raw materials were calculated in parts by weight.
Preparation example 1
The preparation example is used for illustrating the preparation of the modified carbon dioxide-based polycarbonate diol, and the specific reaction steps are as follows:
step one: 0.68g of SalenCo (III) NO 3 The catalyst is placed in a high-pressure reaction kettle, and the reaction kettle is vacuumized and filled with CO at 60 ℃ for 2 hours 2 Treatment in CO 2 209g of propylene oxide and 29.8g of 1, 2-epoxy-4-vinylcyclohexane were added to the reaction vessel under protection, stirred, passed through CO 2 The pressure regulator introduces CO into the kettle 2 The autoclave is placed in a constant temperature bath for copolymerization reaction for 6 hours under 28.5-32.0atm, and after the reaction is finished, the autoclave is cooled to below 20 ℃ to slowly release the residual CO 2 397g of carbon dioxide based polycarbonate diol were obtained;
step two: 350g of carbon dioxide-based polycarbonate dihydric alcohol, 28.52g of 3-mercaptopropyl trimethoxy silane, 2.68g of free radical photoinitiator DMPA and 500mL of thoroughly dried tetrahydrofuran are added into a reaction kettle, and then the mixture is stirred until the solid is completely dissolved, and the mixture is irradiated and reacted for 8 hours under ultraviolet light to obtain a mercapto alkene reaction product;
step three: concentrating the sulfhydryl alkene reaction product, slowly adding the concentrated product into non-solvent anhydrous diethyl ether to dissolve and precipitate a polymer, filtering and drying to obtain the modified carbon dioxide-based polycarbonate diol with the number average molecular weight of 3470.
Preparation example 2
The preparation example is used for illustrating the preparation of the modified carbon dioxide-based polycarbonate diol, and the specific reaction steps are as follows:
step one: 0.11g of SalenCo (III) NO 3 The catalyst is placed in a high-pressure reaction kettle, and the reaction kettle is vacuumized and filled with CO at 60 ℃ for 2 hours 2 Treatment in CO 2 209g of propylene oxide and 29.8g of 1, 2-epoxy-4-vinylcyclohexane were added to the reaction vessel under protection, stirred, passed through CO 2 The pressure regulator introduces CO into the kettle 2 Placing the autoclave in a constant temperature bath at 28.5-32.0atm for copolymerization reaction for 6h, cooling the autoclave to below 20deg.C after the reaction is finished, and slowly releasing residual CO 2 244g of carbon dioxide based polycarbonate diol are obtained;
step two: 200g of carbon dioxide-based polycarbonate diol, 33.16g of 3-mercaptopropyl trimethoxysilane, 3.10g of free radical photoinitiator DMPA and 300mL of thoroughly dried tetrahydrofuran are added into a reaction kettle, and the mixture is stirred until the solid is completely dissolved and is irradiated for reaction for 8 hours under ultraviolet light;
step three: concentrating the sulfhydryl alkene reaction product, slowly adding the concentrated product into non-solvent anhydrous diethyl ether to dissolve and precipitate a polymer, filtering and drying to obtain the modified carbon dioxide-based polycarbonate diol with the number average molecular weight of 1780.
Preparation example 3
10.0mg of DMC catalyst and 25.0g of sebacic acid chain transfer agent are placed in a high-pressure reaction kettle, and the reaction kettle is vacuumized and filled with CO at 60 ℃ for 2 hours 2 Treatment in CO 2 100g of propylene oxide was added to the reaction vessel under protection of (C), stirred, passed through CO 2 The pressure regulator introduces CO into the kettle 2 Placing the autoclave in a constant temperature bath at 28.5-32.0atm for copolymerization reaction for 6h, cooling the autoclave to below 20deg.C after the reaction is finished, and slowly releasing residual CO 2 90mg of tris (pentafluorophenyl) borane and 10g of propylene oxide were added to the reaction vessel, and the reaction was continued by heating to 100℃for 2 hours. After the reaction was completed, the reaction vessel for polymerization was cooled to room temperature with a cold water bath having a temperature of 12 to 15 ℃, unreacted propylene oxide was distilled off, and the residue was dried in a vacuum oven at 40 ℃ to constant weight, thereby obtaining 126.9g of poly (carbonate-ether) glycol having a number average molecular weight of 1500.
Example 1 preparation of carbon dioxide-based two-component polyurethane Heat-conducting adhesive
And (3) preparation of the component A: adding 20 parts of modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 and 7.5 parts of castor oil polyol into a reaction kettle, heating to 120 ℃, stirring and mixing uniformly under the condition that the vacuum degree is lower than-0.085 MPa, dehydrating for 2 hours, cooling and introducing dry nitrogen to restore normal pressure, adding 10 parts of polyisocyanate and 0.6 part of first catalyst, stirring while heating, heating to 75 ℃, continuing to react for 4 hours under the protection of nitrogen, and then adding 10 parts of D 50 35 parts of spherical aluminum nitride of 35 μm, 35 parts of D 50 Spherical alumina of 20 μm, 20 parts of D 50 5 μm spherical alumina, 1 part of gamma-aminopropyl trimethoxysilane, 0.2 part of defoamer BYK535 and 2 parts of fumed silica TS720, stirring and mixing for 1 hour under the protection of nitrogen, and then vacuum defoaming for 1 hour to obtain the component A；
And (3) preparation of a component B: 20 parts of polyether polyol, 15 parts of polybutadiene polyol and 2 parts of micromolecular polyol are put into another reaction kettle, and then 0.6 part of second catalyst and 10 parts of D are added 50 35 parts of spherical aluminum nitride of 35 μm, 35 parts of D 50 Spherical alumina of 20 μm and 20 parts of D 50 5 mu m spherical alumina, 1 part of gamma-aminopropyl trimethoxysilane, 0.2 part of defoamer BYK535 and 2 parts of fumed silica TS720, stirring and mixing, heating to 120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is lower than-0.085 MPa, cooling, introducing dry nitrogen and recovering normal pressure to obtain a component B;
the volume ratio of the component A to the component B in the carbon dioxide-based double-component polyurethane heat-conducting adhesive is 2:1, wherein the component A and the component B are respectively and independently stored.
Example 2 preparation of carbon dioxide-based two-component polyurethane Heat-conducting adhesive
And (3) preparation of the component A: 10 parts of modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 and 5 parts of castor oil polyol are put into a reaction kettle, heated to 120 ℃, stirred and mixed uniformly under the condition that the vacuum degree is lower than minus 0.085MPa, dehydrated for 2 hours, cooled and introduced with dry nitrogen to restore normal pressure, 5 parts of polyisocyanate and 0.3 part of first catalyst are added, heated and stirred, reacted for 4 hours under the protection of nitrogen after the temperature is raised to 75 ℃, and then 5 parts of D are added 50 Spherical aluminum nitride of 35 μm, 25 parts of D 50 Spherical alumina of 20 μm, 15 parts of D 50 5 mu m spherical alumina, 0.7 part of gamma-aminopropyl trimethoxysilane, 0.1 part of defoamer BYK535 and 2 parts of fumed silica TS720, stirring and mixing for 1 hour under the protection of nitrogen, and then vacuum defoaming for 1 hour to obtain a component A;
and (3) preparation of a component B: 10 parts of polyether polyol, 10 parts of polybutadiene polyol and 1.5 parts of micromolecular polyol are put into another reaction kettle, then 0.3 part of second catalyst is added, and 5 parts of D are added in sequence 50 Spherical aluminum nitride of 35 μm, 25 parts of D 50 Spherical alumina of 20 μm, 15 parts of D 50 Spherical alumina of 5 μm, 0.7 part of gamma-aminopropyl trisMethoxy silane, 0.1 part of defoamer BYK535 and 2 parts of fumed silica TS720 are stirred and mixed, then heated to 120 ℃, dehydrated for 2 hours under the condition that the vacuum degree is lower than-0.085 MPa, cooled, and dried nitrogen is introduced to restore normal pressure, thus obtaining the component B;
the volume ratio of the component A to the component B in the carbon dioxide-based double-component polyurethane heat-conducting adhesive is 1:1, wherein the component A and the component B are respectively and independently stored.
Example 3 preparation of carbon dioxide-based two-component polyurethane Heat-conducting adhesive
And (3) preparation of the component A: adding 30 parts of modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 and 10 parts of castor oil polyol into a reaction kettle, heating to 120 ℃, stirring and mixing uniformly under the condition that the vacuum degree is lower than-0.085 MPa, dehydrating for 2 hours, cooling and introducing dry nitrogen to restore normal pressure, adding 15 parts of polyisocyanate and 1 part of first catalyst, stirring while heating, heating to 75 ℃, continuing to react for 4 hours under the protection of nitrogen, and then adding 15 parts of D 50 Spherical aluminum nitride of 35 μm, 42 parts of D 50 Spherical alumina of 20 μm, 28 parts of D 50 5 mu m spherical alumina, 1.4 parts of gamma-aminopropyl trimethoxysilane, 0.3 part of defoamer BYK535 and 2 parts of fumed silica TS720, stirring and mixing for 1 hour under the protection of nitrogen, and then vacuum defoaming for 1 hour to obtain a component A;
and (3) preparation of a component B: 30 parts of polyether polyol, 20 parts of polybutadiene polyol and 3 parts of micromolecular polyol are put into another reaction kettle, then 1 part of second catalyst is added, and 15 parts of D are sequentially added 50 Spherical aluminum nitride of 35 μm, 42 parts of D 50 Spherical alumina of 20 μm, 28 parts of D 50 5 mu m spherical alumina, 1.4 parts of gamma-aminopropyl trimethoxysilane, 0.3 part of defoamer BYK535 and 2 parts of fumed silica TS720, stirring and mixing, heating to 120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is lower than-0.085 MPa, cooling, introducing dry nitrogen and recovering normal pressure to obtain a component B;
the volume ratio of the component A to the component B in the carbon dioxide-based double-component polyurethane heat-conducting adhesive is 1.5:1, wherein the component A and the component B are respectively and independently stored.
Example 4
The carbon dioxide-based two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 1, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the modified carbon dioxide-based polycarbonate diol prepared in preparation example 2 in the same parts by weight, and the remaining conditions were the same as in example 1, to obtain a carbon dioxide-based two-component polyurethane heat-conducting adhesive.
Example 5
The carbon dioxide-based two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 2, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the same weight part of the modified carbon dioxide-based polycarbonate diol prepared in preparation example 2, and the remaining conditions were the same as in example 2, to obtain a carbon dioxide-based two-component polyurethane heat-conducting adhesive.
Example 6
The carbon dioxide-based two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 3, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the same weight part of the modified carbon dioxide-based polycarbonate diol prepared in preparation example 2, and the remaining conditions were the same as in example 3, to obtain a carbon dioxide-based two-component polyurethane heat-conducting adhesive.
Comparative example 1
A carbon dioxide-based two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 1, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the poly (carbonate-ether) diol prepared in preparation example 3 in the same parts by weight, and the remaining conditions were the same as in example 1, to obtain a carbon dioxide-based two-component polyurethane heat-conducting adhesive.
Comparative example 2
A carbon dioxide-based two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 2, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the poly (carbonate-ether) diol prepared in preparation example 3 in the same parts by weight, and the remaining conditions were the same as in example 2, to obtain a carbon dioxide-based two-component polyurethane heat-conducting adhesive.
Comparative example 3
A carbon dioxide-based two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 3, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the poly (carbonate-ether) diol prepared in preparation example 3 in the same parts by weight, and the remaining conditions were the same as in example 3, to obtain a carbon dioxide-based two-component polyurethane heat-conducting adhesive.
Comparative example 4
A two-component polyurethane heat-conducting adhesive was prepared in the same manner as in example 1, except that the modified carbon dioxide-based polycarbonate diol prepared in preparation example 1 was replaced with the same weight part of commercial polyester diol (Dynacoll 7250 from Yingchuang Co.) under the same conditions as in example 1, to obtain a two-component polyurethane heat-conducting adhesive.
Test case
The samples obtained in examples 1-6 and comparative examples 1-4 were subjected to the following performance tests, respectively:
(1) Adhesive properties (tensile shear strength): the test was performed according to the standard GB/T7124-2008 "determination of tensile shear Strength of Adhesives (rigid Material versus rigid Material)". Specifically, an aluminum plate with the size of 100mm multiplied by 25mm multiplied by 2mm is selected, two aluminum plates are lapped together, the bonding area is 12.5mm multiplied by 25mm, the thickness of a glue layer is ensured to be 0.2mm, a lapped spline is placed in a constant temperature and humidity room with the temperature of 25 ℃ and the humidity of 50% RH for curing for seven days at room temperature, and a universal material tensile force tester is used for testing the tensile shear strength with the tensile speed of 5mm/min. The results obtained are shown in Table 1.
(2) Thermal conductivity coefficient: firstly, injecting a double-component polyurethane heat-conducting adhesive into a standard tetrafluoroethylene mold after passing through a static mixer, strickling, and putting into a constant temperature and humidity room with the temperature of 25 ℃ and the humidity of 50%RH for curing for 7 days at room temperature; and then taking out the cured sample, testing by adopting the method in ISO 22007-2, and recording the heat conductivity coefficient data. The results obtained are shown in Table 1.
TABLE 1
As can be seen from the results in Table 1, the carbon dioxide-based bi-component polyurethane heat-conducting adhesive provided by the invention still has higher adhesive strength under the condition of obtaining the heat conductivity coefficient of more than 1.86W/(m.K), namely, has good adhesive strength and heat-conducting property. In addition, the modified carbon dioxide-based polycarbonate diol adopts carbon dioxide as a raw material, and the corresponding double-component polyurethane heat-conducting adhesive has the advantages of environmental friendliness, low cost and the like, is beneficial to realizing carbon emission reduction, accords with the sustainable development concept, and accords with economic and social benefits.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (15)
1. The carbon dioxide-based bi-component polyurethane heat-conducting adhesive is characterized by comprising a component A and a component B in a volume ratio of (1-2) 1; the component A comprises an isocyanate double-end-capped polyurethane prepolymer, a first heat-conducting filler and an optional first auxiliary agent, wherein the isocyanate double-end-capped polyurethane prepolymer is prepared by nucleophilic addition reaction of modified carbon dioxide-based polycarbonate dihydric alcohol, castor oil polyol and polyisocyanate optionally in the presence of a first catalyst; the component B comprises polyether polyol, polybutadiene polyol, small molecule polyol, a second heat-conducting filler, and optional second catalyst and second auxiliary agent; the modified carbon dioxide-based polycarbonate diol contains a structural unit shown in a formula (I), a structural unit shown in a formula (II) and a structural unit shown in a formula (III) at the same time:
in the formula (III), R 1 、R 2 And R is 3 Each independently is C 1 -C 5 Is a hydrocarbon group.
2. The carbon dioxide-based two-component polyurethane heat-conducting adhesive according to claim 1, wherein in the component A, the content of the isocyanate two-terminated polyurethane prepolymer is 20-60 parts by weight, the content of the first heat-conducting filler is 45-85 parts by weight, and the content of the first auxiliary agent is 0.1-5 parts by weight; in the component B, the content of the polyether polyol is 10-30 parts by weight, the content of the polybutadiene polyol is 10-20 parts by weight, the content of the micromolecular polyol is 1-5 parts by weight, the content of the second heat conducting filler is 50-80 parts by weight, the content of the second catalyst is 0-1 part by weight, and the content of the second auxiliary agent is 0.1-5 parts by weight.
3. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 1, wherein the modified carbon dioxide-based polycarbonate diol is prepared according to the following method:
s1, placing a third catalyst into a high-pressure reaction kettle, vacuumizing the high-pressure reaction kettle for at least 2 hours at 50-80 ℃ and filling CO 2 Treatment in CO 2 Adding propylene oxide and 1, 2-epoxy-4-vinylcyclohexane into a high-pressure reaction kettle under the protection of (1), stirring, and passing CO 2 The pressure regulator introduces CO into the kettle 2 The high-pressure reaction kettle is placed in a constant temperature bath for copolymerization reaction for 4 to 8 hours under the condition of 28.5 to 32.0atm, and after the reaction is finished, the high-pressure reaction kettle is cooled to the temperature below 20 ℃ to slowly release the residual CO 2 Obtaining carbon dioxide-based polycarbonate diol;
s2, adding carbon dioxide-based polycarbonate dihydric alcohol, 3-mercaptopropyl trialkoxysilane, a free radical photoinitiator and an organic solvent into a reaction kettle, stirring until the solid is completely dissolved, and then carrying out reaction under ultraviolet irradiation to obtain a mercapto alkene reaction product;
s3, concentrating the sulfhydryl alkene reaction product, slowly adding the concentrated product into a non-solvent to precipitate a polymer, filtering and drying to obtain the modified carbon dioxide-based polycarbonate diol.
4. The carbon dioxide-based two-component polyurethane heat-conducting adhesive as claimed in claim 3, wherein the molar ratio of the amount of the third catalyst to the total amount of propylene oxide and 1, 2-epoxy-4-vinylcyclohexane is 1 (2000-7000); the molar ratio of the 1, 2-epoxy-4-vinylcyclohexane to the propylene oxide is 1 (13-55).
5. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 3, wherein the third catalyst is selected from at least one of a zinc carboxylate catalyst system, a zinc phenoxide catalyst system, a beta-diimine zinc catalyst system, a pyridine-zinc catalyst system, a porphyrin-based catalyst system, a SalenMX-based catalyst system, a rare earth catalyst system, a double metal cyanide catalyst system, and a supported catalyst system.
6. The carbon dioxide-based two-component polyurethane heat-conducting adhesive according to claim 3, wherein, the free radical photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl phenyl propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholino) -1-propanone, 2-phenylbenzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone ], 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-1-hexanone, bis 2, 6-difluoro-3-pyrrolidinophenone titanocene, methyl benzoate, benzophenone, 4-methylbenzophenone, at least one of 4-phenylbenzophenone, 4-chlorobenzophenone, methyl o-benzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone and 2-ethyl anthraquinone.
7. The carbon dioxide-based two-component polyurethane heat-conducting adhesive according to claim 1, wherein in the preparation process of the isocyanate double-ended polyurethane prepolymer, the amount of the modified carbon dioxide-based polycarbonate diol is 10-30 parts by weight, the amount of the castor oil polyol is 5-10 parts by weight, the amount of the polyisocyanate is 5-15 parts by weight, and the amount of the first catalyst is 0-1 part by weight.
8. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 1, wherein the polyisocyanate is selected from one or more of toluene-2, 4-diisocyanate, 4' -diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, lysine diisocyanate, liquefied diphenylmethane diisocyanate, low-viscosity HDI trimer, and polymethylene polyphenyl polyisocyanate.
9. The carbon dioxide-based two-component polyurethane heat-conducting adhesive according to claim 1, wherein the polyether polyol is selected from one or more of polyethylene oxide glycol, polypropylene oxide glycol, polytetrahydrofuran glycol and its copolyglycols; the polyether polyol has a number average molecular mass of 400-1000.
10. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 1, wherein the polybutadiene polyol is selected from one or more of a hydroxyl-terminated polybutadiene polyol, a hydrogenated hydroxyl-terminated polybutadiene polyol, and a hydroxyl-terminated polybutadiene-acrylonitrile polyol; the polybutadiene polyol has a number average molecular mass of 1000-3000.
11. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 1, wherein the small molecule polyol is selected from one or more of propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, and triethanolamine.
12. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 1, wherein the first catalyst and the second catalyst are each independently selected from one or more of dibutyl tin dilaurate, 2-dimorpholinodiethyl ether, an organobismuth catalyst, and stannous octoate.
13. The carbon dioxide-based two-component polyurethane heat-conducting adhesive glue according to claim 1, wherein the first heat-conducting filler and the second heat-conducting filler both contain a heat-conducting filler I and a heat-conducting filler II; the heat conducting filler I is composed of a particle size D 50 Spherical alumina of 3-8 μm and particle diameter D 50 A mixture of spherical alumina 10-30 μm in a mass ratio of (0.5-2.0): 1; the second heat conducting filler is selected from one or more of magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, graphene, carbon nano tube, carbon fiber powder, aluminum hydroxide and magnesium hydroxide.
14. The carbon dioxide-based two-component polyurethane heat-conducting adhesive of claim 1, wherein the first and second auxiliary agents are each independently selected from one or more of an interfacial treatment agent, an antifoaming agent, a thixotropic agent, a stabilizer, a water scavenger, a diluent, a toughening agent, an anti-aging agent, a pigment, and a filler.
15. The method for preparing a carbon dioxide-based two-component polyurethane heat-conducting adhesive according to any one of claims 1 to 14, comprising the steps of:
and (3) preparation of the component A: adding modified carbon dioxide-based polycarbonate dihydric alcohol and castor oil polyhydric alcohol into a reaction kettle, heating to 110-130 ℃, stirring and mixing uniformly under the condition that the vacuum degree is lower than-0.085 MPa, dehydrating for 1-2 hours, cooling to room temperature, introducing dry nitrogen to restore normal pressure, adding polyisocyanate and a first catalyst, heating and stirring, heating to 70-80 ℃, continuing to react for 3-5 hours under the protection of nitrogen, adding a first heat-conducting filler and optionally a first auxiliary agent, vacuumizing, stirring and mixing uniformly to obtain a component A;
and (3) preparation of a component B: and uniformly stirring and mixing polyether polyol, polybutadiene polyol, micromolecular polyol, a second heat-conducting filler, an optional second catalyst and a second auxiliary agent, heating to 110-130 ℃, dehydrating under the condition that the vacuum degree is lower than-0.085 MPa, cooling to room temperature, and introducing dry nitrogen to restore normal pressure to obtain the component B.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117106403A (en) * | 2023-07-17 | 2023-11-24 | 韦尔通科技股份有限公司 | Flexible solvent-free double-component PU (polyurethane) structural adhesive and preparation method thereof |
| CN117264596A (en) * | 2023-10-10 | 2023-12-22 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
| CN117264596B (en) * | 2023-10-10 | 2024-05-10 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117106403A (en) * | 2023-07-17 | 2023-11-24 | 韦尔通科技股份有限公司 | Flexible solvent-free double-component PU (polyurethane) structural adhesive and preparation method thereof |
| CN117264596A (en) * | 2023-10-10 | 2023-12-22 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
| CN117264596B (en) * | 2023-10-10 | 2024-05-10 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
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