CN110591627B - Novel adhesive and heat-conducting interface material - Google Patents
Novel adhesive and heat-conducting interface material Download PDFInfo
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- CN110591627B CN110591627B CN201910836775.5A CN201910836775A CN110591627B CN 110591627 B CN110591627 B CN 110591627B CN 201910836775 A CN201910836775 A CN 201910836775A CN 110591627 B CN110591627 B CN 110591627B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
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- 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
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- 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
- C09J175/06—Polyurethanes from polyesters
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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
- C08K3/02—Elements
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- C08K2003/0812—Aluminium
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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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to the technical field of heat conduction materials, and particularly relates to a novel adhesive and a heat conduction interface material. The invention discloses a novel adhesive which is prepared from the following raw materials in parts by weight: 3-8 parts of polyester polyol, 10-16 parts of isocyanate, 1-4 parts of chain extender, 0.1-2 parts of catalyst, 47-58 parts of heat-conducting filler and 20-25 parts of carbon material.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a novel adhesive and a heat conduction interface material.
Background
With the rapid development of science and technology, polymer materials are more applied to heavy machinery, high-power electrical appliances, electronic products and the like. Products applied in the fields usually bear a lot of heat, if the generated heat cannot be timely led out, the polymer bears the heat, the service performance of the polymer material can be reduced, the service life of the polymer material is shortened, and even safety accidents such as fire disasters can be caused.
Because of its many advantages in structure and performance, the development of heat-conducting polyurethane materials has become one of the research hotspots in the field of polymer materials. CN105237723 disperses graphene oxide in polyurethane prepolymer to prepare polytetrahydrofuran type polyurethane material, which has the characteristics of high strength, wear resistance, excellent thermal conductivity and the like, and greatly improves the thermal conductivity of the synthesized polyurethane material, however, the stability of the reaction system is reduced by the method of physically dispersing graphene oxide. CN102627937 is through adopting the modified heat conduction filler and taking place the chemical reaction between the polyether type polyurethane prepolymer, thus make the heat conduction filler form very good chemical bond and link in the polyurethane molecule, reach stable heat conduction effect, it is with low costs at the same time. However, the heat-conducting filler used in the invention has a greatly improved heat-conducting property, and thus the heat-radiating requirement of electronic products cannot be met.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a novel adhesive which comprises the following raw materials in parts by weight: 3-8 parts of polyester polyol, 10-16 parts of isocyanate, 1-4 parts of chain extender, 0.1-2 parts of catalyst, 47-58 parts of heat-conducting filler and 20-25 parts of carbon material.
As a preferred embodiment, the polyester polyol is at least one selected from polycarbonate polyol, phthalic anhydride polyester polyol, polybutadiene polyol, polyhexamethylene adipate glycol, polycaprolactone polyol, polydiethylene adipate glycol polyol, polyethyleneglycoladipate glycol polyol, and polysulfide polyol.
As a preferred technical scheme, the polyester polyol is a mixture of phthalic anhydride polyester polyol and polyethylene glycol adipate butanediol polyester polyol.
As a preferred embodiment, the isocyanate is at least one selected from the group consisting of alkylene diisocyanate, isophorone diisocyanate, diphenyl alkane diisocyanate, alkylbenzene diisocyanate, and naphthalene diisocyanate.
In a preferred embodiment, the isocyanate is an alkyl benzene diisocyanate.
As a preferable technical scheme, the coating also comprises 0.5 to 3 parts by weight of polymeric siloxane.
In a preferred embodiment, the polymeric siloxane is at least one of polymeric aminosiloxane, polymeric bisaminosiloxane, polymeric epoxysiloxane and polymeric vinylsiloxane.
As a preferable technical scheme, the hydroxyl value of the polyester polyol is 50-120 mgKOH/g.
The second aspect of the present invention provides a method for preparing the adhesive, comprising the steps of:
s1: adding polyester polyol, polymeric siloxane, a heat-conducting filler and a carbon material into 300 parts by weight of 100-plus-one solvent, and stirring for 1-3 hours at 60-90 ℃ at the rotation speed of 500-plus-one 1500 rpm;
s2: and (4) adding isocyanate, a catalyst and a chain extender into the mixture obtained in the step S1, reacting for 4-6h at 70-90 ℃, and then carrying out vacuum distillation and cooling at 80-90 ℃ to obtain the catalyst.
The third aspect of the invention provides the application of the adhesive, and the heat-conducting interface material is used for heat dissipation in the field of electronic products.
Has the advantages that: the adhesive has excellent chemical bonding force with base materials containing active hydrogen and materials with smooth surfaces such as metal, rubber and the like, can be well filled in gaps of a thermal interface, reduces interface thermal resistance, and improves the heat dissipation efficiency of electronic components; the heat conduction structure can be widely applied to heat conduction between a heat source and a radiator of an electronic product, and improves the heat radiation performance of the electronic product.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to solve the technical problems, the invention provides a novel adhesive which comprises the following raw materials in parts by weight: 3-8 parts of polyester polyol, 10-16 parts of isocyanate, 1-4 parts of chain extender, 0.1-2 parts of catalyst, 47-58 parts of heat-conducting filler and 20-25 parts of carbon material.
As a preferred embodiment, the novel adhesive is prepared from the following raw materials in parts by weight: 5 parts of polyester polyol, 14 parts of isocyanate, 2 parts of a chain extender, 0.5 part of a catalyst, 50 parts of a heat-conducting filler and 23 parts of a carbon material.
As a preferred embodiment, the novel adhesive further comprises 0.5 to 3 parts by weight of a polymerizable siloxane.
Preferably, the novel adhesive further comprises 2 parts by weight of polymeric siloxane.
Polyester polyols
In the present application, the polyester polyol refers to a polyester polyol prepared by condensing an organic dicarboxylic acid (anhydride or ester) and a polyhydric alcohol or polymerizing a lactone and a polyhydric alcohol. Among them, the organic dicarboxylic acids include: phthalic acid, phthalic anhydride or an ester thereof, adipic acid, halogenated phthalic acid, and the like. The polyols may be exemplified by: ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, 1, 4-butanediol, and the like.
As a preferred embodiment, the polyester polyol is at least one selected from the group consisting of polycarbonate polyol, phthalic anhydride polyester polyol, polybutadiene polyol, polyhexamethylene adipate glycol diol, polycaprolactone polyol, polydiethylene adipate polyol, polyethyleneglycoladipate glycol polyol, and polysulfide polyol.
As a preferred embodiment, the polyester polyol is a mixture of a phthalic anhydride polyester polyol and a polyethylene adipate butanediol polyester polyol.
Preferably, the weight ratio of the phthalic anhydride polyester polyol to the polyethylene glycol adipate butanediol ester polyol is (1-3): 1.
preferably, the weight ratio of the phthalic anhydride polyester polyol to the polyethylene glycol adipate butanediol ester polyol is 2: 1.
in a preferred embodiment, the polyester polyol has a hydroxyl value of 50 to 120 mgKOH/g.
The polyester polyol has the characteristics of high reaction activity, hydrolysis resistance, stability and the like.
Isocyanates
In a preferred embodiment, the isocyanate is at least one selected from the group consisting of alkylene diisocyanate, isophorone diisocyanate, diphenyl alkane diisocyanate, alkylbenzene diisocyanate, and naphthalene diisocyanate.
In a preferred embodiment, the isocyanate is an alkyl benzene diisocyanate.
Examples of the alkylbenzene diisocyanate include, but are not limited to, xylene diisocyanate, p-phenylene diisocyanate, 1, 3-phenylene diisocyanate, toluene-2, 4-diisocyanate.
Preferably, the isocyanate is xylene diisocyanate.
Chain extender
As a preferred embodiment, the chain extender is an amine chain extender and/or an alcohol chain extender.
Examples of alcohol chain extenders include, but are not limited to, 1, 6-hexanediol, methyl propanediol, 1, 4-butanediol.
Examples of amine chain extenders include, but are not limited to, ethylenediamine, isophoronediamine, 3 '-dichloro-4, 4' -diaminodiphenylmethane.
Preferably, the chain extender is a mixture of 1, 4-butanediol and 1, 6-hexanediol.
Preferably, the weight ratio of the 1, 4-butanediol to the 1, 6-hexanediol is (2-5): 1.
More preferably, the weight ratio of 1, 4-butanediol to 1, 6-hexanediol is 3: 1.
Catalyst and process for preparing same
As a preferred embodiment, the catalyst is selected from at least one of dibutyl tin dilaurate, N-dimethylethanolamine, stannous octoate, dibutyl tin diacetate, dibutyl tin di (dodecylthio), dimorpholinodiethyl ether, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, and N-methylimidazole, triethanolamine, triethylamine.
Preferably, the catalyst is dibutyl tin dilaurate.
The applicant prepares the hydrolysis-resistant and stable polyurethane adhesive by using polyester diol, isocyanate and a chain extender. The polyurethane adhesive contains isocyanate, hydroxyl and other groups, has high activity and polarity, and has excellent chemical adhesive force with base materials containing active hydrogen and materials with smooth surfaces such as metal, rubber and the like. The polyurethane adhesive is suitable for various structural adhesion fields, has excellent flexibility, can adapt to adhesion of base materials with different thermal expansion coefficients, forms a soft-hard transition layer between the base materials, and has strong adhesion force, and excellent buffering and shock absorption functions.
Heat conductive filler
In one embodiment, the thermally conductive filler is at least one selected from the group consisting of copper powder, aluminum powder, silver powder, iron powder, zinc powder, nickel powder, tin powder, copper oxide, aluminum oxide, silver oxide, iron oxide, zinc oxide, nickel oxide, tin oxide, aluminum nitride, silicon nitride, and tin nitride.
As a preferred embodiment, the heat conductive filler is composed of aluminum powder and aluminum nitride.
As a preferred embodiment, the weight ratio of the aluminum powder to the aluminum nitride is (1-3): 1.
in a preferred embodiment, the weight ratio of the aluminum powder to the aluminum nitride is 1.7: 1.
in a preferred embodiment, the aluminum powder is a spherical powder.
As a preferred embodiment, the aluminum powder has an average particle diameter of 1 to 70 μm;
preferably, the aluminum powder consists of aluminum powder with the average particle size of 1-10 microns and aluminum powder with the average particle size of 30-50 microns;
preferably, the aluminum powder consists of aluminum powder with an average particle size of 5 micrometers and aluminum powder with an average particle size of 40 micrometers.
More preferably, the weight ratio of the aluminum powder with the average particle size of 5 microns to the aluminum powder with the average particle size of 40 microns is (0.9-1.2): 1.
More preferably, the weight ratio of the aluminum powder with the average particle size of 5 microns to the aluminum powder with the average particle size of 40 microns is 1: 1.
In a preferred embodiment, the aluminum nitride is a spherical powder.
As a preferred embodiment, the aluminum nitride has an average particle size of 1 to 7 μm;
preferably, the aluminum nitride is composed of aluminum nitride having an average particle size of 1 micrometer and aluminum nitride having an average particle size of 5 micrometers.
More preferably, the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is (1-1.2): 1.
More preferably, the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
Carbon material
As a preferred embodiment, the carbon material is selected from at least one of carbon fiber, carbon nanotube, carbon nanowire, graphite, graphene, and carbon nanosheet.
Preferably, the carbon material is carbon fiber.
The carbon fiber is a high-strength and high-modulus fiber material with the carbon content of more than 95%, and is a microcrystalline graphite material which is obtained by piling organic fibers such as flaky graphite microcrystals along the axial direction of the fiber and performing carbonization and graphitization treatment.
Preferably, the carbon fibers have an average length of 50 to 150 micrometers.
Preferably, the carbon fibers have an average length of 100 microns.
Polymeric siloxanes
In a preferred embodiment, the polymeric siloxane is one of polymeric aminosiloxane, polymeric bisaminosiloxane, polymeric epoxysiloxane, polymeric vinylsiloxane or a combination thereof.
Preferably, the polymeric siloxane is a polymeric aminosiloxane.
AP-8125 belongs to a polymeric silane coupling agent, is an excellent adhesion promoting and reinforcing agent, has special effects on systems of silicate, metal, ceramic, filler and the like, can obviously improve the characteristics of products and enhance the adhesion between interfaces.
The polymerized aminosiloxane is AP-8125 and is purchased from Wuhan substrate science and technology development limited company.
According to the invention, the polyurethane adhesive is prepared through the crosslinking reaction of the polymeric siloxane, isocyanate, a chain extender and the like, the polar group of the polymeric siloxane can effectively coat the heat-conducting filler and the carbon material, so that the heat-conducting filler and the polyurethane matrix are ensured to be in good contact, the heat-conducting filler forms effective aggregation of a heat-conducting network under high loading capacity, the aggregation is not separated out like other irregular materials, and meanwhile, the heat-conducting filler is easy to be mutually connected in the matrix to form the heat-conducting network, so that the thermal contact resistance is lower.
A second aspect of the present invention provides a method for preparing the adhesive, comprising the steps of:
s1: adding polyester polyol, polymeric siloxane, a heat-conducting filler and a carbon material into 300 parts by weight of 100-plus-one solvent, and stirring for 1-3 hours at 60-90 ℃ at the rotation speed of 500-plus-one 1500 rpm;
s2: and (4) adding isocyanate, a catalyst and a chain extender into the mixture obtained in the step S1, reacting for 4-6h at 70-90 ℃, and then carrying out vacuum distillation and cooling at 80-90 ℃ to obtain the catalyst.
The solvent used in step S1 is not particularly limited, and may be, for example, methanol, ethanol, dichloromethane, isopropanol, acetone, or the like, which can improve the compatibility of the respective raw materials without affecting the object of the present invention.
In the present application, the solvent in step S1 is a mixture of dichloromethane and acetone, and the weight ratio of dichloromethane to acetone is 1: 1.
the third aspect of the invention provides the application of the novel adhesive, and the novel adhesive is used for heat dissipation in the field of electronic products.
The electronic product described in this application refers to a related product based on electric energy, including but not limited to: watches, smart phones, telephones, televisions, video disc players (VCD, SVCD, DVD), video recorders, camcorders, radios, radio cassettes, combination speakers, compact disc players (CD), computers, mobile communication products, and the like.
In the application, the heat dissipation of the novel adhesive in the field of electronic products means that the novel adhesive can be directly coated between a chip and a substrate, so that the novel adhesive not only plays a role in bonding, but also plays a role in heat dissipation.
The novel adhesive is used for heat dissipation in the field of electronic products, and means that the novel adhesive can be coated on a PET film to be made into a heat-conducting adhesive tape.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The novel adhesive is prepared from the following raw materials in parts by weight: 5 parts of polyester polyol, 14 parts of isocyanate, 2 parts of a chain extender, 0.5 part of a catalyst, 50 parts of a heat-conducting filler, 23 parts of a carbon material and 2 parts of polymeric siloxane.
The polyester polyol is a mixture of phthalic anhydride polyester polyol and polyethylene glycol adipate butanediol polyester polyol; the weight ratio of the phthalic anhydride polyester polyol to the polyethylene glycol adipate butanediol polyester polyol is 2: 1; the phthalic anhydride polyester polyol is HF-8011, and is purchased from Zhejiang Huafeng New materials Co., Ltd; the polyethylene glycol adipate butanediol ester polyol is PE-1320, and is purchased from Zhejiang Huafeng New materials GmbH.
The isocyanate is xylene diisocyanate.
The chain extender is a mixture of 1, 4-butanediol and 1, 6-hexanediol; the weight ratio of the 1, 4-butanediol to the 1, 6-hexanediol is 3: 1.
The catalyst is dibutyltin dilaurate.
The heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 1.7: 1; the aluminum powder consists of aluminum powder with the average particle size of 5 microns and aluminum powder with the average particle size of 40 microns; the weight ratio of the aluminum powder with the average particle size of 5 micrometers to the aluminum powder with the average particle size of 40 micrometers is 1: 1; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The carbon material is carbon fiber; the carbon fibers have an average length of 100 microns.
The polymerized siloxane is AP-8125, and is purchased from Wuhan substrate science and technology development Inc.
The preparation method of the adhesive comprises the following steps:
s1: adding polyester polyol, polymeric siloxane, a heat-conducting filler and carbon fiber into 200 parts by weight of solvent, and stirring at 80 ℃ for 2 hours at the rotating speed of 800 rpm;
s2: and (4) adding isocyanate, a catalyst and a chain extender into the mixture obtained in the step S1, reacting for 5 hours at 85 ℃, and then carrying out vacuum distillation and cooling at 85 ℃ to obtain the catalyst.
The solvent in the step S1 is a mixture of dichloromethane and acetone, and the weight ratio of dichloromethane to acetone is 1: 1.
example 2
The novel adhesive is prepared from the following raw materials in parts by weight: 3 parts of polyester polyol, 10 parts of isocyanate, 1 part of chain extender, 0.1 part of catalyst, 47 parts of heat-conducting filler, 20 parts of carbon material and 0.5 part of polymeric siloxane.
The polyester polyol is a mixture of phthalic anhydride polyester polyol and polyethylene glycol adipate butanediol polyester polyol; the weight ratio of the phthalic anhydride polyester polyol to the polyethylene glycol adipate butanediol polyester polyol is 1: 1; the phthalic anhydride polyester polyol is HF-8011, and is purchased from Zhejiang Huafeng New materials Co., Ltd; the polyethylene glycol adipate butanediol ester polyol is PE-1320, and is purchased from Zhejiang Huafeng New materials GmbH.
The isocyanate is xylene diisocyanate.
The chain extender is a mixture of 1, 4-butanediol and 1, 6-hexanediol; the weight ratio of the 1, 4-butanediol to the 1, 6-hexanediol is 2: 1.
The catalyst is dibutyltin dilaurate.
The heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 1: 1; the aluminum powder consists of aluminum powder with the average particle size of 5 microns and aluminum powder with the average particle size of 40 microns; the weight ratio of the aluminum powder with the average particle size of 5 micrometers to the aluminum powder with the average particle size of 40 micrometers is 1: 1; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The carbon material is carbon fiber; the carbon fibers have an average length of 100 microns.
The polymerized siloxane is AP-8125, and is purchased from Wuhan substrate science and technology development Inc.
The preparation method of the adhesive comprises the specific steps of example 1.
Example 3
The novel adhesive is prepared from the following raw materials in parts by weight: 8 parts of polyester polyol, 16 parts of isocyanate, 4 parts of a chain extender, 0.1 part of a catalyst, 58 parts of a heat-conducting filler, 25 parts of a carbon material and 3 parts of polymeric siloxane.
The polyester polyol is a mixture of phthalic anhydride polyester polyol and polyethylene glycol adipate butanediol polyester polyol; the weight ratio of the phthalic anhydride polyester polyol to the polyethylene glycol adipate butanediol polyester polyol is 3: 1; the phthalic anhydride polyester polyol is HF-8011, and is purchased from Zhejiang Huafeng New materials Co., Ltd; the polyethylene glycol adipate butanediol ester polyol is PE-1320, and is purchased from Zhejiang Huafeng New materials GmbH.
The isocyanate is xylene diisocyanate.
The chain extender is a mixture of 1, 4-butanediol and 1, 6-hexanediol; the weight ratio of the 1, 4-butanediol to the 1, 6-hexanediol is 5: 1.
The catalyst is dibutyltin dilaurate.
The heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 3: 1; the aluminum powder consists of aluminum powder with the average particle size of 5 microns and aluminum powder with the average particle size of 40 microns; the weight ratio of the aluminum powder with the average particle size of 5 micrometers to the aluminum powder with the average particle size of 40 micrometers is 1: 1; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The carbon material is carbon fiber; the carbon fibers have an average length of 100 microns.
The polymerized siloxane is AP-8125, and is purchased from Wuhan substrate science and technology development Inc.
The preparation method of the adhesive comprises the specific steps of example 1.
Example 4
The specific components and weight parts of the novel adhesive are the same as those of example 1, except that the polymeric siloxane is replaced by gamma-aminopropyltriethoxysilane.
The preparation method of the adhesive has the same specific steps as example 1.
Example 5
The specific components and the weight parts of the novel adhesive are the same as those of the embodiment 1, and the difference is that the heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 5: 1; the aluminum powder consists of aluminum powder with the average particle size of 5 microns and aluminum powder with the average particle size of 40 microns; the weight ratio of the aluminum powder with the average particle size of 5 micrometers to the aluminum powder with the average particle size of 40 micrometers is 1: 1; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The preparation method of the adhesive has the same specific steps as example 1.
Example 6
The specific components and the weight parts of the novel adhesive are the same as those of the embodiment 1, and the difference is that the heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 0.5: 1; the aluminum powder consists of aluminum powder with the average particle size of 5 microns and aluminum powder with the average particle size of 40 microns; the weight ratio of the aluminum powder with the average particle size of 5 micrometers to the aluminum powder with the average particle size of 40 micrometers is 1: 1; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The preparation method of the adhesive has the same specific steps as example 1.
Example 7
The specific components and the weight parts of the novel adhesive are the same as those of the embodiment 1, and the difference is that the heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 1.7: 1; the average grain diameter of the aluminum powder is 5 microns; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The preparation method of the adhesive has the same specific steps as example 1.
Example 8
The specific components and the weight parts of the novel adhesive are the same as those of the embodiment 1, and the difference is that the heat-conducting filler consists of aluminum powder and aluminum nitride; the weight ratio of the aluminum powder to the aluminum nitride is 1.7: 1; the average grain diameter of the aluminum powder is 40 micrometers; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns; the weight ratio of the aluminum nitride with the average grain diameter of 1 micron to the aluminum nitride with the average grain diameter of 5 microns is 1.1: 1.
The preparation method of the adhesive has the same specific steps as example 1.
Performance testing
Coefficient of thermal conductivity: the thermal conductivity was measured at 180 ℃ after 1 hour of curing of the adhesive in units of W/(m.K), as shown in Table 1.
Peel strength: the adhesive is coated on a PET base material, and 180-degree stripping test is carried out under the condition of the tensile speed of 300mm/min by referring to the standard GB/T2792-2014, wherein the unit is N/20 mm. As a result, the peel strengths of examples 1 to 3 were 20 to 25N/20mm, and the peel strength of example 4 was 10N/20 mm.
TABLE 1
| Examples | Coefficient of thermal conductivity |
| Example 1 | 16 |
| Example 2 | 12.7 |
| Example 3 | 14.1 |
| Example 4 | 9.8 |
| Example 5 | 9.6 |
| Example 6 | 7.5 |
| Example 7 | 4 |
| Example 8 | 6.4 |
The above-mentioned embodiments are provided only for illustrative purposes and should not be construed as limiting the scope of the present invention, and any method that can be substituted or modified equivalently according to the technical solution and the inventive concept thereof should be included in the scope of the present invention.
Claims (8)
1. The adhesive is characterized by comprising the following preparation raw materials in parts by weight: 3-8 parts of polyester polyol, 10-16 parts of isocyanate, 1-4 parts of chain extender, 0.1-2 parts of catalyst, 47-58 parts of heat-conducting filler, 20-25 parts of carbon material and 0.5-3 parts of polymeric siloxane;
the polymeric siloxane is polymeric aminosiloxane;
the heat-conducting filler is composed of aluminum powder and aluminum nitride, and the aluminum powder is composed of aluminum powder with the average particle size of 5 micrometers and aluminum powder with the average particle size of 40 micrometers; the aluminum nitride consists of aluminum nitride with the average grain diameter of 1 micron and aluminum nitride with the average grain diameter of 5 microns;
the weight ratio of the aluminum powder to the aluminum nitride is (1-3): 1.
2. the adhesive of claim 1, wherein the polyester polyol is selected from at least one of polycarbonate polyol, phthalic anhydride polyester polyol, polyhexamethylene adipate glycol diol, polycaprolactone polyol, polydiethylene adipate glycol polyol, and polyethyleneglycoladipate glycol diol polyol.
3. The adhesive of claim 1 or 2, wherein the polyester polyol is a mixture of a phthalic anhydride polyester polyol and a polyethylene glycol adipate butanediol polyol.
4. The adhesive of claim 1, wherein the isocyanate is selected from at least one of alkylene diisocyanate, isophorone diisocyanate, diphenyl alkane diisocyanate, alkyl benzene diisocyanate, and naphthalene diisocyanate.
5. The adhesive of claim 4, wherein the isocyanate is an alkyl benzene diisocyanate.
6. The adhesive according to claim 1 or 2, wherein the polyester polyol has a hydroxyl value of 50 to 120 mgKOH/g.
7. The method of preparing the adhesive of claim 1, comprising the steps of:
s1: adding polyester polyol, polymeric siloxane, a heat-conducting filler and a carbon material into 300 parts by weight of 100-plus-one solvent, and stirring for 1-3 hours at 60-90 ℃ at the rotation speed of 500-plus-one 1500 rpm;
s2: and (4) adding isocyanate, a catalyst and a chain extender into the mixture obtained in the step S1, reacting for 4-6h at 70-90 ℃, and then carrying out vacuum distillation and cooling at 80-90 ℃ to obtain the catalyst.
8. Use of an adhesive according to any of claims 1-6 for heat dissipation in the field of electronics.
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| CN112280520A (en) * | 2020-10-10 | 2021-01-29 | 永一胶粘(中山)有限公司 | High-thermal-conductivity waterborne polyurethane/polysiloxane pressure-sensitive adhesive and preparation method and application thereof |
| JPWO2022259968A1 (en) * | 2021-06-11 | 2022-12-15 | ||
| CN113930020B (en) * | 2021-10-20 | 2023-03-21 | 杭州永腾橡塑实业有限公司 | Damping ring and preparation method thereof |
| CN114501695B (en) * | 2022-01-25 | 2024-03-15 | 佛山市顺德区永利华运动用品有限公司 | High-heat-conductivity graphene heating body, electric heating glove and preparation method thereof |
| CN115160537A (en) * | 2022-08-03 | 2022-10-11 | 广东粤港澳大湾区国家纳米科技创新研究院 | High-heat-conduction material with bonding and sealing performances and preparation method thereof |
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