CN113563832B - Composite adhesive and preparation method thereof - Google Patents
Composite adhesive and preparation method thereof Download PDFInfo
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- CN113563832B CN113563832B CN202110867643.6A CN202110867643A CN113563832B CN 113563832 B CN113563832 B CN 113563832B CN 202110867643 A CN202110867643 A CN 202110867643A CN 113563832 B CN113563832 B CN 113563832B
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Classifications
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention provides a composite adhesive and a preparation method thereof, wherein the composite adhesive is an acrylic adhesive/graphene microchip composite heat conduction adhesive, and is prepared by uniformly mixing a dispersion liquid, an acrylic acid derivative polymer solution and graphene nanoplatelets, adding azobisisobutyronitrile, dispersing and carrying out ultrasonic treatment, wherein TiO is added into a solvent 2 、SiO 2 And silane coupling agent to obtain pre-dispersed mother liquor, and adding TiO 2 、SiO 2 And isocyanate to prepare a dispersion; the acrylic acid derivative polymer solution is prepared by adding methyl methacrylate, butyl acrylate and dimethyldiethoxysilane to a solvent and stirring/ultrasonic treating. The prepared composite adhesive combines the adhesive property of the adhesive and the heat-conducting property of graphene, and compared with the heat-conducting coefficient of an acrylic adhesive without graphene micro-sheets, the heat-conducting coefficient of the prepared composite heat-conducting adhesive is 19 to 30 times that of the acrylic adhesive.
Description
Technical Field
The invention relates to a composite adhesive and a preparation method thereof, belonging to the field of composite adhesive materials.
Background
The electronic components of integrated circuits are becoming smaller and more complex, which has become a necessary trend in the development of electronic technology. High-power electronic devices and portable devices (smart phones, tablet computers, and the like) inevitably generate a large amount of heat during use, thereby causing a decrease in performance and service life of electronic components. In addition, the advent of the 5G communication era has placed higher demands on heat dissipation management. Meanwhile, the appearance of electronic products is receiving more and more attention and attention from consumers. This places more stringent requirements on the properties of the double-sided adhesive tape used to bond electronic components.
The acrylic acid adhesive material is an adhesive with a wide application range, is suitable for bonding various base materials, and is used for radiating a heating device by attaching a heat-conducting film made of the adhesive to a heating part, but the material has the defect of low heat conductivity coefficient (generally not exceeding 2.5W/m.K), which influences the conduction of heat from the heating part to the heat-conducting film to a certain extent.
Disclosure of Invention
The invention aims to provide a composite adhesive and a preparation method thereof, and aims to solve the problem that the adhesive in the prior art is poor in heat conduction and heat dissipation.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
a preparation method of the composite adhesive comprises the following steps:
and uniformly mixing the dispersion liquid, the acrylic acid derivative polymer solution and the graphene nanoplatelets, adding azobisisobutyronitrile, and performing dispersion and ultrasonic treatment to obtain the composite adhesive.
Further, the preparation steps of the dispersion are as follows:
adding TiO into solvent 2 、SiO 2 And a silane coupling agent to prepare a pre-dispersion mother liquor;
adding TiO into pre-dispersed mother liquor 2 、SiO 2 And isocyanate to prepare a dispersion.
Further, the preparation method of the acrylic acid derivative polymer solution comprises the following steps:
methyl methacrylate, butyl acrylate and dimethyldiethoxysilane are added into a solvent for stirring/ultrasonic treatment to prepare an acrylic acid derivative polymer solution.
Further, the TiO is used in the preparation of a predispersed mother liquor 2 、SiO 2 All are micron-sized powder; preparation of the Dispersion TiO 2 、SiO 2 All are nano-scale powder; the nano-scale TiO 2 The powder diameter is 25nm; nanoscale SiO 2 The powder diameter was 12nm.
Further, the TiO is used in the preparation of a predispersed mother liquor 2 0.1 to 0.4 part by weight of SiO 2 0.1-0.4 weight portion, 1.1-1.6 weight portions of silane coupling agent;
preparation of the Dispersion TiO 2 1.8-2.4 parts by weight of SiO 2 2.0 to 2.6 portions of silane coupling agent and 0.7 to 0.9 portion of silane coupling agent.
Further, the methacrylate is 70-73 parts by weight, the butyl acrylate is 32-34 parts by weight, and the dimethyldiethoxysilane is 15-17 parts by weight.
Further, the graphene nanoplatelets are 30-50 parts by weight.
Further, the azobisisobutyronitrile is 1.2 to 1.5 parts by weight.
Further, the solvent is any one or a mixture of more of acetone, butanone, n-hexane, cyclohexane, benzene, toluene, xylene, ethyl acetate and methyl isobutyl ketone.
The invention also provides the composite adhesive prepared by the preparation method of any one of the composite adhesives.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the graphene micro-sheets are dispersed in the adhesive material matrix to obtain the composite adhesive material, the adhesive property of the adhesive is combined with the heat-conducting property of the graphene, and the graphene micro-sheets can effectively contact with each other in the adhesive to form the graphene heat-conducting link by preparing the composite heat-conducting adhesive. The interface thermal resistance is reduced by utilizing the large specific surface area of the graphene microchip, so that the heat can be rapidly transferred among the graphene nanoplatelets without passing through an adhesive matrix, and the effect of heat conduction and permeation is achieved, and the heat can be better conducted to a heat conduction film from a heating part to dissipate heat. In addition, the thermal conductivity coefficient of the acrylic adhesive without the graphene microchip is generally not more than 2.5W/m.K, and the thermal conductivity coefficient of the prepared composite thermal conductive adhesive is 19 to 30 times that of the acrylic adhesive.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
0.1 part by weight of micron-sized TiO 2 Powder and 0.4 weight part of micron-sized SiO 2 Adding the powder and 1.6 parts of silane coupling agent into toluene, and stirring/ultrasonically treating to obtain a pre-dispersion mother solution;
1.8 parts by weight of nano-TiO 2 Powder, 2.6 weight portions of nano SiO 2 Adding the powder and 0.9 weight part of isocyanate into pre-dispersion mother liquor, and stirring/ultrasonically treating to obtain prepared pre-dispersion mother liquor;
adding 70 parts by weight of methyl methacrylate, 32 parts by weight of butyl acrylate and 15 parts by weight of dimethyldiethoxysilane into toluene, and stirring/ultrasonically treating to obtain an acrylic derivative polymer solution;
uniformly mixing the dispersion liquid, the acrylic acid derivative polymer solution and 30 parts by weight of graphene nanoplatelets, adding 1.2 parts by weight of azobisisobutyronitrile, and performing high-speed dispersion/ultrasonic treatment to obtain the acrylic acid adhesive/graphene nanoplatelets composite heat-conducting adhesive.
The acrylic adhesive/graphene microchip composite thermal conductive adhesive prepared in example 1 was measured for thermal conductivity, and the thermal conductivity was 47W/m.k.
Example 2
0.2 part by weight of micron-sized TiO 2 Powder, 0.3 weight part of micron-sized SiO 2 Adding the powder and 1.5 parts of silane coupling agent into toluene, and stirring/ultrasonically treating to obtain pre-dispersed mother liquor;
2.0 parts by weight of nano-TiO 2 Powder, 2.4 parts by weight of nano SiO 2 Adding the powder and 0.8 part by weight of isocyanate into pre-dispersion mother liquor, and stirring/ultrasonically treating to obtain a prepared pre-dispersion mother liquor;
adding 71 parts by weight of methyl methacrylate, 33 parts by weight of butyl acrylate and 16 parts by weight of dimethyldiethoxysilane into toluene, and stirring/ultrasonically treating to obtain an acrylic derivative polymer solution;
uniformly mixing the dispersion liquid, the acrylic acid derivative polymer solution and 40 parts by weight of graphene nanoplatelets, adding 1.3 parts by weight of azobisisobutyronitrile, and performing high-speed dispersion/ultrasonic treatment to obtain the acrylic acid adhesive/graphene nanoplatelet composite heat-conducting adhesive.
The acrylic adhesive/graphene microchip composite thermal conductive adhesive prepared in example 2 was measured for thermal conductivity, and the thermal conductivity was 75W/m.k.
Example 3
0.2 part by weight of micron-sized TiO 2 Powder, 0.3 weight part of micron-sized SiO 2 Adding the powder and 1.5 parts of silane coupling agent into toluene, and stirring/ultrasonically treating to obtain pre-dispersed mother liquor;
2.4 parts by weight of nano-TiO 2 Powder, 2.2 parts by weight of sodiumMeter grade SiO 2 Adding the powder and 0.7 weight part of isocyanate into pre-dispersion mother liquor, and stirring/ultrasonically treating to obtain a prepared pre-dispersion mother liquor;
adding 72 parts by weight of methyl methacrylate, 34 parts by weight of butyl acrylate and 17 parts by weight of dimethyldiethoxysilane to toluene, and stirring/ultrasonic treating to obtain an acrylic acid derivative polymer solution;
uniformly mixing the dispersion liquid, the acrylic acid derivative polymer solution and 40 parts by weight of graphene nanoplatelets, adding 1.4 parts by weight of azobisisobutyronitrile, and performing high-speed dispersion/ultrasonic treatment to obtain the acrylic acid adhesive/graphene nanoplatelets composite heat-conducting adhesive.
The acrylic adhesive/graphene microchip composite thermal conductive adhesive prepared in example 3 was measured for thermal conductivity, and the thermal conductivity was 60W/mK.
Example 4
0.3 part by weight of micron-sized TiO 2 Powder and 0.2 weight part of micron-sized SiO 2 Adding the powder and 1.4 parts of silane coupling agent into toluene, and stirring/ultrasonically treating to obtain pre-dispersed mother liquor;
2.6 parts by weight of nano TiO2 powder and 2.0 parts by weight of nano SiO 2 Adding the powder and 0.7 weight part of isocyanate into pre-dispersion mother liquor, and stirring/ultrasonically treating to obtain prepared pre-dispersion mother liquor;
adding 73 parts by weight of methyl methacrylate, 34 parts by weight of butyl acrylate and 17 parts by weight of dimethyldiethoxysilane into toluene, and stirring/ultrasonic treating to obtain a polymer solution;
uniformly mixing the pre-dispersion liquid, the acrylic acid derivative polymer solution and 50 parts by weight of graphene nanoplatelets, adding 1.5 parts by weight of azobisisobutyronitrile, and performing high-speed dispersion/ultrasonic treatment to obtain the acrylic acid adhesive/graphene nanoplatelets composite heat-conducting adhesive.
The acrylic adhesive/graphene microchip composite thermal conductive adhesive prepared in example 4 was measured for thermal conductivity, and the thermal conductivity was 53W/mK.
Comparative example 1
Different from the embodiment 1, the graphene microchip is not added in the preparation process, and the heat conductivity coefficient of the finally prepared product is measured, wherein the heat conductivity coefficient is 2.5W/mK.
According to the experimental data, the thermal conductivity coefficient of the acrylic adhesive without the graphene microchip is generally not more than 2.5W/mK, and the thermal conductivity coefficient of the composite thermal conductive adhesive prepared in the invention is 19 to 30 times that of the acrylic adhesive.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The preparation method of the composite adhesive is characterized by comprising the following steps:
uniformly mixing the dispersion liquid, the acrylic acid derivative polymer solution and the graphene nanoplatelets, adding azobisisobutyronitrile, and performing dispersion and ultrasonic treatment to obtain the composite adhesive;
the preparation steps of the acrylic acid derivative polymer solution are as follows:
adding 70-73 parts by weight of methyl methacrylate, 32-34 parts by weight of butyl acrylate and 15-17 parts by weight of dimethyl diethoxy silane into a solvent for stirring/ultrasonic treatment to prepare an acrylic acid derivative polymer solution;
the preparation steps of the dispersion liquid are as follows:
adding TiO into solvent 2 、SiO 2 And silane coupling agent, preparing pre-dispersion mother liquor;
adding TiO into pre-dispersed mother liquor 2 、SiO 2 And isocyanate to prepare a dispersion.
2. The preparation method of the composite adhesive according to claim 1, wherein the TiO is used for preparing a pre-dispersion mother solution 2 、SiO 2 All are micron-sized powder; tiO in preparing dispersions 2 、SiO 2 All are nano-scale powder; the nano-sized TiO 2 The diameter of the powder is 25nm; nanoscale SiO 2 The powder diameter is 12nm.
3. The preparation method of the composite adhesive according to claim 1, wherein the TiO is used for preparing a pre-dispersion mother solution 2 0.1 to 0.4 part by weight of SiO 2 0.1-0.4 weight parts, 1.1-1.6 weight parts of silane coupling agent;
TiO in preparing dispersions 2 1.8-2.4 parts by weight of SiO 2 2.0 to 2.6 portions of silane coupling agent and 0.7 to 0.9 portion of silane coupling agent.
4. The preparation method of the composite adhesive according to claim 1, wherein the graphene nanoplatelets are 30-50 parts by weight.
5. The preparation method of the composite adhesive according to claim 1, wherein the azodiisobutyronitrile is 1.2 to 1.5 parts by weight.
6. The preparation method of the composite adhesive according to claim 1, wherein the solvent is any one or more of acetone, butanone, n-hexane, cyclohexane, benzene, toluene, xylene, ethyl acetate and methyl isobutyl ketone.
7. A composite adhesive prepared by the preparation method of the composite adhesive as claimed in any one of claims 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110867643.6A CN113563832B (en) | 2021-07-30 | 2021-07-30 | Composite adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110867643.6A CN113563832B (en) | 2021-07-30 | 2021-07-30 | Composite adhesive and preparation method thereof |
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| CN113563832A CN113563832A (en) | 2021-10-29 |
| CN113563832B true CN113563832B (en) | 2023-04-04 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176455A (en) * | 2014-01-09 | 2015-12-23 | 苏州斯迪克新材料科技股份有限公司 | Preparation process of pressure-sensitive non-bright adhesive |
| CN105907341A (en) * | 2016-05-17 | 2016-08-31 | 湖南省和祥润新材料有限公司 | High-viscosity acrylic adhesive and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105086887A (en) * | 2014-01-09 | 2015-11-25 | 斯迪克新型材料（江苏）有限公司 | Preparation method of adhesives for high-stability electronic products |
| US10696790B2 (en) * | 2014-12-02 | 2020-06-30 | Ningbo Zkjh New Material Co., Ltd. | Graphene dispersant and application thereof |
| CN107142034A (en) * | 2017-05-09 | 2017-09-08 | 北京化工大学 | A kind of heat conduction pressure sensitive adhesive and preparation method that graphene is peeled off comprising physics |
| CN109852274B (en) * | 2018-12-29 | 2021-06-15 | 苏州环明电子科技有限公司 | Graphene heat-conducting adhesive film and preparation process thereof |
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- 2021-07-30 CN CN202110867643.6A patent/CN113563832B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176455A (en) * | 2014-01-09 | 2015-12-23 | 苏州斯迪克新材料科技股份有限公司 | Preparation process of pressure-sensitive non-bright adhesive |
| CN105907341A (en) * | 2016-05-17 | 2016-08-31 | 湖南省和祥润新材料有限公司 | High-viscosity acrylic adhesive and preparation method thereof |
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