CN108192136B - Heat-conducting filler composition, high-heat-conducting insulating composite material and preparation method thereof - Google Patents
Heat-conducting filler composition, high-heat-conducting insulating composite material and preparation method thereof Download PDFInfo
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- CN108192136B CN108192136B CN201711498957.3A CN201711498957A CN108192136B CN 108192136 B CN108192136 B CN 108192136B CN 201711498957 A CN201711498957 A CN 201711498957A CN 108192136 B CN108192136 B CN 108192136B
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Classifications
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K3/02—Elements
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- 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
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
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- C08K3/28—Nitrogen-containing compounds
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a heat-conducting filler composition, which is characterized by comprising the following components in parts by weight: 90-95 parts of component A and 5-10 parts of component B; wherein the component A contains heat-conducting filler and silane coupling agent, and the silane coupling agent accounts for 1-3% of the total weight of the component A; the component B comprises graphene oxide and isocyanate, wherein the isocyanate accounts for 70-80% of the total weight of the component B. The invention also discloses a high-thermal-conductivity insulation composite material and a high-thermal-conductivity insulation base film containing the thermal-conductivity filler composition, and preparation methods of the composite material and the base film. The high-thermal-conductivity insulating composite material has high thermal conductivity, good insulativity and mechanical property, good dielectric property and high water vapor barrier property.
Description
Technical Field
The invention relates to the field of heat conduction materials, in particular to a heat conduction filler composition, a high heat conduction insulating composite material and a preparation method thereof.
Background
As electronic components and electronic devices are miniaturized and miniaturized, more and more heat is accumulated in a limited space, and thus, higher requirements are placed on heat conduction and heat dissipation of an insulating material. The heat conductivity coefficient of common polymer materials is difficult to meet the heat dissipation requirement.
At present, there are two main approaches to improve the thermal conductivity of polymers: (1) synthesizing polymers with high heat conductivity coefficient structures, such as polyacetylene, polyaniline, polypyrrole and the like, and mainly conducting electricity through an electronic heat conduction mechanism; or complete crystallinity is realized, and heat conduction is realized through phonons; (2) the heat conducting composite material is prepared by adding high heat conducting inorganic matter into a polymer system to realize heat conduction. The first approach does not need to add heat-conducting filler, realizes heat conduction by the polymer, has narrow application range, and cannot be applied to the insulation field due to self electric conduction; the second approach is to add inorganic heat-conducting fillers to contact each other in a polymer system to form a heat-conducting path to realize heat conduction, and the application range is wide, however, the heat-conducting coefficient of common inorganic heat-conducting fillers is still low, and the compatibility with the polymer system is poor, and the high heat-conducting function can be realized only by adding 50-90 wt% of inorganic heat-conducting fillers, which often causes the reduction of the mechanical property and the insulating property of the polymer material.
There remains a need for improved thermally conductive filler materials that achieve high thermal conductivity at low addition levels.
Disclosure of Invention
In view of the above need, in one aspect, the present invention provides a thermally conductive filler composition, characterized in that the thermally conductive filler composition comprises, by weight:
90-95 parts of component a, said component a comprising: a thermally conductive filler and a silane coupling agent; the silane coupling agent accounts for 1-3% of the total weight of the component A;
and
5-10 parts of component B, which comprises: graphene oxide and isocyanate; the isocyanate accounts for 70-80% of the total weight of the component B.
Optionally, the thermally conductive filler is selected from the group consisting of: aluminum oxide, aluminum nitride, boron nitride, and combinations thereof.
Optionally, the general structural formula of the silane coupling agent is Y- (CH)2)n-SiX3Wherein n is 0-3; three X are each independently selected from-OCH3or-OCH2CH3(ii) a Y is amino, epoxy group BOne of alkenyl groups. Optionally, the silane coupling agent is selected from the group consisting of: KH171, KH151, KH792, KH550, KH560, KH570, KH530, and combinations thereof.
Optionally, the graphene oxide is few-layer graphene oxide, the number of layers of the few-layer graphene oxide is 1 to 10, and preferably, the number of layers of the few-layer graphene oxide is 4 to 5.
Optionally, the isocyanate is selected from the group consisting of: aliphatic isocyanates, cycloaliphatic isocyanates, aromatic isocyanates, and combinations thereof, preferably the isocyanates are selected from the group consisting of: diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and combinations thereof.
In yet another aspect, the present invention provides a high thermal conductivity insulation composite material, characterized in that the high thermal conductivity insulation composite material comprises by weight:
75-90 parts of a polymer, wherein the polymer is selected from one of polyester, polynaphthalene ester and polyimide;
10-25 parts of the above-described thermally conductive filler composition; and
0.1-0.2 part of antioxidant.
Optionally, the polymer is polyethylene terephthalate, polyethylene naphthalate, or polyimide.
In yet another aspect, the present invention provides a method for preparing the above-mentioned high thermal conductivity insulation composite material, wherein the method comprises:
mixing the heat-conducting filler with the silane coupling agent in a solvent to prepare the component A;
mixing the graphene oxide with the isocyanate in a solvent to prepare the component B;
mixing the component A and the component B to prepare the thermally conductive filler composition;
mixing the heat-conducting filler composition, a polymer precursor and an antioxidant, and polymerizing the polymer precursor into the polymer to obtain the heat-conducting and insulating composite material.
Optionally, the component B and/or the thermally conductive filler composition is prepared by ultrasonic dispersion.
In yet another aspect, the present invention provides the use of the above-described high thermal conductive insulation composite as a thermal conductive insulation base film.
According to the heat-conducting filler composition, the silane coupling agent is used for surface grafting of the modified heat-conducting filler and the isocyanate functional modified graphene oxide, the coupling agent modified heat-conducting filler and the functional modified graphene oxide are mixed, and the covalent bond bonding is generated between the heat-conducting filler and the graphene oxide by utilizing the reaction of-NCO and hydroxyl, amino, epoxy and other groups, so that the strong interface interaction is generated between the heat-conducting filler and the graphene oxide, the interface thermal resistance between the heat-conducting filler is reduced, and the heat-conducting property of the heat-conducting filler can be greatly improved under the condition of a small addition amount of the graphene oxide. The heat-conducting filler composition has good dispersibility in polymers and excellent heat-conducting property, can greatly reduce the using amount of the heat-conducting filler, and keeps excellent mechanical property and insulating property. Furthermore, surprisingly, the addition of the thermally conductive filler composition significantly improves the water vapor barrier properties of the highly thermally conductive insulating base film while providing it with excellent dielectric properties.
Detailed Description
The present invention provides a thermally conductive filler composition comprising by weight:
90-95 parts of component a, said component a comprising: a thermally conductive filler and a silane coupling agent; the silane coupling agent accounts for 1-3% of the total weight of the component A;
and
5-10 parts of component B, which comprises: graphene oxide and isocyanate; the isocyanate accounts for 70-80% of the total weight of the component B.
The component A comprises a heat-conducting filler and a silane coupling agent. After the two are mixed, the mixture can react to form the silane coupling agent surface grafting modified heat-conducting filler. The silane coupling agent is grafted on the surface of the heat-conducting filler and provides the surface of the heat-conducting filler with groups such as hydroxyl, epoxy, amino and the like. The reaction may optionally be carried out under heating. In the component a comprising the thermally conductive filler and the silane coupling agent of the present invention, the thermally conductive filler and the silane coupling agent may have been already bonded to each other.
Thermally conductive fillers are fillers added to a matrix material to increase the thermal conductivity of the material. Commonly used thermally conductive fillers are inorganic thermally conductive fillers including metallic or non-metallic oxides, nitrides, carbides, and the like. Some examples include aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, and the like. They may be in the form of micro-or nano-sized powders. In the present invention, preferably, the thermally conductive filler may be alumina, aluminum nitride, boron nitride, or a combination thereof.
The silane coupling agent can be grafted and bonded to the surface of the heat-conducting filler, and plays a role in modifying the surface of the heat-conducting filler. The silane coupling agent surface modified filler has hydroxyl, amino, epoxy and other groups. A preferred silane coupling agent for use in the present invention may have Y- (CH)2)n-SiX3Wherein n is 0-3; x represents a group bonded to Si, and three X's may be the same or different and are each independently selected from-OCH3or-OCH2CH3(ii) a Y is one of amino, epoxy and vinyl. Such a silane coupling agent is good in reactivity with the heat conductive filler and is well combined with the following component B. Examples of the silane coupling agent that can be used in the present invention preferably include, but are not limited to, KH171, KH151, KH792, KH550, KH560, KH570, KH530, and combinations thereof. The silane coupling agent surface modification improves the compatibility of the thermally conductive filler with the polymer matrix material in which it is used, on the one hand, and provides good bonding of the thermally conductive filler with the graphene of component B, as described below, on the other hand.
The silane coupling agent accounts for 1 to 3 percent of the total weight of the component A. The silane coupling agent proportion can provide enough surface modification for the heat-conducting filler and proper amount of chemical bonding with the graphene oxide, so that the interface thermal resistance is reduced, the heat-conducting filler and the graphene oxide are difficult to disperse, and the heat-conducting efficiency is reduced.
And the component B comprises graphene oxide and isocyanate. After the two are mixed, the mixture can react to form isocyanate functional modified graphene oxide. The surface of the isocyanate modified graphene oxide has-NCO groups. The reaction is preferably carried out under ultrasonic dispersion. In the component B comprising graphene oxide and isocyanate according to the present invention, the graphene oxide and the isocyanate may be already combined with each other.
As a graphene precursor, graphene oxide is well known. Graphene is a novel two-dimensional carbon nanomaterial with a single-layer sheet structure composed of carbon atoms. The graphene has extremely high heat-conducting property, and the theoretical heat-conducting coefficient of the single-layer graphene can reach 5000W (m.K)-1Above, much higher than the currently known thermally conductive materials. However, graphene is an excellent electrical conductor with a resistivity of only 10-6Omega cm, has extremely fast electron transfer rate and electric conductivity, and is not suitable for the field of high-heat-conductivity insulating composite materials. In the graphene oxide, the conjugated structure of the graphene oxide is destroyed due to the presence of the oxygen-containing group, and the graphene oxide no longer has electrical conductivity but still has high thermal conductivity. Furthermore, oxygen-containing functional groups such as hydroxyl, epoxy, carbonyl, carboxyl, ester and the like exist on the surface of the graphene oxide, and the graphene oxide has good compatibility with organism systems. In the present invention, a few-layer graphene oxide is preferably used. The few-layer graphene oxide is graphene oxide with the number of layers not higher than 10. The smaller the number of layers of graphene oxide, the more excellent the heat conductivity. More preferably, a few-layer graphene oxide having 4 to 5 layers is used. Although the graphene oxide with less than 4 layers has better heat-conducting property, the preparation process is complex and difficult to prepare in batch, and the graphene oxide with more than 5 layers has poorer heat-conducting property, so that the graphene oxide with 4-5 layers can obtain excellent comprehensive performance and good cost performance.
The isocyanate includes aliphatic isocyanate, alicyclic isocyanate, aromatic isocyanate and the like. When the isocyanate is mixed with the graphene oxide, the isocyanate may react with oxygen-containing groups on the surface of the graphene oxide, chemically bond to the surface of the graphene oxide, and provide-NCO groups for the surface of the graphene oxide particles. The reaction may preferably be performed under ultrasonic dispersion to obtain uniform modified graphene oxide, preventing them from agglomeration. In the present invention, preferably, the isocyanate is selected from the group consisting of: diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and combinations thereof. They are preferred because the isocyanate is difunctional and does not form a three-dimensional cross-linked network structure, facilitating the dispersion of the graphene oxide and the thermally conductive filler in the polymer system.
The isocyanate accounts for 70-80% of the total weight of the component B. The proportion of the isocyanate can provide enough surface modification for the graphene oxide and proper chemical bonding of the heat-conducting filler, so that the interface thermal resistance is reduced, the heat-conducting filler and the graphene oxide are difficult to disperse, and the heat-conducting efficiency is reduced.
The thermally conductive filler composition of the present invention comprises component a and component B. When the two components are mixed, the hydroxyl, amino, epoxy and other groups on the surface of the silane coupling agent grafted and modified heat-conducting filler in the component A react with-NCO groups on the surface of the isocyanate functionalized and modified graphene oxide in the component B to form covalent bond combination between the heat-conducting filler and the graphene oxide, so that strong interface interaction between the heat-conducting filler and the graphene oxide occurs, and the interface thermal resistance between the heat-conducting filler is reduced. The heat-conducting filler and the graphene oxide jointly form a high heat-conducting path. When the graphene oxide/graphene oxide composite material is used for a polymer matrix, on one hand, compared with a heat conduction path formed by singly using graphene oxide, the graphene oxide is less in use amount, the heat conduction performance of the heat conduction filler can be greatly improved under the condition of smaller addition amount of the graphene oxide, and the cost is greatly reduced; on the other hand, compared with the use of the common heat conductive filler, the high heat conductive insulating composite material, namely the polymer mixed with the heat conductive filler composition, can keep excellent mechanical property and insulating property by reducing the using amount of the heat conductive filler while obtaining excellent heat conductive property. The thermally conductive filler composition of the present invention is easily dispersed in and well compatible with the polymer matrix. In particular, the silane coupling agent and isocyanate used for surface modification do not adversely affect the heat conductive property of the heat conductive filler composition of the present invention due to the above-described strong interaction formed between the heat conductive filler and graphene oxide and thus low interface thermal resistance. Furthermore, the inventors have also surprisingly found that the addition of the thermally conductive filler composition of the present invention can also significantly improve the moisture barrier properties of the highly thermally conductive insulating base film. In addition, when the heat conductivity of the polymer is improved by using the common heat conductive filler, the dielectric property is reduced due to the large addition amount of the heat conductive filler, and the high heat conductivity and the low dielectric property are a contradiction which is difficult to be coordinated and are difficult to realize simultaneously. However, the heat-conducting filler composition can obtain high heat-conducting property with a small addition amount, so that the dielectric property of the high heat-conducting insulating base film cannot be greatly reduced, the high heat-conducting property is realized, the good dielectric property is kept, and the problem that the common dielectric property of a high heat-conducting product is poor is solved.
The heat-conducting filler composition can be used in various applications requiring heat-conducting fillers or heat-conducting agents, and is particularly suitable for the application of high-heat-conducting insulating composite materials taking polymers as substrates.
The invention provides a high-thermal-conductivity insulating composite material, which comprises the following components in percentage by weight:
75-90 parts of a polymer, wherein the polymer is selected from one of a polyester, a polynaphthalene ester and a polyimide;
10-25 parts of the thermally conductive filler composition of the present invention; and
0.1-0.2 part of antioxidant.
When the common inorganic heat-conducting filler is added, the high heat-conducting function can be realized only under the addition of 50-90 wt%, and in the high heat-conducting insulating composite material, the polymer can account for more than 75 wt%. This is very advantageous for maintaining the mechanical properties of the matrix material.
The polymer may be any polymer. The heat-conducting filler composition has good compatibility with organic base materials. Preferably, the polymer is selected from one of polyester, polynaphthalene ester and polyimide. More preferably, the polymer is polyethylene terephthalate, polyethylene naphthalate or polyimide. The polymers have good comprehensive performance and are particularly suitable to be used as a matrix of a high-thermal-conductivity insulating composite material.
Preferably, the polymer of the present invention is a polymer formed by polymerization after mixing the thermally conductive filler composition into the polymerization monomer. In this way, the thermally conductive filler composition can be uniformly and firmly dispersed and incorporated into the polymer formed by polymerization.
The high-thermal-conductivity insulating composite material also comprises an antioxidant. Antioxidants are well known to those skilled in the art. The antioxidant which can be used in the present invention is not particularly limited, and is preferably one or both of a hindered phenol antioxidant and a phosphite antioxidant, and commercially available are: antioxidant 1010, antioxidant 168, antioxidant 1098, antioxidant 245, antioxidant 626, and combinations thereof.
The invention also provides a method for preparing the high-thermal-conductivity insulating composite material, which comprises the following steps:
mixing the heat-conducting filler with the silane coupling agent in a solvent to prepare the component A;
mixing the graphene oxide with the isocyanate in a solvent to prepare the component B;
mixing the component A and the component B to prepare the thermally conductive filler composition;
mixing the heat-conducting filler composition, a polymer precursor and an antioxidant, and polymerizing the polymer precursor into the polymer to obtain the high heat-conducting and insulating composite material.
The preparation of component A is carried out in a solvent, for example in an absolute ethanol solution. The inventors of the present invention found that adjusting the reaction environment to be weakly basic is advantageous for preparing the component A having good properties. For example, the pH of the reaction solution may be adjusted to 8 to 9. The pH can be adjusted with an alkaline solution, for example with a 10% strength aqueous NaOH solution.
When component a is prepared, the surface modification reaction may be accelerated by heating in some cases. For example at temperatures around 80 c, sufficient surface modification can be achieved after 30 minutes.
After the reaction, the reaction solution may be dried to obtain a dried component a.
The preparation of component B is also carried out in a solvent, for example in anhydrous Dimethylformamide (DMF).
The preparation of component B is preferably carried out under ultrasonic dispersion. The ultrasonic dispersion is beneficial to further stripping of the graphene oxide, prevents the graphene oxide from agglomerating, accelerates the surface modification process of the graphene oxide and obtains a uniform product.
The preparation of the thermally conductive filler composition is also carried out in a solvent. The solvent may be the same solvent as the solvent for preparing component B. Thus, the prepared and dried component a may be added to the solvent containing component B, the reaction is continued, and then filtered and dried to obtain the thermally conductive filler composition.
The preparation of the thermally conductive filler composition is also preferably carried out under ultrasonic dispersion. Ultrasonic dispersion helps to form a uniform bond of the thermally conductive filler and the graphene oxide.
The thermally conductive filler composition of the present invention can be dispersed in a polymer material to form a highly thermally conductive and insulating composite. However, the high thermal conductive insulating composite can also be obtained by in-situ polymerization after mixing the thermally conductive filler composition into the polymerization monomer. By performing in-situ polymerization, the thermally conductive filler composition can be incorporated into the polymerized polymer through various suitable groups and uniformly dispersed therein, and form a thermally conductive path. Typical polymers include polyesters, polynaphthalenes, polyimides, and the like, and specific examples include polyethylene terephthalate, polyethylene naphthalate, polyimides, and the like. Suitable polymeric monomers can be selected to form the polymer in the high thermal conductivity insulating composite.
In one example, polyethylene terephthalate can be formed from the polycondensation of terephthalic acid and ethylene glycol. The polycondensation process can be accomplished by various known processes as long as the thermally conductive filler composition of the present invention is compatible with such processes. When the high thermal conductive insulating composite material is used as the high thermal conductive insulating base film, it is generally molded by a melt casting method. In the present invention, the polyethylene terephthalate preferably has an intrinsic viscosity of 0.5 to 1.3 dL/g. The polyethylene terephthalate with the intrinsic viscosity has proper molecular weight, is easy to form by a melt casting method, and is suitable for being used as the high-heat-conductivity insulating composite material.
In one example, polyethylene naphthalate may be copolymerized from 2, 6-naphthalene dicarboxylic acid and ethylene glycol. The copolymerization process can be accomplished by various known processes as long as the thermally conductive filler composition of the present invention is compatible with such processes. The preferred intrinsic viscosity of the polyethylene naphthalate is from 0.5 to 1.5 dL/g. The polyethylene naphthalate with the intrinsic viscosity has proper molecular weight, is easy to form by a melt casting method, and is suitable for being used as the high-heat-conductivity insulating composite material.
In one example, the polyimide may be obtained by condensation polymerization of aromatic diamine, aromatic dianhydride in an organic solvent; the molar ratio of the aromatic diamine to the aromatic dianhydride is 1: 0.9-1: 1.1. The polycondensation process can be accomplished by various known processes as long as the thermally conductive filler composition of the present invention is compatible with such processes.
The aromatic diamine may be selected from, but is not limited to, p-phenylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, and the like.
The aromatic dianhydride may be selected from, but not limited to, pyromellitic anhydride, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, and the like.
The organic solvent may be selected from one or more of, but not limited to, N-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), and Dimethylsulfoxide (DMSO).
The invention is further illustrated by the following examples. The examples are for illustrative purposes only and do not limit the present invention in any way.
Examples
Preparation of thermally conductive filler composition
The alumina can be spherical alumina or/and angular alumina; angle alumina commercially available from American Yabao as MZS-3; AM-210, AM-43, LA4000 of Sumitomo; m15 of Buddha mountain Huaya. Spherical alumina is purchased as BAK-2 and BAK-10 of hundred-picture high-new material science and technology; AS-10 and AS-05 of Showa electrician.
Aluminum nitride is commercially available from Toyo aluminum Japan, TFZ-N01P, TFZ-A02P, and the like;
boron nitride is JYBN-0010 and JYBN-0100 of Unionidae Xin source material technology; baitu high and new materials science and technology BBN-10C, BBN-30C.
The graphene oxide used in the examples was prepared by Hummers method. Specifically, concentrated sulfuric acid is added into an ice water bath, a proper amount of graphite and sodium nitrate are added under the condition of magnetic stirring, and potassium permanganate is added in several times. Controlling the reaction temperature at 6 ℃, keeping the reaction for 2 hours, then heating to 35 ℃, and keeping the temperature for 30 minutes under stirring; water was continuously added, the temperature was raised to 90 ℃ and the reaction was carried out for 30 minutes, followed by dilution with distilled water and addition of an appropriate amount of hydrogen peroxide solution so that the solution became bright yellow. The solution is filtered while hot and washed repeatedly with dilute hydrochloric acid solution until the sulfate radicals are completely removed. And putting the product into an oven to dry, and then drying in a vacuum drying oven to obtain the graphite oxide. And adding graphite oxide into deionized water for ultrasonic dispersion, and drying to obtain the graphene oxide.
Example of Filler 1
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.15g of silane coupling agent KH171 in absolute ethanol, adjusting the pH value to 8 by using 10% sodium hydroxide aqueous solution, then adding 10g of alumina MZS-3, stirring and reacting at 80 ℃ for 30 minutes, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler.
(2) Functional modification of graphene oxide: and adding 0.18g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.45g of diphenylmethane diisocyanate, and performing ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: and (3) adding the silane coupling agent modified heat-conducting filler prepared in the step (1) into the reaction solution, continuing to react for 12 hours, and filtering and drying to obtain the heat-conducting filler composition 1.
Example of Filler 2
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.3g of silane coupling agent KH560 in absolute ethanol, adjusting the pH value to 9 by using 10% sodium hydroxide aqueous solution, adding 15g of boron nitride JYBN-0010, stirring and reacting for 30 minutes at 80 ℃, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler.
(2) Functional modification of graphene oxide: adding 0.3g of graphene oxide into anhydrous DMF, carrying out ultrasonic dispersion for 25 minutes, adding 0.9g of hexamethylene diisocyanate, and carrying out ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: and (3) adding the silane coupling agent modified heat-conducting filler prepared in the step (1) into the reaction solution, continuing to react for 12 hours, and filtering and drying to obtain a heat-conducting filler composition 2.
Example of Filler 3
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.3g of silane coupling agent KH792 in absolute ethyl alcohol, adjusting the pH value to 9 by using 10% sodium hydroxide aqueous solution, adding 9.8g of aluminum nitride TFZ-N01P, stirring and reacting at 80 ℃ for 30 minutes, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler.
(2) Surface functionalization modification of graphene oxide: and adding 0.23g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.83g of toluene diisocyanate, and performing ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: adding the coupling agent modified heat-conducting filler into the reaction solution, continuing the reaction for 12 hours, filtering and drying to obtain the heat-conducting filler composition 3.
Example of Filler 4
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.28g of silane coupling agent KH171 in absolute ethanol, adjusting the pH value to 8 by using 10% sodium hydroxide aqueous solution, then adding 10.5g of aluminum nitride TFZ-A02P, stirring and reacting for 30 minutes at 80 ℃, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler.
(2) Surface functionalization modification of graphene oxide: and adding 0.2g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.56g of isophorone diisocyanate, and performing ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: adding the coupling agent modified heat-conducting filler into the reaction solution, continuing to react for 12 hours, and filtering and drying to obtain the heat-conducting filler composition 4.
Example 5 of Filler
The thermally conductive filler composition was prepared by the following steps.
1) Surface modification of the heat-conducting filler: dissolving 0.31g of silane coupling agent KH792 in absolute ethanol, adjusting pH to 8 with 10% sodium hydroxide aqueous solution, adding 10.35g of alumina BAK-2, stirring at 80 deg.C for reaction for 30 min, and vacuum drying to obtain silane coupling agent modified heat-conducting filler
(2) Surface functionalization modification of graphene oxide: and adding 0.22g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.81g of toluene diisocyanate, and performing ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: adding the coupling agent modified heat-conducting filler into the reaction solution, continuing to react for 12 hours, filtering and drying to obtain the heat-conducting filler composition 5.
Example of Filler 6
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.38g of silane coupling agent KH570 in absolute ethanol, adjusting the pH value to 8 by using 10% sodium hydroxide aqueous solution, adding 13g of boron nitride BBN-30C, stirring and reacting at 80 ℃ for 30 minutes, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler
(2) Surface functionalization modification of graphene oxide: and adding 0.19g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.52g of diphenylmethane diisocyanate, and performing ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: adding the coupling agent modified heat-conducting filler into the reaction solution, continuing to react for 12 hours, filtering and drying to obtain the heat-conducting filler composition 6.
Example of Filler 7
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.2g of silane coupling agent KH530 in absolute ethanol, adjusting the pH value to 9 by using 10% sodium hydroxide aqueous solution, then adding 7.49g of boron nitride JYBN-0100, stirring and reacting for 30 minutes at 80 ℃, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler.
(2) Surface functionalization modification of graphene oxide: and adding 0.1g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.4g of isophorone diisocyanate, and performing ultrasonic reaction for 24 hours.
(3) Preparation of the heat-conducting filler composition: adding the coupling agent modified heat-conducting filler into the reaction solution, continuing to react for 12 hours, filtering and drying to obtain the heat-conducting filler composition 7.
Preparation of comparative Heat-conducting Filler
Comparative example 1 of Filler
The heat conductive filler is prepared by the following steps.
Surface modification of the heat-conducting filler: dissolving 0.2g of silane coupling agent KH151 in absolute ethyl alcohol, adjusting the pH value to 8 by using 10% sodium hydroxide aqueous solution, then adding 13g of boron nitride BBN-30C, stirring and reacting for 30 minutes at 80 ℃, and drying in vacuum to obtain the relatively heat-conducting filler 1.
Comparative filler example 2
The heat conductive filler is prepared by the following steps.
Surface functionalization modification of graphene oxide: adding 1g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 2.5g of diphenylmethane diisocyanate, and performing ultrasonic reaction for 24 hours to obtain the comparative heat-conducting filler 2.
Comparative filler example 3
The thermally conductive filler composition was prepared by the following steps.
10g of alumina MZS-3 was mixed directly with 0.18g of graphene oxide and reacted for 12 hours to provide comparative thermally conductive filler composition 3.
Comparative filler example 4
The thermally conductive filler composition was prepared by the following steps.
(1) Surface modification of the heat-conducting filler: dissolving 0.3g of silane coupling agent KH792 in absolute ethyl alcohol, adjusting the pH value to 9 by using 10% sodium hydroxide aqueous solution, adding 9.8g of aluminum nitride TFZ-N01P, stirring and reacting at 80 ℃ for 30 minutes, and drying in vacuum to obtain the silane coupling agent modified heat-conducting filler.
(2) Preparation of the heat-conducting filler composition: and (3) mixing 0.23g of graphene oxide with the coupling agent modified heat-conducting filler prepared in the step (1), and continuously reacting for 12 hours to obtain a comparative heat-conducting filler composition 4.
Comparative filler example 5
The thermally conductive filler composition was prepared by the following steps.
(1) Surface functionalization modification of graphene oxide: and adding 0.1g of graphene oxide into anhydrous DMF, performing ultrasonic dispersion for 25 minutes, adding 0.4g of isophorone diisocyanate, and performing ultrasonic reaction for 24 hours.
(2) Preparation of the heat-conducting filler composition: adding 7.49g of boron nitride JYBN-0100 into the reaction solution, continuing to react for 12 hours, filtering and drying to obtain a comparative heat-conducting filler composition 5.
The formulation of the thermally conductive filler composition is listed in table 1.
TABLE 1 thermally conductive filler composition formulation
TABLE 1 (continuation)
Preparation of heat-conducting insulating composite material film
Insulating film example 1
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of high thermal conductivity polyester: the required monomer amount is calculated according to the polymer content in the following formula table 2, terephthalic acid, ethylene glycol, an antioxidant 1010 and a heat-conducting filler composition 1 are added into a reaction kettle, 0.03 percent of ethylene glycol antimony relative to the mass of the ethylene glycol is added as a catalyst, reflux reaction is carried out at 260 ℃, the intrinsic viscosity of the product is controlled to be 0.5dL/g, and the product is cut into particles to prepare the high heat-conducting polyester.
Preparing a high-thermal-conductivity polyester film: and (2) performing casting extrusion on the heat-conducting polyester film resin at 270 ℃ to obtain a PET thick sheet, and performing biaxial stretching on a static biaxial stretcher to obtain the heat-conducting PET film.
Insulating film example 2
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of high thermal conductivity polyester: the required monomer amount is calculated according to the polymer content in the following formula table 2, terephthalic acid, ethylene glycol, an antioxidant 1098 and a heat-conducting filler composition 2 are added into a reaction kettle, then ethylene glycol antimony which is 0.03 percent of the mass of the ethylene glycol is added as a catalyst, reflux reaction is carried out at 300 ℃, the intrinsic viscosity of the product is controlled to be 1.3dL/g, and the product is cut into particles to prepare the high heat-conducting polyester.
Preparing a high-thermal-conductivity polyester film: and (2) performing casting extrusion on the heat-conducting polyester resin at 280 ℃ to obtain a PET thick sheet, and performing biaxial stretching on a static biaxial stretcher to obtain the high-heat-conducting PET film.
Insulating film example 3
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of high thermal conductivity polynaphthalene: the monomer amount needed is calculated according to the polymer content in the following formula table 2, 6-naphthalene dicarboxylic acid, ethylene glycol, antioxidant 1010, antioxidant 168 and heat-conducting filler composition 3 are added into a reaction kettle, then ethylene glycol antimony which is 0.03 percent of the mass of ethylene glycol is added as a catalyst, reflux reaction is carried out at 240 ℃, the intrinsic viscosity of the product is controlled to be 0.5dL/g, and the product is cut into particles to prepare the high heat-conducting polynaphthylene ester.
Preparing a high-thermal-conductivity polynaphthalene film: and (3) carrying out curtain coating extrusion on the high-thermal-conductivity polynaphthalene resin to obtain a PEN thick sheet, and then carrying out bidirectional stretching on the PEN thick sheet on a static bidirectional stretching machine to obtain the high-thermal-conductivity PEN film.
Insulating film example 4
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of high thermal conductivity polynaphthalene: the monomer amount needed is calculated according to the polymer content in the following formula table 2, 6-naphthalene dicarboxylic acid, ethylene glycol, an antioxidant 245 and a heat-conducting filler composition 4 are added into a reaction kettle, then ethylene glycol antimony which is 0.03 percent of the mass of the ethylene glycol is added as a catalyst, reflux reaction is carried out at 250 ℃, the intrinsic viscosity of the product is controlled to be 1.3dL/g, and the product is cut into particles to prepare the high heat-conducting polynaphthylene ester.
Preparing a high-thermal-conductivity polynaphthalene film: and (3) carrying out curtain coating extrusion on the high-thermal-conductivity polynaphthalene resin to obtain a PEN thick sheet, and then carrying out bidirectional stretching on the PEN thick sheet on a static bidirectional stretching machine to obtain the high-thermal-conductivity PEN film.
Example of insulating film 5
A thermally conductive, electrically insulating composite film is prepared by the following steps.
Preparing a heat-conducting polyimide film: calculating the required monomer amount according to the polymer content in the following formula table 2, adding p-phenylenediamine, pyromellitic dianhydride, antioxidant 626 and heat-conducting filler composition 5 into DMF to react for 12 hours to form polyamic acid solution, casting to form a film, then performing stage heat treatment at 60 ℃, 120 ℃, 200 ℃, 280 ℃ and 370 ℃ for 2-60 minutes respectively to perform imidization, and naturally cooling to obtain the high-heat-conducting polyimide film.
Example of insulating film 6
A thermally conductive, electrically insulating composite film is prepared by the following steps.
Preparing a heat-conducting polyimide film: the required monomer amount is calculated according to the polymer content in the following formula table 2, 4, 4 ' -diaminodiphenyl ether, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, antioxidant 1010 and heat-conducting filler composition 6 are added into DMAc to react for 12 hours to form polyamic acid solution, the polyamic acid solution is cast into a film, then the film is imidized by stage heat treatment for 2-60 minutes at 60 ℃, 120 ℃, 200 ℃, 280 ℃ and 370 ℃, and the polyimide film with high heat conductivity is obtained after natural cooling.
Example of insulating film 7
A thermally conductive, electrically insulating composite film is prepared by the following steps.
Preparing a heat-conducting polyimide film: the required monomer amount is calculated according to the polymer content in the following formula table 2, 4, 4 ' -diaminodiphenylmethane, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, antioxidant 1010, antioxidant 245 and heat-conducting filler composition 7 are added into NMP to react for 12 hours to form polyamic acid solution, the polyamic acid solution is cast into a film, then the film is imidized by stage heat treatment at 60 ℃, 120 ℃, 200 ℃, 280 ℃ and 370 ℃ for 2-60 minutes respectively, and the polyimide film with high heat conductivity is obtained after natural cooling. Comparative insulating film example 1
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of thermally conductive polyester: the required monomer amount is calculated according to the polymer content in the following formula table 2, terephthalic acid, ethylene glycol, an antioxidant 1098 and a comparative heat-conducting filler composition 1 are added into a reaction kettle, then ethylene glycol antimony which is 0.03 percent of the mass of ethylene glycol is added as a catalyst, reflux reaction is carried out at 270 ℃, the intrinsic viscosity of the product is controlled to be 0.8dL/g, and the product is cut into particles to prepare the heat-conducting polyester.
Preparing a heat-conducting polyester film: and (2) performing casting extrusion on the heat-conducting polyester film resin at 270 ℃ to obtain a PET thick sheet, and performing biaxial stretching on a static biaxial stretcher to obtain the heat-conducting PET film.
Comparative insulating film example 2
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In situ polymerization of heat conductive naphthalene ester: the amount of monomers required is calculated according to the polymer content in the following formula table 2, 6-naphthalene dicarboxylic acid, ethylene glycol, an antioxidant 168 and a comparative heat-conducting filler composition 2 are added into a reaction kettle, 0.03 percent of ethylene glycol antimony relative to the mass of the ethylene glycol is added as a catalyst, reflux reaction is carried out at 240 ℃, the intrinsic viscosity of the product is controlled to be 1.3dL/g, and the product is cut into particles to prepare the heat-conducting polynaphthylene ester.
Preparing a heat-conducting polynaphthalene film: and (3) carrying out tape casting extrusion on the heat-conducting polynaphthalene ester resin to obtain a PEN thick sheet, and then carrying out bidirectional stretching on the PEN thick sheet on a static bidirectional stretching machine to obtain the heat-conducting PEN film.
Comparative insulating film example 3
A thermally conductive, electrically insulating composite film is prepared by the following steps.
Preparing a heat-conducting polyimide film: the monomer amount needed is calculated according to the polymer content in the following formula table 2, p-phenylenediamine, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, antioxidant 1098 and comparative heat-conducting filler composition 2 are added into DMF to react for 12 hours to form polyamic acid solution, the polyamic acid solution is cast into a film, then periodic heat treatment is carried out for 2-60 minutes at 60 ℃, 120 ℃, 200 ℃, 280 ℃ and 370 ℃ respectively to imidize, and the imidization heat-conducting polyimide film is obtained after natural cooling.
Comparative insulating film example 4
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of thermally conductive polyester: the required monomer amount is calculated according to the polymer content in the following formula table 2, terephthalic acid, ethylene glycol, an antioxidant 1010 and a comparative heat-conducting filler composition 3 are added into a reaction kettle, then ethylene glycol antimony which is 0.03 percent of the mass of ethylene glycol is added as a catalyst, reflux reaction is carried out at 260 ℃, the intrinsic viscosity of the product is controlled to be 0.5dL/g, and the product is cut into granules to prepare the heat-conducting polyester.
Preparing a heat-conducting polyester film: and (2) performing casting extrusion on the heat-conducting polyester film resin at 270 ℃ to obtain a PET thick sheet, and performing biaxial stretching on a static biaxial stretcher to obtain the heat-conducting PET film.
Comparative insulating film example 5
A thermally conductive, electrically insulating composite film is prepared by the following steps.
In-situ polymerization of high thermal conductivity polynaphthalene: the monomer amount needed is calculated according to the polymer content in the following formula table 2, 6-naphthalene dicarboxylic acid, ethylene glycol, antioxidant 1010, antioxidant 168 and comparative heat-conducting filler composition 4 are added into a reaction kettle, then ethylene glycol antimony which is 0.03 percent of the mass of ethylene glycol is added as a catalyst, reflux reaction is carried out at 240 ℃, the intrinsic viscosity of the product is controlled to be 0.5dL/g, and the product is granulated, so that the high heat-conducting polynaphthalene ester is prepared.
Preparing a high-thermal-conductivity polynaphthalene film: and (3) carrying out curtain coating extrusion on the high-thermal-conductivity polynaphthalene resin to obtain a PEN thick sheet, and then carrying out bidirectional stretching on the PEN thick sheet on a static bidirectional stretching machine to obtain the high-thermal-conductivity PEN film.
Comparative insulating film example 6
A thermally conductive, electrically insulating composite film is prepared by the following steps.
Preparing a heat-conducting polyimide film: the monomer amount required is calculated according to the polymer content in the following formula table 2, 4, 4 ' -diaminodiphenylmethane, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, antioxidant 1010, antioxidant 245 and comparative heat-conducting filler composition 5 are added into DMSO to react for 12 hours to form polyamic acid solution, the polyamic acid solution is cast into a film, then the film is imidized by carrying out stage heat treatment for 2-60 minutes at 60 ℃, 120 ℃, 200 ℃, 280 ℃ and 370 ℃, and the heat-conducting polyimide film is obtained after natural cooling.
TABLE 2 insulating film formulation
Table 2 (continuation)
Characterization of insulating film Properties
The following property characterization was performed for the insulating films prepared in insulating films 1 to 7 and comparative insulating film examples 1 to 6. The characterization results are shown in Table 3.
(1) Tensile Properties
The tensile strength and elongation at break were measured according to GB/T13542.2-2009 with a tensile rate of 100mm/min and a nip length of 100 mm.
(2) Heat conductivity
Thermal conductivity was tested according to ASTM D5470.
(3) Electric strength
Testing according to GB/T1408.1-2006.
(4) Volume resistivity and surface resistance
Tested according to GB/T1410-2006.
(5) Dielectric constant and dielectric loss tangent
Test according to ASTM D150-2011.
(6) Water vapor transmission rate
Tested according to GB/T21529-2008.
TABLE 3 characterization of insulating film Properties
Table 3 (continuation)
The thermally conductive insulating composite film of the present invention in the insulating film example has a much higher thermal conductivity than the comparative insulating film example.
The thermally conductive, electrically insulating composite film of the present invention in the insulating film example had higher volume resistivity and surface resistance than the comparative insulating film example.
The thermally conductive, electrically insulating composite films of the present invention in the insulating film example possess lower dielectric constants and dielectric loss tangents, indicating good dielectric properties despite their greatly improved thermal conductivity.
The thermally conductive insulating composite film of the present invention in the insulating film example has a lower water vapor transmission rate than the comparative insulating film example. Therefore, the heat-conducting filler composition provided by the invention enables the heat-conducting insulating composite material to have better water vapor barrier property.
The polyester films of insulating film examples 1-2, like the polyester films, had higher tensile strength and elongation at break than the polyester films of comparative insulating film examples 1, 4. The heat conductive filler composition of insulating film example 1 and comparative insulating film example 4 were added in the same amount, but the heat conductive filler and graphene oxide of comparative insulating film example 4 were not surface-treated, did not form effective chemical bonds, and had poor compatibility with organic systems, so the heat conductive performance, adhesive performance, insulating performance, moisture barrier property, and dielectric performance of comparative insulating film example 4 were inferior to that of insulating film example 1.
The polynaphthalene films of insulating film examples 3 to 4 had higher tensile strength and elongation at break than the polynaphthalene films of comparative insulating film examples 2, 5, as well as the polynaphthalene films. The thermal conductive filler composition of insulating film example 3 and comparative insulating film example 5 were added in the same amount, but the graphene oxide of comparative insulating film example 5 was not functionalized, and the graphene oxide failed to form an effective chemical bond with the thermal conductive filler, so the thermal conductive performance, adhesive performance, insulating performance, moisture barrier performance, and dielectric performance of comparative insulating film example 5 were inferior to that of insulating film example 3.
The polyimide films of insulating film examples 5 to 7, like the polyimide film, had higher tensile strength and elongation at break than the polyimide films of comparative insulating film examples 3, 6. The heat conductive filler composition of insulating film example 7 and comparative insulating film example 6 were added in the same amount, but the heat conductive filler of comparative insulating film example 6 was not surface-treated, so that graphene oxide could not form effective chemical bonds with the heat conductive filler, and the compatibility of the heat conductive filler with an organic system was poor, so the heat conductive performance, adhesive performance, insulating performance, moisture barrier property, and dielectric performance of comparative insulating film example 6 were inferior to those of insulating film example 7.
In conclusion, when the heat-conducting filler composition is adopted, efficient heat-conducting network channels can be formed under the condition of small addition amount of the heat-conducting filler, excellent heat-conducting performance is obtained, and the heat-conducting coefficients are all larger than 20W/(m.K). Moreover, the heat-conducting filler composition has excellent compatibility with the insulating base film body, and can maintain excellent insulating property and mechanical property. The thermally conductive filler composition increases the resistance to water vapor permeation, thereby allowing the water vapor transmission rate of the insulating base film to be greatly reduced as compared to the comparative example. In addition, the composite heat-conducting filler is less in addition, so that the prepared insulating base film has excellent dielectric property, and the contradiction between the dielectric property and the heat-conducting property is solved.
The above description is only a preferred embodiment of the present invention, and it will be obvious to those skilled in the art that various other changes and modifications may be made according to the technical solution and the technical concept of the present invention, and all such changes and modifications should fall within the scope of the claims of the present invention.
Claims (13)
1. A thermally conductive filler composition, characterized in that it comprises by weight:
90-95 parts of component a, said component a comprising: a thermally conductive filler and a silane coupling agent; the silane coupling agent accounts for 1-3% of the total weight of the component A;
and
5-10 parts of component B, which comprises: graphene oxide and isocyanate; the isocyanate accounts for 70 to 80 percent of the total weight of the component B,
wherein the silane coupling agent and the-NCO group of the isocyanate form a covalent bond between the thermally conductive filler and the graphene oxide.
2. The thermally conductive filler composition of claim 1, wherein the thermally conductive filler is selected from the group consisting of: aluminum oxide, aluminum nitride, boron nitride, and combinations thereof.
3. The thermally conductive filler composition of claim 1, wherein the silane coupling agent has the general structural formula Y- (CH)2)n-SiX3Wherein n is 0-3; three X are each independently selected from-OCH3or-OCH2CH3(ii) a Y is one of amino, epoxy and vinyl.
4. The thermally conductive filler composition according to claim 1, wherein the graphene oxide is a few-layer graphene oxide, and the number of layers of the few-layer graphene oxide is 1 to 10.
5. The thermally conductive filler composition according to claim 4, wherein the number of the few-layered graphene oxide layers is 4 to 5.
6. The thermally conductive filler composition of claim 1, wherein the isocyanate is selected from the group consisting of: aliphatic isocyanates, cycloaliphatic isocyanates, aromatic isocyanates, and combinations thereof.
7. The thermally conductive filler composition of claim 6, wherein the isocyanate is selected from the group consisting of: diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and combinations thereof.
8. A high thermal conductivity insulation composite, comprising by weight:
75-90 parts of a polymer, wherein the polymer is selected from one of polyester and polyimide;
10-25 parts of the thermally conductive filler composition of claim 1; and
0.1-0.2 part of antioxidant.
9. The high thermal conductivity insulating composite of claim 8, wherein the polyester is a polynaphthalene ester.
10. The high thermal conductivity insulating composite of claim 8, wherein the polymer is polyethylene terephthalate, polyethylene naphthalate, or polyimide.
11. A method for preparing the high thermal conductivity insulation composite material of claim 8, wherein the method comprises:
mixing the heat-conducting filler with the silane coupling agent in a solvent to prepare the component A;
mixing the graphene oxide with the isocyanate in a solvent to prepare the component B;
mixing the component A and the component B such that the silane coupling agent and the-NCO groups of the isocyanate form a covalent bond between the thermally conductive filler and the graphene oxide to produce the thermally conductive filler composition;
mixing the heat-conducting filler composition, a polymer precursor and an antioxidant, and polymerizing the polymer precursor into the polymer to obtain the heat-conducting and insulating composite material.
12. The method of claim 11, wherein the component B and/or the thermally conductive filler composition is prepared by ultrasonic dispersion.
13. Use of the high thermal conductive insulation composite material according to claim 8 as a high thermal conductive insulation base film.
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| CN110577716B (en) * | 2019-09-23 | 2021-10-08 | 南通伟越电器有限公司 | Preparation method of high-impact-resistance polystyrene special material for television shell |
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| CN113502000A (en) * | 2021-06-18 | 2021-10-15 | 中北大学 | Covalently-bonded low-interface-thermal-resistance high-thermal-conductivity modified graphene functional particle and natural rubber composite material thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183889A (en) * | 2013-03-21 | 2013-07-03 | 上海交通大学 | High-thermal-conductivity and insulating polymer composite material and preparation method thereof |
| CN103725002A (en) * | 2013-12-27 | 2014-04-16 | 中国科学院深圳先进技术研究院 | Aluminum oxide composite material and preparation method thereof, and copper clad base plate |
| CN104610780A (en) * | 2015-01-12 | 2015-05-13 | 中国科学院宁波材料技术与工程研究所 | Modification method for silicon carbide particles |
| CN105349114A (en) * | 2015-10-27 | 2016-02-24 | 中国科学院深圳先进技术研究院 | Boron nitride doped composite material and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105385106B (en) * | 2015-12-02 | 2018-10-23 | 安捷利（番禺）电子实业有限公司 | A kind of preparation method of high heat conductivity insulation composite |
| CN107488251A (en) * | 2017-08-01 | 2017-12-19 | 广东工业大学 | A kind of aqueous polyurethane Heat Conduction Material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183889A (en) * | 2013-03-21 | 2013-07-03 | 上海交通大学 | High-thermal-conductivity and insulating polymer composite material and preparation method thereof |
| CN103725002A (en) * | 2013-12-27 | 2014-04-16 | 中国科学院深圳先进技术研究院 | Aluminum oxide composite material and preparation method thereof, and copper clad base plate |
| CN104610780A (en) * | 2015-01-12 | 2015-05-13 | 中国科学院宁波材料技术与工程研究所 | Modification method for silicon carbide particles |
| CN105349114A (en) * | 2015-10-27 | 2016-02-24 | 中国科学院深圳先进技术研究院 | Boron nitride doped composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Flexible polyimide films hybrid with functionalized boron nitride and graphene oxide simultaneously to improve thermal conduction and dimensional stability;Mei-Hui Tsai,et al.;《Applied Materials & Interfaces》;20140527;正文第8639-8645页 * |
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