CN110724320B - Heat-conducting rubber composite material and preparation method thereof - Google Patents
Heat-conducting rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heat-conducting rubber composite material and a preparation method thereof, wherein the composite material comprises 100 parts by mass of a rubber matrix, 50-400 parts by mass of metal ion modified inorganic heat-conducting filler and 1-5 parts by mass of a vulcanizing agent. The preparation method of the metal ion modified inorganic heat-conducting filler comprises the following steps: dissolving inorganic heat-conducting particles into a tannic acid aqueous solution, dripping a ferric trichloride solution into the tannic acid aqueous solution, then adjusting the pH value of the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface to 6.0-10 and 0 by adopting trihydroxymethyl aminomethane, adding the inorganic heat-conducting particle aqueous solution into a silver ammonia solution, adding a glucose solution under the stirring condition, and reacting at room temperature to obtain the metal ion modified inorganic heat-conducting filler. The invention not only has high heat-conducting property, high dielectric constant and excellent physical and mechanical properties, but also has the advantages of simple operation, mild reaction conditions, low cost, economy and environmental protection, and is suitable for the field of electronic devices.
Description
Technical Field
The invention relates to the field of heat-conducting rubber, in particular to a heat-conducting rubber composite material and a preparation method thereof.
Background
With the rapid development of science and technology, electronic components tend to be more and more integrated and miniaturized, and the problem to be faced is how to dissipate the heat generated by the electronic components due to the increase of the operating power, and the high dielectric property necessary for the electronic components is also considered. The rubber matrix has good physical and mechanical properties and chemical stability, but has poor thermal conductivity, so that the thermal conductivity of the rubber matrix is improved by filling a high thermal conductivity inorganic filler or a metal filler. However, the interface compatibility between the inorganic filler with high thermal conductivity and the rubber matrix is poor, which affects the improvement of the thermal conductivity of the composite material to a certain extent, while the cost of the metal filler is high, which can also seriously reduce the insulation performance of the composite material, so that the thermal conductive filler with low cost needs to be prepared, which not only has good compatibility with the rubber matrix, but also can effectively improve the thermal conductivity of the composite material.
The Chinese patent application with the application number of 201910509565.5 discloses a polypropylene composite material filled with a core-shell structure heat-conducting filler, wherein flaky amino modified boron nitride is adopted to coat the surface of spherical epoxy modified aluminum oxide to form the core-shell structure heat-conducting filler, and the core-shell structure heat-conducting filler is filled into a polypropylene matrix to prepare the high heat-conducting composite material. However, the preparation method of the core-shell structure heat-conducting particle is complex, and the reaction process is harsh and tedious, which is not beneficial to industrial practical application.
The Chinese patent application with the application number of 201710340700.9 discloses a method for improving the heat and electricity conductivity of a polyvinylidene fluoride composite material by chemical silver plating, and provides a method for improving the heat and electricity conductivity of the polyvinylidene fluoride composite material by chemical silver plating. Although the method is beneficial to improving the heat conduction and electric conductivity of the composite material, the preparation method has complicated steps and strict reaction conditions.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the heat-conducting rubber composite material and the preparation method thereof, which not only have high heat-conducting property, high dielectric constant and excellent physical and mechanical properties, but also have the advantages of simple operation, mild reaction conditions, low cost, economy and environmental protection, and are suitable for the field of electronic devices.
The purpose of the invention is realized by the following technical scheme:
a heat-conducting rubber composite material comprises a rubber matrix, metal ion modified inorganic heat-conducting filler and a vulcanizing agent, wherein:
100 parts by mass of a rubber substrate,
1 to 5 parts by mass of a vulcanizing agent,
50-400 parts by mass of metal ion modified inorganic heat-conducting filler.
Preferably, the preparation method of the metal ion modified inorganic heat-conducting filler comprises the following steps:
step A, adding inorganic heat-conducting particles into a tannic acid aqueous solution to obtain an inorganic heat-conducting particle aqueous solution with a tannic acid layer deposited on the surface;
b, dripping a ferric trichloride solution into the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid layer to obtain the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating;
and step C, regulating the pH value of the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface to 6.0-10, 0 by adopting trihydroxymethyl aminomethane, then adding the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface into a silver ammonia solution, adding a glucose solution under the stirring condition, reacting at room temperature, and filtering, washing and drying after the reaction is stopped to obtain the metal ion modified inorganic heat-conducting filler.
Preferably, the rubber matrix is natural rubber, silicone rubber, acrylate rubber, ethylene propylene diene monomer or nitrile rubber.
Preferably, the vulcanizing agent is a sulfur system vulcanizing agent or an organic peroxide system vulcanizing agent; the sulfur system vulcanizing agent is one of sulfur, zinc oxide and stearic acid; the organic peroxide system vulcanizing agent is one of di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
A preparation method of a heat-conducting rubber composite material comprises the following steps:
step A, adding inorganic heat-conducting particles into a tannic acid aqueous solution to obtain an inorganic heat-conducting particle aqueous solution with a tannic acid layer deposited on the surface;
b, dripping a ferric trichloride solution into the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid layer to obtain the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating;
step C, regulating the pH value of the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating to 6.0-10, 0 by adopting trihydroxymethyl aminomethane, then adding the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating into a silver ammonia solution, adding a glucose solution under the stirring condition, reacting at room temperature, and filtering, washing and drying after the reaction is stopped to prepare the metal ion modified inorganic heat-conducting filler;
and D, adding 50-400 parts by mass of the metal ion modified inorganic heat-conducting filler into 100 parts by mass of the rubber matrix, adding 1-5 parts by mass of a vulcanizing agent, and carrying out vulcanization crosslinking to obtain the heat-conducting rubber composite material.
Preferably, in the step a, the inorganic heat conducting particles are dissolved in 30-80 g/L aqueous solution of tannic acid, and stirred at room temperature at a stirring speed of 600-1000 r/min for 1-2 h, so as to obtain the aqueous solution of inorganic heat conducting particles with the tannic acid layer deposited on the surface.
Preferably, in the step B, the concentration of the ferric trichloride solution is 10-20 g/L.
Preferably, in step C, the method for preparing the silver ammonia solution comprises: and titrating the silver nitrate solution with the concentration of 10-30 g/L by using ammonia water until the precipitate just disappears to obtain the silver ammonia solution.
Preferably, in the step C, the inorganic heat conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating is added into a silver-ammonia solution, a glucose solution with a concentration of 20-60 g/L is added under a stirring condition, the mixture is stirred and reacted for 1-4 hours at a stirring speed of 600-1000 r/min at room temperature, and after the reaction is stopped, the mixture is filtered, washed and dried, so that the metal ion modified inorganic heat conducting filler is prepared.
Preferably, in the step D, 100 parts by mass of the rubber matrix is mixed in an open mill at 20-50 ℃, 50-400 parts by mass of the metal ion-modified inorganic heat-conducting filler and 1-5 parts by mass of the vulcanizing agent are gradually added, the mixture is uniformly mixed and then placed for 8 hours, and then the vulcanization crosslinking is performed on a flat vulcanizing machine, so as to obtain the heat-conducting rubber composite material.
According to the technical scheme provided by the invention, the preparation method of the heat-conducting rubber composite material provided by the invention has the advantages that the adsorbability of tannic acid is utilized to tightly coat inorganic heat-conducting particles, and meanwhile, due to the chelation of the tannic acid and metal ions, the tannic acid and iron ions can generate metal ion complexes within 10-20 s, so that a tannic acid-iron ion complex coating is formed on the surface of the inorganic heat-conducting particles; placing the inorganic heat-conducting particles coated with the tannic acid-iron ion complex compound coating in a silver-ammonia solution, and adding a reducing agent glucose solution to ensure that silver ions are uniformly and effectively reduced on the surface of the inorganic heat-conducting particles to form the metal ion modified inorganic heat-conducting filler. The inorganic heat-conducting filler modified by the metal ions is filled into the rubber matrix, and can be uniformly distributed in the rubber matrix, so that the agglomeration phenomenon is reduced, and the inorganic heat-conducting filler modified by the metal ions has good interface binding force with the rubber matrix, a compact heat-conducting network is formed, and the heat-conducting coefficient of the composite material is improved; meanwhile, the silver particles in the metal ion modified inorganic heat-conducting filler can effectively improve the dielectric constant of the composite material, and finally the heat-conducting rubber composite material with excellent physical and mechanical properties is obtained. The method has the advantages of simple operation, mild reaction conditions, rapid reaction time, low cost, economy and environmental protection, can obtain the heat-conducting rubber composite material with more excellent performance under the same cost condition, and is suitable for the field of electronic devices.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The heat conductive rubber composite material and the preparation method thereof provided by the present invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
A thermally conductive rubber composite may include a rubber matrix, a metal ion-modified inorganic thermally conductive filler, and a vulcanizing agent, wherein:
100 parts by mass of a rubber substrate,
1 to 5 parts by mass of a vulcanizing agent,
50-400 parts by mass of metal ion modified inorganic heat-conducting filler.
Specifically, the thermally conductive rubber composite may include the following embodiments:
(1) the rubber substrate can be made of natural rubber, silicon rubber, acrylate rubber, ethylene propylene diene monomer or nitrile rubber.
(2) The vulcanizing agent is a sulfur system vulcanizing agent or an organic peroxide system vulcanizing agent; the sulfur system vulcanizing agent is one of sulfur, zinc oxide and stearic acid; the organic peroxide system vulcanizing agent is one of bis (4-methylbenzoyl) Peroxide (PMB), dibenzoyl peroxide (BPO), dicumyl peroxide (DCP) and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane (DBPMH, also called bis-2, 5).
(3) The inorganic heat-conducting filler can adopt aluminum oxide (Al)2O3) Aluminum nitride (AlN), Boron Nitride (BN), silicon nitride (Si)3N4) One of (1); the average particle size of the inorganic heat-conducting filler is 100 nm-3 mu m, and the average thickness of the tannin-metal ion complex coating on the surface of the inorganic heat-conducting filler is 1-4 nm.
Further, the preparation method of the heat-conducting rubber composite material can comprise the following steps:
step A, adding inorganic heat-conducting particles into a tannic acid aqueous solution with the concentration of 30-80 g/L, and stirring at the room temperature at the stirring speed of 600-1000 r/min for 1-2 h to obtain the inorganic heat-conducting particle aqueous solution with the tannic acid layer deposited on the surface. In practical application, the inorganic heat-conducting particles can adopt aluminum oxide (Al)2O3) Aluminum nitride (AlN), Boron Nitride (BN), silicon nitride (Si)3N4) And the average particle diameter of the inorganic heat-conducting particles is 100nm to 3 μm.
And B, dripping a ferric trichloride solution with the concentration of 10-20 g/L into the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid layer to obtain the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating.
And step C, regulating the pH value of the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface to 6.0-10 and 0 by adopting trihydroxymethyl aminomethane, then adding the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface into a silver ammonia solution, adding a glucose solution with the concentration of 20-60 g/L under the stirring condition, stirring and reacting for 1-4 h at the stirring speed of 600-1000 r/min at the room temperature, and filtering, washing and drying after the reaction is stopped to obtain the metal ion modified inorganic heat-conducting filler. The preparation method of the silver ammonia solution comprises the following steps: and titrating the silver nitrate solution with the concentration of 10-30 g/L by using ammonia water until the precipitate just disappears to obtain the silver ammonia solution.
And D, mixing 100 parts by mass of the rubber matrix on an open mill at 20-50 ℃, gradually adding 50-400 parts by mass of the metal ion modified inorganic heat-conducting filler and 1-5 parts by mass of a vulcanizing agent, standing for 8 hours after uniform mixing, and then carrying out vulcanization crosslinking on a flat vulcanizing machine, thereby obtaining the heat-conducting rubber composite material of the metal ion modified inorganic heat-conducting filler. The heat conductivity coefficient of the heat-conducting rubber composite material is 3.35-5.50W/mK, the dielectric constant is 7.33-20.81, the elastic modulus is 2.81-4.68, and the elongation at break is 321-865%.
According to the preparation method of the heat-conducting rubber composite material, inorganic heat-conducting particles react with a tannic acid aqueous solution to prepare an inorganic heat-conducting particle aqueous solution with a tannic acid layer deposited on the surface, and iron ions rapidly react with tannic acid due to the adsorption effect and the reducibility of a catechol structure and a pyrogallol group on the surface of the tannic acid and the chelation property of the tannic acid and metal ions, so that a tannic acid-iron ion complex coating is generated on the surface of the inorganic heat-conducting particles, and further silver particles can uniformly and stably grow on the surface of the tannic acid-iron ion complex coating to form the metal ion modified inorganic heat-conducting filler; the reaction time of the inorganic heat conducting particles with the tannic acid layer deposited on the surface and the iron ions is very short, only 10-20 s is needed, and favorable conditions are provided for the distribution and growth of silver ions. The inorganic heat-conducting filler modified by metal ions can be uniformly distributed in the rubber matrix, so that the agglomeration phenomenon is reduced, and the inorganic heat-conducting filler has good interface binding force with the rubber matrix, so that a compact heat-conducting network is formed, and the heat-conducting coefficient of the composite material is improved. Meanwhile, the silver particles also effectively improve the dielectric constant of the composite material, and finally the composite material with excellent physical and mechanical properties is obtained. The method has the advantages of mild reaction conditions, rapid reaction time, more excellent performance under the same cost condition, simple and convenient operation, economy and environmental protection, and is suitable for the field of electronic devices.
In conclusion, the embodiment of the invention has the advantages of high heat-conducting property, high dielectric constant, excellent physical and mechanical properties, simple operation, mild reaction conditions, low cost, economy and environmental protection, and is suitable for the field of electronic devices.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the following detailed description of the heat conductive rubber composite material and the preparation method thereof provided by the embodiments of the present invention are provided in specific embodiments.
Example 1
A preparation method of the heat-conducting rubber composite material can comprise the following steps:
step a, taking 100mL of 30g/L tannic acid aqueous solution, adding 5g of alumina particles (adopting the alumina particles as inorganic heat conducting particles) with the particle size of 100nm, and stirring at room temperature at a stirring speed of 600r/min for 1h to obtain the inorganic heat conducting particle aqueous solution with the tannic acid layer deposited on the surface.
And b, dripping a ferric trichloride solution with the concentration of 10g/L into the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid layer, and stirring for 10s to obtain the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating.
And c, regulating the pH value of the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface to 9.0 by adopting trihydroxymethyl aminomethane, and performing suction filtration, washing and vacuum drying after 1min to obtain the heat-conducting particles with the tannic acid-iron ion complex coating coated with the aluminum oxide.
D, titrating in a silver nitrate solution with the concentration of 20g/L by using ammonia water until the precipitate just disappears to obtain a silver-ammonia solution; adding the heat conducting particles coated with the aluminum oxide by the tannic acid-iron ion complex coating into 100mL of the silver-ammonia solution, adding 100mL of glucose solution with the concentration of 30g/L under the stirring condition, stirring and reacting for 1h at the temperature of 25 ℃ at the stirring speed of 600-1000 r/min, filtering after the reaction is stopped, washing with deionized water to be neutral, and then drying in vacuum to obtain the metal ion modified inorganic heat conducting filler.
And e, plasticating 100 parts by mass of nitrile rubber (adopting the nitrile rubber as a rubber matrix) on a double-roll open mill at room temperature, gradually adding 100 parts by mass of the metal ion modified inorganic heat-conducting filler into the nitrile rubber, gradually adding 2 parts by mass of dicumyl peroxide (adopting the dicumyl peroxide as a vulcanizing agent), and beating and uniformly mixing the mixture in a triangular bag for multiple times to obtain the rubber compound. And standing the mixed rubber for 8 hours after uniform mixing, then carrying out vulcanization crosslinking on the mixed rubber on a flat vulcanizing machine, setting the pressure of the flat vulcanizing machine to be 15MPa, and vulcanizing at 160 ℃ for 90min to obtain the metal ion modified alumina particle heat-conducting rubber composite material.
Specifically, in the heat-conductive rubber composite material prepared in embodiment 1 of the present invention, 100 parts by mass of the rubber matrix, 100 parts by mass of the metal ion-modified inorganic heat-conductive filler, and 2 parts by mass of the vulcanizing agent are included.
Example 2
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: boron nitride particles are used as inorganic heat conducting particles instead of alumina particles, and natural rubber is used as a rubber matrix instead of nitrile rubber; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 3
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: the concentration of the aqueous solution of the tannic acid in the step a is 80 g/L; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 4
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: in the step d, the concentration of silver nitrate is 30g/L, and the concentration of a glucose solution is 40 g/L; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 5
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: in the step e, the dosage of dicumyl peroxide is 5 parts by mass; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 5 parts by mass of a vulcanizing agent are adopted.
Example 6
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: the using amount of the inorganic heat-conducting filler modified by the metal ions in the step e is 400 parts by mass; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 400 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are added.
Example 7
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 2 of the present invention, and is characterized in that: the particle size of the boron nitride particles is 3 μm; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 8
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 2 of the present invention, and is characterized in that: stirring the aqueous solution of the tannic acid and the boron nitride particles in the step a for 1 h; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 9
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 2 of the present invention, and is characterized in that: d, stirring for 3 hours after the glucose solution is added in the step d; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 10
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 2 of the present invention, and is characterized in that: dibenzoyl peroxide is adopted to replace dicumyl peroxide as a vulcanizing agent; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 11
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 2 of the present invention, and is characterized in that: the using amount of the inorganic heat-conducting filler modified by the metal ions in the step e is 400 parts by mass; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 400 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are added.
Example 12
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: aluminum nitride particles are used as inorganic heat conducting particles instead of aluminum oxide particles, and silicon rubber is used as a rubber matrix instead of nitrile rubber; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Example 13
A heat-conducting rubber composite material, which is basically the same as the preparation method of embodiment 1 of the present invention, and is characterized in that: silicon nitride particles are used as inorganic heat-conducting particles instead of aluminum oxide particles, and acrylate rubber is used as a rubber matrix instead of nitrile rubber; in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 100 parts by mass of a metal ion-modified inorganic heat-conducting filler and 2 parts by mass of a vulcanizing agent are adopted.
Comparative example 1
Nitrile rubber without any added high thermal conductive filler particles.
Comparative example 2
A heat-conducting rubber composite material, similar to the preparation method of embodiment 2 of the present invention, is different in that: step a, step b, step c and step d are not needed, and 100 parts by mass of unmodified boron nitride particles are adopted to replace 100 parts by mass of metal ion modified inorganic heat-conducting filler in step e, so that 100 parts by mass of a rubber matrix, 100 parts by mass of unmodified boron nitride particles and 2 parts by mass of a vulcanizing agent in the finally prepared heat-conducting rubber composite material.
Comparative example 3
A heat-conducting rubber composite material, similar to the preparation method of embodiment 2 of the present invention, is different in that: step a, step b, step c and step d are not needed, and in step e, 400 parts by mass of unmodified boron nitride particles are adopted to replace 100 parts by mass of metal ion modified inorganic heat-conducting filler, so that in the finally prepared heat-conducting rubber composite material, 100 parts by mass of a rubber matrix, 400 parts by mass of unmodified boron nitride particles and 2 parts by mass of a vulcanizing agent are adopted.
Comparative example 4
A heat-conductive rubber composite material, similar to the preparation method of embodiment 13 of the present invention, is different in that: step a, step b, step c and step d are not needed, and 100 parts by mass of unmodified silicon nitride particles are adopted to replace 100 parts by mass of metal ion modified inorganic heat-conducting filler in step e, so that 100 parts by mass of a rubber matrix, 100 parts by mass of unmodified silicon nitride particles and 2 parts by mass of a vulcanizing agent in the finally prepared heat-conducting rubber composite material.
Performance detection
The following tests of thermal conductivity, dielectric properties and tensile properties were performed on the above inventive examples 1 to 13 and comparative examples 1 to 4:
(1) the heat conductivity coefficients of the materials of examples 1 to 13 of the present invention and comparative examples 1 to 4 were respectively measured using a DXF-500 model thermal conductivity meter of TA corporation, and the results are shown in table 1 below.
(2) The materials of examples 1 to 13 of the present invention and comparative examples 1 to 4 were tested at room temperature, 1 to 10 respectively, using a German Novocontrol Alpha-A impedance meter6The dielectric constant in the frequency range of Hz, and thus the dielectric constant at 1kHz for each material, is shown in table 1 below.
(3) According to the national standard GB/T528-2009, a microcomputer-controlled electronic universal tester with the model number of American Instron 3366 is adopted to test the stress-strain curves of the materials in the above-mentioned examples 1-13 of the invention and comparative examples 1-4 respectively, the elongation at break is obtained from the stress-strain curves, and the elastic modulus is calculated, and the test results are shown in the following table 1.
TABLE 1
As can be seen from table 1: the inorganic heat-conducting filler modified by metal ions is filled in the rubber matrix, so that the heat conductivity coefficient of the heat-conducting rubber composite material can be remarkably improved, the maximum value of the heat conductivity coefficient is 5.50W/mK, the dielectric constant of the heat-conducting rubber composite material is as high as 20.87, the excellent mechanical property is maintained, and the heat-conducting rubber composite material can be widely applied to the field of microelectronics.
In conclusion, the embodiment of the invention has the advantages of high heat-conducting property, high dielectric constant, excellent physical and mechanical properties, simple operation, mild reaction conditions, low cost, economy and environmental protection, and is suitable for the field of electronic devices.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The heat-conducting rubber composite material is characterized by comprising a rubber matrix, metal ion modified inorganic heat-conducting filler and a vulcanizing agent, wherein:
100 parts by mass of a rubber substrate,
1 to 5 parts by mass of a vulcanizing agent,
50-400 parts by mass of metal ion modified inorganic heat-conducting filler;
the preparation method of the metal ion modified inorganic heat-conducting filler comprises the following steps:
step A, adding inorganic heat-conducting particles into a tannic acid aqueous solution to obtain an inorganic heat-conducting particle aqueous solution with a tannic acid layer deposited on the surface;
b, dripping a ferric trichloride solution into the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid layer to obtain the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating;
and step C, regulating the pH value of the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface to 6.0-10, 0 by adopting trihydroxymethyl aminomethane, then adding the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface into a silver ammonia solution, adding a glucose solution under the stirring condition, reacting at room temperature, and filtering, washing and drying after the reaction is stopped to obtain the metal ion modified inorganic heat-conducting filler.
2. The heat-conducting rubber composite material as claimed in claim 1, wherein the rubber matrix is natural rubber, silicone rubber, acrylate rubber, ethylene propylene diene monomer rubber or nitrile rubber.
3. The heat-conductive rubber composite material according to claim 1 or 2, wherein the vulcanizing agent is a sulfur-system vulcanizing agent or an organic peroxide-system vulcanizing agent; the sulfur system vulcanizing agent is one of sulfur, zinc oxide and stearic acid; the organic peroxide system vulcanizing agent is one of di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
4. The preparation method of the heat-conducting rubber composite material is characterized by comprising the following steps of:
step A, adding inorganic heat-conducting particles into a tannic acid aqueous solution to obtain an inorganic heat-conducting particle aqueous solution with a tannic acid layer deposited on the surface;
b, dripping a ferric trichloride solution into the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid layer to obtain the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating;
step C, regulating the pH value of the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating to 6.0-10, 0 by adopting trihydroxymethyl aminomethane, then adding the inorganic heat-conducting particle aqueous solution with the surface deposited with the tannic acid-iron ion complex coating into a silver ammonia solution, adding a glucose solution under the stirring condition, reacting at room temperature, and filtering, washing and drying after the reaction is stopped to prepare the metal ion modified inorganic heat-conducting filler;
and D, adding 50-400 parts by mass of the metal ion modified inorganic heat-conducting filler into 100 parts by mass of a rubber matrix, adding 1-5 parts by mass of a vulcanizing agent, and carrying out vulcanization crosslinking to obtain the heat-conducting rubber composite material as claimed in any one of claims 1-3.
5. The method for preparing the heat-conducting rubber composite material as claimed in claim 4, wherein in the step A, the inorganic heat-conducting particles are dissolved in the tannic acid aqueous solution with the concentration of 30-80 g/L, and stirred at the stirring speed of 600-1000 r/min for 1-2 h at room temperature, so as to obtain the inorganic heat-conducting particle aqueous solution with the tannic acid layer deposited on the surface.
6. The preparation method of the heat-conducting rubber composite material as claimed in claim 4 or 5, wherein in the step B, the concentration of the ferric trichloride solution is 10-20 g/L.
7. The method for preparing a heat conductive rubber composite material according to claim 4 or 5, wherein in the step C, the method for preparing the silver ammonia solution comprises: and titrating the silver nitrate solution with the concentration of 10-30 g/L by using ammonia water until the precipitate just disappears to obtain the silver ammonia solution.
8. The preparation method of the heat-conducting rubber composite material as claimed in claim 4 or 5, wherein in the step C, the inorganic heat-conducting particle aqueous solution with the tannic acid-iron ion complex coating deposited on the surface is added into the silver ammonia solution, the glucose solution with the concentration of 20-60 g/L is added under the stirring condition, the stirring reaction is carried out at the stirring speed of 600-1000 r/min for 1-4 h under the room temperature condition, and after the reaction is stopped, the inorganic heat-conducting filler modified by the metal ions is obtained by filtering, washing and drying.
9. The preparation method of the heat-conducting rubber composite material according to claim 4 or 5, wherein in the step D, 100 parts by mass of the rubber matrix is mixed on an open mill at 20-50 ℃, 50-400 parts by mass of the metal ion modified inorganic heat-conducting filler and 1-5 parts by mass of a vulcanizing agent are gradually added, the mixture is uniformly mixed and then placed for 8 hours, and then vulcanization crosslinking is performed on a flat vulcanizing machine, so that the heat-conducting rubber composite material is obtained.
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