CN111892753B - Preparation method of modified hexagonal boron nitride heat-conducting film - Google Patents
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- CN111892753B CN111892753B CN202010833213.8A CN202010833213A CN111892753B CN 111892753 B CN111892753 B CN 111892753B CN 202010833213 A CN202010833213 A CN 202010833213A CN 111892753 B CN111892753 B CN 111892753B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2307/00—Characterised by the use of natural rubber
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- 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
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- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention relates to a preparation method of a modified hexagonal boron nitride heat-conducting film, which comprises the following steps: 1) uniformly mixing boron nitride and ethanol in proportion, obtaining hexagonal Boron Nitride Nanosheets (BNNS) by an ultrasonic-assisted stripping method, 2) sequentially adding a coupling agent, a catalyst and Hyperbranched Polyamide (HPBA) into an ethanol solution of the boron nitride nanosheets to obtain h-BNNS-g-HPBA, 3) uniformly mixing the h-BNNS-g-HPBA with deproteinized natural rubber latex (DPNRL), and curing at room temperature to form a film. The modified hexagonal boron nitride heat-conducting film prepared by the invention can realize the uniform dispersion of hexagonal boron nitride nanosheets in deproteinized natural rubber latex and realize low sensitivity and high heat conductivity to a human body. By adopting the method, 30% of hexagonal boron nitride nanosheets can be filled in the deproteinized natural rubber, so that the composite material has high heat conductivity, simple and easy process and wide actual application range, and can be used in the fields of biomedical devices, electronic packaging and the like.
Description
Technical Field
The invention relates to the field of inorganic-organic composite materials, in particular to a preparation method of a modified hexagonal boron nitride heat-conducting film.
Background
In recent years, thermally conductive and electrically insulating materials have become increasingly important due to the miniaturization of electronic devices. Polymers have been extensively studied to determine effective thermal conductors due to their low cost, light weight, low electrical conductivity, corrosion resistance, and good processability. However, the thermal conductivity of the polymer is generally low, about 0.2W/(m · K) at room temperature, and cannot meet the heat dissipation requirement of the electronic device industry. An effective and widely used method to overcome this drawback is to add fillers with high thermal conductivity in the polymer matrix to obtain polymer composites with high thermal conductivity, while retaining the outstanding properties of the polymer. Hexagonal Boron Nitride (BN) is of particular interest for its unique physicochemical properties. The layered lattice structure of boron nitride has good lubricating property and is not wetted by most molten metal, glass and salt, so that the layered lattice structure of boron nitride has high chemical erosion resistance; it has high dielectric breakdown strength, high volume resistivity and good oxidation resistance. Based on these characteristics, it has wide application in the fields of optical storage, medical treatment, photocatalysis, photoelectric devices, electrical insulation and the like. Boron nitride also has high thermal conductivity and excellent high temperature resistance, combined with low density, making it a suitable candidate material for the latest electronics, communication equipment and lighting equipment.
The natural rubber is called as four major industrial raw materials, is an important strategic resource, is also related to the basic industry of the national civilization, and has irreplaceability. Deproteinized natural rubber is widely used for manufacturing various products such as adhesive tapes, medical hoses, etc. due to its excellent biocompatibility and high elasticity. However, the low thermal conductivity of deproteinized natural rubber limits its application in the field of heat dissipation.
Currently, boron nitride particles produced on an industrial scale are still plate-like. Considering that the plate-shaped boron nitride has low filling density, is unevenly dispersed and is easy to agglomerate in the deproteinized natural rubber, so that a heat conduction path cannot be effectively established in the polymer matrix, and the heat conduction performance of the material is seriously influenced. Therefore, the boron nitride nanosheets can be subjected to grafting modification, so that the hexagonal boron nitride can be uniformly dispersed in the deproteinized natural rubber matrix, an effective heat conduction path is constructed, and the use performance of the material is improved.
Aiming at the problems, the technical problem solved by the invention is to carry out ultrasonic-assisted stripping and grafting of hyperbranched polyamide on hexagonal boron nitride, so that uniform dispersion of the hexagonal boron nitride in deproteinized natural rubber latex is realized, a good heat conduction path is formed in the composite material, the heat conductivity is improved, and the process steps are optimized.
Disclosure of Invention
The invention provides a preparation method of a modified hexagonal boron nitride heat-conducting film, which comprises the steps of taking hexagonal boron nitride and deproteinized natural rubber latex as raw materials, obtaining a hexagonal boron nitride nanosheet through an ultrasonic-assisted stripping method, grafting hyperbranched polyamide and curing at room temperature to form a film so as to prepare the modified hexagonal boron nitride heat-conducting film; the preparation method comprises the following steps:
(1) uniformly mixing hexagonal boron nitride and ethanol in a certain mass ratio, performing ultrasonic treatment and centrifugal dispersion to obtain supernatant, and placing the supernatant in a beaker A;
(2) mixing a coupling agent, ethanol and distilled water in a beaker B, and pre-hydrolyzing for a period of time;
(3) pouring the solution in the B into a beaker A, continuing ultrasonic treatment and mechanical stirring, putting into a vacuum oven, heating, drying and grinding to obtain a coupling agent modified hexagonal boron nitride nanosheet C;
(4) uniformly mixing the C and acetone according to a certain mass ratio, gradually adding hyperbranched polyamide and a catalyst, heating, drying and grinding after the reaction is finished to obtain h-BNNS-g-HPBA;
(5) and uniformly mixing the h-BNNS-g-HPBA and the deproteinized natural rubber latex according to a certain proportion, pouring the mixture into a polystyrene culture dish, and curing at room temperature to form a film to obtain the modified hexagonal boron nitride heat-conducting film.
Preferably, in the step (1), the mass ratio of the hexagonal boron nitride to the ethanol is 1:10, the coupling agent is KH-550, the ultrasonic treatment time is 2-3h, the ultrasonic power is 500-.
Preferably, in the step (2), the mass ratio of KH-550 to ethanol to distilled water is (0.1-0.2) to 50: 1, and the pre-hydrolysis lasts for 1-2 h.
Preferably, the ultrasonic treatment in the step (3) is carried out for 2-3h, the ultrasonic power is 500-600W, the oven temperature is 90-120 ℃, and the drying time is 24-48 h.
Preferably, in the step (4), the catalyst is p-toluenesulfonic acid, the mass ratio of the BNNS modified by KH550 to the acetone to the hyperbranched polyester to the p-toluenesulfonic acid is 1:10 to (0.01-0.02), the oven temperature is 90-120 ℃, and the drying time is 24-48 h.
Preferably, in the step (5), h-BNNS-g-HPBA: DPNRL = (0-2.33): 1 is cured at room temperature for 24-48h, and then at 70 ℃ for 12-24 h.
Preferably, the particle size of the hexagonal boron nitride nanosheet prepared by the ultrasonic-assisted mechanical stripping method is 100-500 nm.
The invention has the beneficial effects that:
(1) the hexagonal boron nitride is stripped under the assistance of ultrasonic, and the water dispersibility of the hexagonal boron nitride is improved. The hyperbranched polyamide is grafted, so that uniform dispersion and filling of the hexagonal boron nitride nanosheets in the deproteinized natural rubber matrix are realized, and the filling amount can reach 30%. When the filling amount of the hexagonal boron nitride nanosheet reaches 30%, the thermal conductivity of the modified hexagonal boron nitride heat-conducting film reaches 1.69W/(m.K), which is 8 times of that of deproteinized natural rubber;
(2) the modified hexagonal boron nitride heat-conducting film prepared by the invention takes hexagonal boron nitride, hyperbranched polyamide and deproteinized natural rubber as raw materials, and has good biocompatibility, simple preparation process and little environmental pollution.
Drawings
FIG. 1, examples 1-7 are histograms of thermal conductivity of modified hexagonal boron nitride thermally conductive films
Detailed Description
The invention is further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1.
(1) Weighing 10g of hexagonal boron nitride and 100ml of ethanol, putting the hexagonal boron nitride and the 100ml of ethanol into a beaker, uniformly mixing, carrying out ultrasonic treatment for 2 hours, centrifuging to obtain a supernatant, adding 0.1gKH550, 50ml of ethanol and 1ml of distilled water into the other beaker, uniformly mixing, carrying out prehydrolysis for 1 hour, mixing the solutions in the two beakers together, mechanically stirring and carrying out ultrasonic treatment for 2 hours, and drying and grinding to obtain the KH550 modified hexagonal boron nitride nanosheet. Weighing 2gKH550 modified hexagonal boron nitride nanosheets and 20ml of acetone, uniformly mixing, dropwise adding 0.01g of hyperbranched polyamide and 0.01g of p-toluenesulfonic acid, magnetically stirring for 2h, ending the reaction, washing, drying and grinding to obtain h-BNNS-g-HPBA.
(2) Weighing 0g h-BNNS-g-HPBA in the step (1), adding the weighed solution into deproteinized natural rubber emulsion with the solid content of 2.0g, magnetically stirring the solution at 400rpm for 30min to uniformly mix the solution, pouring the mixed solution into a polystyrene culture dish, curing the mixed solution at room temperature for 24 hours, and curing the mixed solution at 70 ℃ for 18 hours to obtain the modified hexagonal boron nitride heat-conducting film with the h-BNNS-g-HPBA filling amount of 0.
Examples 2-7 were prepared in the same manner as in example 1 except that the amounts of h-BNNS-g-HPBA and deproteinized natural rubber latex were changed so that the mass percentages of h-BNNS-g-HPBA in the modified hexagonal boron nitride heat conductive film were 5%, 10%, 15%, 20%, 25%, 30%, respectively, and the components in examples 2-7 were as shown in table 1. The thermal conductivity of examples 1-7 are shown in figure 1.
TABLE 1 EXAMPLES 2-7 tables of ingredients
| h-BNNS-g-HPBA/g | Deproteinized natural rubber latex solid content/g | |
| Example 2 | 0.1 | 1.9 |
| Example 3 | 0.2 | 1.8 |
| Example 4 | 0.3 | 1.7 |
| Example 5 | 0.4 | 1.6 |
| Example 6 | 0.5 | 1.5 |
| Example 7 | 0.6 | 1.4 |
Claims (6)
1. A preparation method of a modified hexagonal boron nitride heat-conducting film is characterized by comprising the following steps: the modified hexagonal boron nitride heat-conducting film is prepared by taking hexagonal boron nitride, hyperbranched polyamide and deproteinized natural rubber as raw materials, grafting the hyperbranched polyamide on the surface of the hexagonal boron nitride and curing at room temperature to form a film; the preparation method comprises the following steps:
(1) uniformly mixing hexagonal boron nitride and ethanol in a certain mass ratio, performing ultrasonic treatment and centrifugal dispersion to obtain supernatant, and placing the supernatant in a beaker A;
the particle size of the hexagonal boron nitride nanosheet prepared by the ultrasonic-assisted mechanical stripping method is 100-500 nm;
(2) mixing a coupling agent, ethanol and distilled water in a beaker B, and pre-hydrolyzing for a period of time;
(3) pouring the solution in the B into a beaker A, continuing ultrasonic treatment and mechanical stirring, putting into a vacuum oven, heating, drying and grinding to obtain a coupling agent modified hexagonal boron nitride nanosheet C;
(4) uniformly mixing the C and acetone according to a certain mass ratio, gradually adding hyperbranched polyamide and a catalyst, heating, drying and grinding after the reaction is finished to obtain h-BNNS-g-HPBA;
(5) and uniformly mixing the h-BNNS-g-HPBA and the deproteinized natural rubber latex according to a certain proportion, pouring the mixture into a polystyrene culture dish, and curing at room temperature to form a film to obtain the modified hexagonal boron nitride heat-conducting film.
2. The preparation method of the modified hexagonal boron nitride heat-conducting film as claimed in claim 1, wherein the mass ratio of the hexagonal boron nitride to the ethanol in the step (1) is 1:10, the ethanol concentration is 95%, the coupling agent is KH-550, the ultrasonic treatment time is 2-3h, the ultrasonic power is 500-600W, the centrifugal rotation speed is 4000-6000rpm, and the centrifugal time is 10-20 min.
3. The preparation method of the modified hexagonal boron nitride heat-conducting film according to claim 1, wherein in the step (2), the mass ratio of KH-550 to ethanol to distilled water is (0.1-0.2) to 50: 1, and the pre-hydrolysis is carried out for 1-2 h.
4. The preparation method of the modified hexagonal boron nitride heat-conducting film as claimed in claim 1, wherein the ultrasonic treatment in the step (3) is performed for 2-3h with ultrasonic power of 500-600W, the oven temperature of 90-120 ℃ and the drying time of 24-48 h.
5. The preparation method of the modified hexagonal boron nitride heat-conducting film according to claim 1, wherein the catalyst in the step (4) is p-toluenesulfonic acid, the mass ratio of the KH550 modified BNNS to the acetone to the hyperbranched polyester to the p-toluenesulfonic acid is 1:10 to (0.01-0.02), the acetone concentration is 99.5%, the oven temperature is 90-120 ℃, and the drying time is 24-48 h.
6. The method for preparing a modified hexagonal boron nitride thermal conductive film according to claim 1, wherein in the step (5), h-BNNS-g-HPBA: DPNRL (0-2.33) to 1 is cured at room temperature for 24-48h, and then at 70 ℃ for 12-24 h.
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| CN113969040B (en) * | 2021-11-29 | 2023-09-12 | 浙江元盛塑业股份有限公司 | Modified boron nitride/epoxy resin heat conduction composite material and preparation method thereof |
| CN115418100A (en) * | 2022-09-01 | 2022-12-02 | 浙江元盛塑业股份有限公司 | Method for preparing high-thermal-conductivity PA66 composite material by using hyperbranched polyamide |
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