CN111363381A - Surface functionalized BN nano-sheet and preparation method and application thereof - Google Patents
Surface functionalized BN nano-sheet and preparation method and application thereof Download PDFInfo
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Abstract
A surface functionalized BN nano-sheet and a preparation method and application thereof belong to the field of preparation and modification of BN nano-sheets. The preparation method of the surface functionalized BN nano-sheet comprises the following steps: mixing and grinding triton X-100 and BN nano-sheets uniformly, adding the mixture into an organic solvent, heating and stirring under a condensation reflux state, ultrasonically dispersing and stripping to obtain a surface functionalized BN nano-sheet suspension, and removing the solution to obtain the surface functionalized BN nano-sheet. TritonX-100 molecules on the surface of the BN nano-sheet in the surface functionalized BN nano-sheet can enable the BN nano-sheet to be more uniformly dispersed in a polymer matrix and also physically intertwined with polymer matrix molecules, so that the interaction of an intermediate interface between the surface functionalized BN nano-sheet and the polymer matrix is enhanced, and the interface modification obviously improves the mechanical property and the thermal conductivity of a modified polymer system.
Description
Technical Field
The invention relates to the technical field of preparation and modification of BN nano sheets, in particular to a surface functionalized BN nano sheet and a preparation method and application thereof.
Background
Due to their light weight, ease of processing, and low cost, polymer materials are now used to support and protect electronic products, and as modern electronic products evolve to faster speeds and frequencies, smaller sizes, and more functionality, heat dissipation has become a critical issue. Unfortunately, most polymeric materials do not have desirable thermal conductivity properties, for example, epoxy and silicone gels exhibit poor thermal conductivity properties and therefore do not meet the demand for rapid thermal conductivity in modern electronic products.
The heat conductive adhesive is one of polymer materials, and a method for improving the heat conductivity of the heat conductive adhesive is to add a filler with high heat conductivity into resin, wherein the filler with high heat conductivity is common carbon material (C), aluminum nitride (AlN) and aluminum oxide (Al)2O3) Carbon Silicide (SiC) and Boron Nitride (BN) powders. Although carbon materials can increase the thermal conductivity of polymers, such as graphene and carbon nanotubes, the target polymer is inevitably made electrically conductive, thereby affecting its application to electronic products. In the existing high-thermal-conductivity filler, Boron Nitride (BN) nanosheets are increasingly caused to be used in the preparation of polymer composite materials for heat dissipation due to low density, high thermal conductivity, electrical insulation, reaction passivation on acid and melt, excellent oxidation resistance and low friction coefficientMuch attention is paid.
With Boron Nitride (BN) nanoplates, on the one hand, it is considered that with decreasing BN nanoplate thickness, a more uniform dispersion can be achieved for a given fraction and volume of BN/polymer composite, resulting in higher thermal conductivity. On the other hand, in a certain fraction and volume of the polymer, the total number of BN nanosheets and their surface area increase as the thickness of the BN nanosheets decreases, and therefore, it is important to keep the BN nanosheets as thin as possible.
The existing preparation methods of BN nano-sheets include a method of adding an intercalation agent to perform intercalation stripping, a method of forming BN nano-sheets by ultrasonic treatment, and a method of performing functional modification by a chemical reagent (such as a silane coupling agent) to improve the dispersion degree, mechanical properties and thermal conductivity of the BN nano-sheets in a polymer, but the preparation methods have relatively complex process flows.
Disclosure of Invention
The invention aims to provide a surface functionalized BN nano sheet, a preparation method and an application thereof, wherein the surface functionalized BN nano sheet is a 3.41 +/-0.27 nm thick polyethylene glycol octyl phenyl ether (triton X-100) surface modified boron nitride nano sheet which can be used for a heat-conducting, electric-insulating and high-toughness epoxy adhesive, the BN nano sheet is subjected to functional modification, and simultaneously, the peeling of the BN nano sheet is realized, and the obtained surface functionalized BN nano sheet can obviously improve the heat conductivity, the electric insulation and the mechanical property of a subsequent application product, particularly the epoxy adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of a surface functionalized BN nano-sheet, which comprises the following steps:
(1) mixing and grinding polyethylene glycol octyl phenyl ether (triton X-100) and BN nanosheets uniformly to obtain a mixture; wherein, according to the liquid-solid ratio, polyethylene glycol octyl phenyl ether (triton X-100): BN nanosheet ═ 1-5) mL: (0.1-0.5) g, more preferably (1-1.2) mL: 0.1 g.
(2) Adding a mixture obtained by mixing and grinding polyethylene glycol octyl phenyl ether (triton X-100) and BN nano-sheets into an organic solvent, heating and stirring under a condensation reflux state, and performing ultrasonic dispersion and stripping to obtain a surface functionalized BN nano-sheet suspension, thereby finally obtaining the surface functionalized BN nano-sheets contained in the suspension.
In the step (2), the organic solvent is at least one of acetone, isopropanol, butanone, dichloromethane and cyclohexane.
In the step (2), according to the solid-liquid ratio, BN nanosheet: organic solvent ═ (0.1-0.5) g: (20-200) mL.
In the step (2), the heating temperature for heating and stirring is 50-60 ℃, and the heating time is 2-3 h.
In the step (2), the temperature of ultrasonic dispersion is less than or equal to 20 ℃, and the ultrasonic dispersion can promote the processed BN nanosheets to be stripped and dispersed into surface functionalized BN nanosheets; the ultrasonic frequency is 35-40 KHz.
The surface functionalized BN nano-sheet is prepared by adopting the method.
The thickness of the surface functionalized BN nano-flake is 3.41 +/-0.27 nm.
The surface functionalized BN nano-sheet is a product obtained by non-covalent functionalization of the surface of the BN nano-sheet by adopting polyethylene glycol octyl phenyl ether (triton X-100).
The surface functionalized BN nano-flake is used as a filler with high thermal conductivity to improve the thermal conductivity of a polymer material.
The method comprises the following steps: the modified BN/polymer nano composite material is prepared by mixing the surface functionalized BN nano flakes and the polymer matrix in an organic solvent and then removing the organic solvent.
The modified BN/polymer nano composite material, in particular to a modified BN/epoxy resin nano composite adhesive.
The method for preparing the modified BN/epoxy resin nano composite adhesive comprises the following steps:
step 1: uniformly mixing the obtained surface functionalized BN nano-sheet suspension with epoxy resin to obtain a BN/resin mixed solution;
step 2: removing the organic solvent in the BN/resin mixed solution, and degassing to obtain a mixture with the organic solvent removed;
and step 3: and cooling the mixture from which the organic solvent is removed, adding a curing agent, uniformly stirring, degassing again, and heating for curing to obtain the modified BN/epoxy resin nano composite adhesive.
In the step 1, the weight ratio of epoxy resin: surface functionalized BN nanosheets (10-80): 1.
in the step 3, the type and the adding amount of the curing agent are determined according to the type of the epoxy resin.
The prepared modified BN/epoxy resin nano composite adhesive has the thermal conductivity of 0.17-0.30WK-1m-1Volume resistivity of 3 × 1015-7.5×1015Omega.m, the glass transition temperature is 89-97 ℃; young modulus is 2.26-3.0 GPa; the fracture toughness is 248-one and 340 J.m2(ii) a The lap shear strength is 12.4-13.57MPa, the adhesive toughness is 125-197 J.m2。
Compared with pure epoxy resin, the thermal conductivity of the epoxy resin is improved by 68-73%; the glass transition temperature is improved by 15 to 17 percent; the Young modulus is improved by 20 to 25 percent; the fracture toughness is improved by 200-230%; the lap shear strength is improved by 22 to 26 percent; the adhesive toughness is improved by 320-350 percent.
Compared with the prior art, the surface functionalized BN nano-flake provided by the invention has the beneficial effects that:
(1) the surfactant TritonX-100 is used for non-covalent functionalization of the surface of the boron nitride nanosheet, so that the stripping and dispersion of BN are remarkably promoted, and the stripping and surface modification of the BN nanosheet are completed in one step.
(2) TritonX-100 molecules on the surface of the BN nano-sheet can enable the BN nano-sheet to be more uniformly dispersed in a polymer matrix and also physically intertwined with polymer matrix molecules, so that the interaction of an intermediate interface between the surface functionalized BN nano-sheet and the polymer matrix is enhanced, and the interface modification obviously improves the mechanical property and the thermal conductivity of a modified polymer system.
(3) The thickness of the surface functionalized BN nano-flake is 3.41 +/-0.27 nm, and the reduction of the thickness of the surface functionalized BN nano-flake improves the performance of the BN/epoxy resin adhesive because of two important factors influencing the performance of the polymer nano-composite material: the dispersibility of the reinforcing material is enhanced, and the interface interaction between the reinforcing material and the matrix is enhanced.
For the modified BN nanosheets with the same mass fraction, the thickness is reduced, and more uniform dispersion can be realized. The thickness is reduced, the total surface area is increased, and the modified BN nanosheet can form more interface phases with the base body.
Drawings
FIG. 1 is a process flow diagram of a preparation method of surface functionalized BN nano-flakes;
FIG. 2 is a flow chart of a process for preparing a modified BN/epoxy nanocomposite adhesive;
fig. 3 is a TGA diagram of prepared BN nanosheets and surface functionalized BN nanosheets;
fig. 4 is an atomic force microscope image of the prepared surface-functionalized BN nanosheets, wherein (a) is 3D and (b) is 2D.
Detailed Description
The contents of the surface functionalized BN nano-flake, the preparation method and the application thereof are explained in the following by combining the attached drawings and specific examples.
In the following examples, the adopted BN nano-sheet is a boron nitride nano-sheet which is a hexagonal crystal with a thickness of 30-50nm and a purity of more than 99.9 wt%; surfactant TritonX-100 (polyethylene glycol tert-octyl phenyl ether) is adopted; an epoxy resin (E-51); curing agent Jeff-amine D230(J230) all materials were used as received without further purification.
(1) A preparation method of surface functionalized BN nano-flake has a process flow diagram shown in figure 1, and comprises the following steps:
in the embodiment, TritonX-100 is used for modifying BN nano-sheets:
1) mixing 0.1-0.5gBN nanosheets and 1-5mL of triton X-100 in an agate grinding bowl, and manually grinding for 30-40min to obtain a mixture.
2) Adding a mixture obtained by mixing and grinding polyethylene glycol octyl phenyl ether (triton X-100) and BN nano-sheets into acetone, carrying out condensation reflux, reacting for 2-3h at the temperature of 50-60 ℃ under a stirring state to obtain a heated solution, and then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60-80min to obtain a surface functionalized BN nano-sheet suspension, wherein the suspension contains surface functionalized BN nano-sheets (m-BN).
3) Removing the organic solvent of the surface functionalized BN nano-flake suspension, carrying out thermogravimetric and simultaneous thermal analysis (TGA) on the prepared surface functionalized BN nano-flake, and according to a thermogravimetric and simultaneous thermal analysis (TGA) diagram (shown in figure 3), obtaining that triton X-100 successfully carries out functional modification on the BN nano-flake; the surface-functionalized BN nanosheets were subjected to atomic force microscopy analysis (see fig. 4) and calculated to have an average thickness of 3.41 ± 0.27 nm.
(2) The prepared surface functionalized BN nano slice is applied to preparing a modified BN/epoxy resin nano composite adhesive, and the steps are as follows:
1) preparing surface functionalized BN nano-sheets:
I. mixing 0.1-0.5gBN nanosheets and 1-5mL of triton X-100 in an agate grinding bowl, and manually grinding for 30-40min to obtain a mixture;
II, adding a mixture obtained by mixing and grinding polyethylene glycol octyl phenyl ether (triton X-100) and BN nano-sheets into acetone, carrying out condensation reflux, reacting for 2-3h at the temperature of 50-60 ℃ under a stirring state to obtain a heated solution, and carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60-80min to obtain a surface functionalized BN nano-sheet (m-BN) suspension.
2) The flow chart of the preparation process of the modified BN/epoxy resin nano composite adhesive is shown in figure 2:
uniformly mixing epoxy resin (E-51) and the surface functionalized BN nano-flake suspension by magnetic stirring for 20-30min and then carrying out ultrasonic treatment for 30-35min to obtain a BN/resin mixed solution; wherein, according to the mass ratio, the epoxy resin: surface functionalized BN nanosheets (10-80): 1.
the BN/resin mixture was evaporated with heating plate and magnetic stirring at 70-75 deg.c of acetone, and air bubbles and residual acetone were completely removed from the BN/resin mixture by vacuum degassing at 100 deg.c to obtain a mixture from which the organic solvent was removed.
After cooling the mixture from which the organic solvent was removed to 30 ℃, the curing agent J230 was added and stirred manually for 5-10 min. The resulting well-mixed mixture is then poured into a preheated mold and degassed in an oven for 5-10 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a modified BN/epoxy nanocomposite adhesive.
And analyzing the mechanical property of the prepared modified BN/epoxy resin nano composite adhesive.
The specific embodiment is as follows:
example 1
A preparation method of a modified BN/epoxy resin nano composite adhesive comprises the following steps:
(1) 0.2gBN nanosheets and 2mL triton X-100 were mixed in an agate milling bowl and milled manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 20mL of acetone, and reacting for 2h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 35 KHz.
(3) 3.5g of epoxy resin (E-51) and m-BN suspension are uniformly mixed by magnetic stirring for 20min and then ultrasonic treatment for 30min to obtain a BN/resin mixed solution.
The BN/resin mixture was then evaporated at 70 ℃ using a hot plate and magnetic stirring. Air bubbles and residual acetone were completely removed from the BN/resin mixture by vacuum degassing at 100 ℃ to obtain a mixture from which the organic solvent was removed.
After cooling the organic solvent-removed mixture to 30 ℃, 1.3g of curative J230 was added and stirred manually for 5 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a modified BN/epoxy nanocomposite adhesive.
In the prepared modified BN/epoxy resin nano-composite adhesive, the mass fraction of m-BN is 4 wt%, at the moment, the modified BN/epoxy resin nano-composite adhesive has the most excellent mechanical property, the Young modulus of the modified BN/epoxy resin nano-composite adhesive is 3.0GPa, and compared with pure epoxy resin (comparative example 1), the Young modulus of the modified BN/epoxy resin nano-composite adhesive containing 4 wt% of m-BN is increased by 25%. Fracture toughness K of modified BN/epoxy resin nano composite adhesive1cAnd critical stress energy release rate G1cRespectively from 0.325 +/-0.067 MPa.m of pure epoxy resin1/2And 49.75J.m-2Increased to 1.08MPa.m1/2And 347J.m-2。
Compared with the unmodified BN/epoxy resin nano composite adhesive, the Young modulus of the unmodified BN/epoxy resin nano composite adhesive is 2.63GPa, and the Young modulus of the modified BN/epoxy resin nano composite adhesive containing 4 wt% of m-BN is improved by 14%. Fracture toughness K of modified BN/epoxy resin nano composite adhesive1c0.75MPa.m of unmodified BN/epoxy resin nano composite adhesive1/2The critical stress energy release rate G of the modified BN/epoxy resin nano composite adhesive is improved by 44 percent1c236J.m from unmodified BN/epoxy nanocomposite adhesive-2The improvement is 47 percent.
Modified BN/epoxy nanocomposite adhesive at 4 wt% m-BN with thermal conductivity of 0.15 + -0.01 Wk from neat epoxy (comparative example 1)-1m-1Increase to 0.26 + -0.04 Wk-1m-1Thermal conductivity 0.22 + -0.03 Wk compared to unmodified BN/epoxy nanocomposite adhesive (comparative example 2)-1m-1There is a corresponding increase of 18.2% and a glass transition temperature of 4 wt% m-BN, from 83 ℃ for the neat epoxy (comparative example 1) to 97 ℃ which is also 5.4% higher than the 92 ℃ glass transition temperature of the unmodified BN/epoxy nanocomposite adhesive.
Example 2
A preparation method of a modified BN/epoxy resin nano composite adhesive comprises the following steps:
(1) 0.2gBN nanosheets and 2mL triton X-100 were mixed in an agate milling bowl and milled manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 30mL of acetone, and reacting for 2h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 40 KHz.
(3) 4.9g of epoxy resin (E-51) and m-BN suspension were mixed uniformly by magnetic stirring for 20min and then ultrasonic treatment for 30min to obtain a BN/resin mixed solution.
The BN/resin mixture was then evaporated at 70 ℃ using a hot plate and magnetic stirring. Air bubbles and residual acetone were completely removed from the BN/resin mixture by vacuum degassing at 100 ℃ to obtain a mixture from which the organic solvent was removed.
After cooling the organic solvent-removed mixture to 30 ℃, 1.715g of curative J230 was added and stirred manually for 5 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a modified BN/epoxy nanocomposite adhesive.
The mass fraction of m-BN in the prepared modified BN/epoxy resin nano composite adhesive is 3 wt%, compared with pure epoxy resin, the mechanical property of the modified BN/epoxy resin nano composite adhesive is improved: young's modulus of 2.86GPa and fracture toughness K1cIs 1.01MPa.m1/2Critical stress energy release rate G1cIs 328J.m-2。
Example 3
A preparation method of a modified BN/epoxy resin nano composite adhesive comprises the following steps:
(1) 0.1gBN nanosheets and 1mL triton X-100 were mixed in an agate grinding bowl and ground manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 25mL of acetone, and reacting for 2h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 38 KHz.
(3) 3.7g of epoxy resin (E-51) and m-BN suspension were mixed uniformly by magnetic stirring for 20min and then ultrasonic treatment for 30min to obtain a BN/resin mixed solution.
The BN/resin mixture was then evaporated at 70 ℃ using a hot plate and magnetic stirring. Air bubbles and residual acetone were completely removed from the BN/resin mixture by vacuum degassing at 100 ℃ to obtain a mixture from which the organic solvent was removed.
After cooling the organic solvent-removed mixture to 30 ℃, 1.295g of curative J230 was added and stirred manually for 5 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a modified BN/epoxy nanocomposite adhesive.
The mass fraction of m-BN in the prepared modified BN/epoxy resin nano composite adhesive is 2 wt%, compared with pure epoxy resin, the mechanical property of the modified BN/epoxy resin nano composite adhesive is improved: young's modulus of 2.67GPa and fracture toughness K1cIs 0.89MPa.m1/2Critical stress energy release rate G1cIs 298J.m-2。
Example 4
A preparation method of a modified BN/epoxy resin nano composite adhesive comprises the following steps:
(1) 0.1gBN nanosheets and 1mL triton X-100 were mixed in an agate grinding bowl and ground manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 40mL of acetone, and reacting for 2h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 35 KHz.
(3) 7.4g of epoxy resin (E-51) and m-BN suspension were mixed uniformly by magnetic stirring for 20min and then ultrasonic treatment for 30min to obtain a BN/resin mixed solution.
The BN/resin mixture was then evaporated at 70 ℃ using a hot plate and magnetic stirring. Air bubbles and residual acetone were completely removed from the BN/resin mixture by vacuum degassing at 100 ℃ to obtain a mixture from which the organic solvent was removed.
After cooling the organic solvent-removed mixture to 30 ℃, 2.59g of curative J230 was added and stirred manually for 5 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a modified BN/epoxy nanocomposite adhesive.
Example 5
A preparation method of a modified BN/epoxy resin nano composite adhesive comprises the following steps:
(1) 0.3gBN nanosheets and 3.5mL triton X-100 were mixed in an agate grinding bowl and ground manually for 35min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 80mL of isopropanol, and reacting for 3h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 36 KHz.
(3) By magnetic stirring for 20min and then ultrasonic treatment for 30min, 15g of epoxy resin (E-51) and m-BN suspension were uniformly mixed to obtain a BN/resin mixed solution.
The BN/resin mixture was then used to evaporate isopropanol using a hot plate and magnetic stirring at 75 ℃. The BN/resin mixture was completely freed from bubbles and residual isopropanol by vacuum degassing at 100 c to give a mixture with the organic solvent removed.
After cooling the organic solvent-removed mixture to 30 ℃, 5.25g of curative J230 was added and stirred by hand for 10 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a modified BN/epoxy nanocomposite adhesive.
Example 6
A preparation method of a modified BN/epoxy resin nano composite material comprises the following steps:
(1) 0.1gBN nanosheets and 1mL triton X-100 were mixed in an agate grinding bowl and ground manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 40mL of acetone, and reacting for 2h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 40 KHz.
(3) 7.4g of epoxy resin (E44) and m-BN suspension were mixed uniformly by magnetic stirring for 20min and then ultrasonic treatment for 30min to obtain a BN/resin mixed solution.
Then, 2.22g of curing agent J230 was added to the BN/resin mixture, stirred by hand for 5min, and acetone was evaporated at 70 ℃ using a hot plate and magnetic stirring. The modified BN/epoxy nanocomposite was obtained by vacuum degassing at 100 ℃ to completely remove air bubbles and residual acetone, followed by curing at 80 ℃ for 4h and then at 120 ℃ for 10 h.
Example 7
A preparation method of a modified BN/epoxy resin nano composite material comprises the following steps:
(1) 0.5gBN nanosheets and 5mL triton X-100 were mixed in an agate milling bowl and milled manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 200mL of isopropanol, and reacting for 2h under the conditions of condensation reflux and stirring at 60 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 15 ℃ for 80min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 35 KHz.
(3) 7.4g of epoxy resin (E44) and m-BN suspension were mixed uniformly by magnetic stirring for 30min and then ultrasonic treatment for 35min to obtain a BN/resin mixed solution.
Then 2.22g of curative J230 was added to the BN/resin mixture, stirred by hand for 10min and the isopropanol was evaporated at 75 ℃ using a hot plate and magnetic stirring. The modified BN/epoxy nanocomposite was obtained by vacuum degassing at 100 ℃ to completely remove air bubbles and residual isopropanol, followed by curing at 80 ℃ for 4h and then at 120 ℃ for 10 h.
Example 8
A preparation method of a modified BN/silicone rubber nano composite material comprises the following steps:
(1) 0.1gBN nanosheets and 1.2mL triton X-100 were mixed in an agate grinding bowl and ground manually for 30min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano sheets into 50mL of acetone, and reacting for 3h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 60min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 40 KHz.
(3) Stirring for 20min by magnetic force, then carrying out ultrasonic treatment for 30min, and uniformly mixing 10g of liquid silicone rubber and m-BN suspension to obtain a BN/silicone rubber mixed solution.
The BN/silicone rubber mixture was then evaporated at 70 ℃ using a hot plate and magnetic stirring. Air bubbles and residual acetone were completely removed from the BN/silicone rubber mixture by vacuum degassing at 100 ℃ to obtain an organic solvent-removed mixture.
After cooling the organic solvent-removed mixture to 30 ℃, 1g of a silicone rubber curing agent was added and stirred manually for 10 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h to give a modified BN/silicone rubber nanocomposite.
Example 9
A preparation method of a modified BN/silicone rubber nano composite material comprises the following steps:
(1) 0.4gBN nanosheets and 4mL triton X-100 were mixed in an agate milling bowl and milled manually for 40min to give a mixture.
(2) And adding a mixture obtained by mixing and grinding triton X-100 and BN nano-sheets into 100mL of butanone, and reacting for 3h under the conditions of condensation reflux and stirring at 50 ℃ to obtain a heated solution. And then carrying out ultrasonic treatment on the heated solution at the temperature of below 20 ℃ for 70min to obtain a uniformly dispersed surface functionalized BN nano sheet (m-BN) suspension, wherein the ultrasonic frequency is 35 KHz.
(3) Stirring for 30min by magnetic force, then carrying out ultrasonic treatment for 30min, and uniformly mixing 20g of liquid silicon rubber and m-BN suspension to obtain a BN/silicon rubber mixed solution.
The BN/silicone rubber mixture was then used to evaporate butanone at 75 ℃ using a hot plate and magnetic stirring. Air bubbles and residual butanone were completely removed from the BN/silicone rubber mixture by vacuum degassing at 100 ℃ to give a mixture with the organic solvent removed.
After cooling the organic solvent-removed mixture to 30 ℃, 2g of a silicone rubber curing agent was added and stirred manually for 10 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h to give a modified BN/silicone rubber nanocomposite.
Comparative example 1
0.998g of curing agent was directly added to 3.24g of epoxy resin (E-51), stirred well, and the resulting mixture was poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give a neat epoxy material.
Comparative example 2
A preparation method of an unmodified BN/epoxy resin nano composite adhesive comprises the following steps:
(1) adding 0.2gBN nanosheets into 20mL of acetone, and carrying out ultrasonic treatment at the temperature of below 20 ℃ for 60min to obtain the peeled BN nanosheet suspension, wherein the ultrasonic frequency is 35 KHz.
(2) Stirring by magnetic force for 20min, then carrying out ultrasonic treatment for 30min, and uniformly mixing 3.5g of epoxy resin (E-51) and the peeled BN nanosheet suspension to obtain an unmodified BN/resin mixed solution.
The unmodified BN/resin mixture was then subjected to evaporation of acetone at 70 ℃ using a hot plate and magnetic stirring. The air bubbles and residual acetone were completely removed from the unmodified BN/resin mixture by vacuum degassing at 100 ℃ to give a mixture with the organic solvent removed.
After cooling the organic solvent-removed mixture to 30 ℃, 1.3g of curative J230 was added and stirred manually for 5 min. The resulting well-mixed mixture was then poured into a preheated mold and degassed in an oven for 5 min. This process was then followed by curing at 80 ℃ for 4h, and then at 120 ℃ for 10h to give an unmodified BN/epoxy nanocomposite adhesive.
It should be understood that the above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and to embody the present invention, and not to limit the protection scope of the present invention by this means, and all equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A preparation method of surface functionalized BN nano-flake is characterized by comprising the following steps:
(1) mixing and grinding polyethylene glycol octyl phenyl ether and BN nanosheets uniformly to obtain a mixture; wherein, according to the liquid-solid ratio, the ratio of polyethylene glycol octyl phenyl ether: BN nanosheet ═ 1-5) mL: (0.1-0.5) g;
(2) adding a mixture obtained by mixing and grinding polyethylene glycol octyl phenyl ether and BN nanosheets into an organic solvent, heating and stirring the mixture in a condensation reflux state, and ultrasonically dispersing and stripping the mixture to obtain a surface functionalized BN nanosheet suspension, thereby finally obtaining the surface functionalized BN nanosheets contained in the suspension.
2. The method for preparing surface-functionalized BN nano-flakes according to claim 1, wherein in the step (2), the organic solvent is at least one of acetone, isopropanol, butanone, dichloromethane and cyclohexane.
3. The method for preparing surface functionalized BN nano-flake according to claim 1, wherein in the step (2), the ratio of BN nano-flake to BN nano-flake in solid-to-liquid ratio is as follows: organic solvent ═ (0.1-0.5) g: (20-200) mL.
4. The method for preparing surface-functionalized BN nano-flakes according to claim 1, wherein in the step (2), the heating temperature of the heating and stirring is 50-60 ℃ and the heating time is 2-3 h.
5. The method for preparing surface-functionalized BN nano-flake according to claim 1, wherein in the step (2), the temperature of ultrasonic dispersion is less than or equal to 20 ℃, and the ultrasonic frequency is 35-40 KHz.
6. A surface functionalized BN nanoplatelet produced by the method of any one of claims 1 to 5.
7. The surface-functionalized BN nanoplatelets of claim 6, wherein the surface-functionalized BN nanoplatelets have a thickness of 3.41 ± 0.27 nm.
8. Use of surface-functionalized BN nanosheets according to claim 6 or 7 as a high thermal conductivity filler to increase the thermal conductivity of a polymeric material.
9. The use of surface functionalized BN nanoplatelets according to claim 8 wherein the surface functionalized BN nanoplatelets are used to prepare a modified BN/polymer nanocomposite comprising the surface functionalized BN nanoplatelets and a polymer matrix, the surface functionalized BN nanoplatelets and the polymer matrix are mixed in an organic solvent and the organic solvent is then removed to obtain the modified BN/polymer nanocomposite.
10. The use of surface functionalized BN nanosheets as claimed in claim 9, wherein the modified BN/polymer nanocomposite is a modified BN/epoxy nanocomposite adhesive.
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