CN112209354B - Method for preparing hydrophobic hexagonal boron nitride nanosheets - Google Patents
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Abstract
The invention discloses a method for preparing a hydrophobic hexagonal boron nitride nanosheet, which comprises the following steps: (a) carrying out freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride to prepare expanded hydroxylated hexagonal boron nitride; (b) mixing and stirring the expanded hydroxylated hexagonal boron nitride prepared in the step (a) and a compound shown as a formula (I) in a first solvent in an anhydrous environment at the temperature of 60-78 ℃ to obtain a first mixed solution, adding an unsaturated acid and/or unsaturated anhydride and a second solvent into the obtained first mixed solution, and reacting at the temperature of 85-115 ℃ to prepare a hydrophobic hexagonal boron nitride nanosheet;
wherein R is C1‑6An alkyl of (a); the method not only can realize the stripping and hydrophobic modification one-pot method of the boron nitride nanosheets, but also can realize the high yield of the hydrophobic hexagonal boron nitride nanosheets.
Description
The invention relates to divisional application of Chinese patent application with the application date of 2019, 6 and 26, the application number of 2019105589922 and the name of 'a preparation method of a hydrophobic hexagonal boron nitride nanosheet'.
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for preparing a hydrophobic hexagonal boron nitride nanosheet.
Background
As a common material in industrial manufacturing, heat conductive material has been the research focus of the scientific community. Most of the traditional heat conducting materials are metal and oxide materials with good heat conductivity, but the metal and the oxide thereof are difficult to adapt to the actual use requirements due to poor electrical insulation, chemical corrosion resistance and forming process performance. The heat-conducting polymer material has excellent corrosion resistance, mechanical property, electrical insulation property, processability and the like, gradually replaces the traditional metal and oxide heat-conducting materials thereof, and is widely applied to the fields of electric power, electronics, LED illumination, solar energy, aerospace, national defense, military industry and the like, but most of pure polymer materials are poor heat conductors, so that the polymer needs to be modified, and the preparation of the high heat-conducting polymer from structural modification is difficult, so that the filling modification of the polymer by selecting the high heat-conducting inorganic filler is an effective way for preparing the polymer-based composite material.
The (002) crystal face of the hexagonal boron nitride (h-BN) presents a 2D ordered BN crystal structure and has a plurality of unique properties of a graphitized (002) plane, and when the hexagonal boron nitride is stripped into nano sheets (h-BNNS), the in-plane thermal conductivity of the h-BNNS is as high as 2000W/(m.k), and the hexagonal boron nitride has a plurality of unique characteristics, such as high thermal conductivity, high mechanical strength, high oxidation resistance, corrosion resistance, high thermal conductivity, high heat resistance, low thermal expansion coefficient, low electrical conductivity and the like, and is concerned, particularly, the BN nano sheets (BNNS) are a unique insulating 2D system and can be used as an insulating heat-conducting filler in a polymer matrix composite material.
Common methods for preparing Boron Nitride Nanosheets (BNNS) include a chemical vapor deposition method, a solid-phase synthesis method, a chemical stripping method, a liquid-phase ultrasonic-assisted stripping method, a mechanical stripping method and the like.
For example, Paffett et al (Surface science,1999,429(1): 229-; in 2010, Chatterjee S et al (Chemistry of materials f 2011, 23(20):4414-4416.) prepared 2-5 layers of boron nitride films on copper foil (Cu) on a large scale for the first time: by the hot catalytic vapor deposition method, a Cu substrate was first placed in the center of a tube furnace at Ar/H2Calcining at 600 deg.C for 20min under mixed gas atmosphere, and programming to 1000 deg.C, ammonia borane (NH)3-BH3) Blowing the reaction area by Ar-H gas flow, and forming few layers of boron nitride in 30-60 min; wang et al (Journal of the American Ceramic Society,2011, 94(12): 4496-; in the reaction, no catalyst is used, and ammonia borane (NH) is heated under the conditions of relatively mild atmosphere3BH3) And (3) preparing the nano sheet. Precursor NH3-BH3Gradually breaking the B-H, N-H bond in the heating and purging process, dehydrogenating to form a BN compound with a similar spherical structure, and expanding and releasing hydrogen at the high temperature of 1400 ℃ to form a few-layer BNNS; rao (The Journal of Physical Chemistry C,2009,113(34):15160-15165.) et al obtained small-scale BNNS by reacting boric acid and urea at 900 ℃ in a nitrogen atmosphere, and adjusting The mixing ratio of The two found that The thickness of The BNNS produced related to The ratio of urea to boric acid in The raw material increased, The thickness decreased and The product had poor crystallinity and The layered structure formed was incomplete.
The chemical deposition method or the solid phase deposition method both need higher synthesis temperature (more than 600 ℃) to obtain the BNNS with complete crystal form and have low stripping efficiency.
Also as Robinson et al (Nanoscale,2014,6(20):11671-11675.) Inspired by a preparation method (Hummers method) of graphene oxide, a sulfuric acid and nitric acid mixed acid system is adopted, boron nitride nanosheets are prepared by redox reaction, the obtained product can be stably dispersed in solvents such as ethanol, acetone, isopropanol and deionized water, and the stability of a dispersion liquid is related to the vulcanization modification effect in the stripping process, although the Hummers method can prepare the boron nitride nanosheets, the stripping efficiency is only 25% compared with the graphite stripping process. The Hucken university Hucken topic group (Crystegcomm, 2013,15(9):1782-2SO4Single acid system in KMnO4,H2O2With the action of (3), 65mg of nanosheet is obtained by stripping 1g of parent boron nitride powder, and the stripping efficiency is only 6.5%. HaO et al (Advanced Materials,2013,25(15): 2200-. Lin et al (Phys. chem. lett,2009,1(1):277-283.) modified stripping of boron nitride by using hydrophilic and oleophilic amine molecules, the obtained nanosheets can be stably dispersed in solvents such as tetrahydrofuran, water and the like, octadecylamine CODA or polyethylene glycol (PEG) is used as a modifier to strip boron nitride, and mainly depends on the interaction of Lewis acid and alkali on the surface of boron nitride.
However, the above-mentioned several chemical peeling methods achieve the peeling preparation of the nanosheets from different angles, but the peeling efficiency is not high as a whole.
For example, in the Zhi topic group (Advanced Materials,2009,21(21): 2889-2893), a strong polar solvent Dimethylformamide (DMF) is selected, liquid-phase ultrasonic stripping of the boron nitride nanosheets is realized by utilizing strong interaction of polar DMF molecules and the surface of BN, 0.01mg/mL of dispersion liquid is obtained, and finally, milligram-grade (0.5-1mg) nanosheets are obtained through centrifugal drying treatment. The size of the product is reduced compared with that of the initial sample, and most of the thickness is distributed in the range of 2-10 nm; in the subject group (ACS nano,2010,4(3):1299-1304.), the hexagonal boron nitride is stripped by using the methylbenzenesulfonic acid (MSA) as the dispersing agent for the first time, and research results show that the concentration of the dispersion obtained by stripping is only 0.3mg/mL due to the protonation effect between the BNNS and the MSA molecules, and the whole dispersion is orange; cao et al (Materials Express,2014,4(2):165-171 (7)) use ammonia/isopropanol two solvent method to realize the stripping from top to bottom, the stripping efficiency can only reach 20%, the isopropanol has the function of dispersant because the surface energy is matched with boron nitride; the ammonia molecules in the ammonia water are used as an electron donor, so that B atoms of boron nitride are easily attacked, and Lewis acid-base interaction is formed; lin et al (Journal of Physical Chemistry C,2011, 115(6):2678-2685.) broke the tradition, and water was used as a stripping dispersant without adding any surfactant, and effective stripping was achieved on hexagonal boron nitride which is generally considered hydrophobic through the action of ultrasound; based on the light base appearing at the edge when boron nitride is hydrolyzed, hydrophilic modification is carried out. And simultaneously, cutting the nano-sheets from the matrix powder by hydrolysis to peel off the nano-sheets and release ammonia gas, wherein the method can obtain water-soluble boron nitride nano-sheets, and electron microscope and atomic force microscope results show that the size of the boron nitride nano-sheets is generally reduced relative to the raw materials, the thickness of the boron nitride nano-sheets is generally about several atomic layers, but the peeling yield is only 0.05-0.1 mg/mL. However, the ultrasonic-assisted stripping method mostly selects expensive and partially toxic solvents, the concentration of the nanosheet dispersion is generally low, the stripping efficiency is not high, and the agglomeration is easy to occur in the subsequent treatment process.
For another example, in 2011, hexagonal boron nitride was used as a precursor in Alexey m.glushenkov task group (Journal of Materials Chemistry,2011, 21(32): 11862-11866), and a nanosheet with a reduced size and a good crystal form was prepared by mild shear force stripping. Benzyl benzoate (C) is selected14H12O2) As a wet grinding ingredient, the grinding ball impact is reduced to a certain extent and the pollution in the ball milling process is avoided. Similarly, Liu et al (Chemistry Letters,2013,42(11): 1415-1416) also use ball milling method to strip few-layer nanosheets, except that ammonia borane is used as ball milling agent and mixed with boron nitride powder according to a certain proportion, and finally thin-layer two-dimensional nanosheets with considerable yield are obtained. Furthermore, Lee et al (Nano letters,2X15,15(2):1238-The sodium oxide solution (NaOH) is improved, and the nano-sheets are prepared by stripping from the surface of parent boron nitride powder under the combined action of mechanical shearing force and chemical intercalation, and the stripping efficiency is only 18%. However, mechanical stripping methods, such as ball milling methods, have long production periods and unsatisfactory yield, although the ball milling pot has a simple process and is sealed to a certain extent so as to avoid the influence of air in the stripping process.
In conclusion, a simple method capable of producing high-quality boron nitride nanosheets/or modifying boron nitride nanosheets in a large scale is developed, so that the method has important significance for basic research of the boron nitride nanosheets and can powerfully promote the practical application of the boron nitride nanosheets.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel method for preparing hydrophobic hexagonal boron nitride nanosheets, which not only can realize the stripping and hydrophobic modification one-pot method of the boron nitride nanosheets, but also can realize the high yield of the hydrophobic hexagonal boron nitride nanosheets.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a hydrophobic hexagonal boron nitride nanosheet comprises the following steps:
(1) carrying out surface hydroxylation modification on the hexagonal boron nitride to prepare hydroxylated hexagonal boron nitride;
(2) carrying out freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride;
(3) mixing and stirring the expanded hydroxylated hexagonal boron nitride prepared in the step (2) and a compound shown in a formula (I) in a first solvent to obtain a first mixed solution, adding unsaturated acid and/or unsaturated anhydride and a second solvent into the obtained first mixed solution, and reacting to prepare the hydrophobic hexagonal boron nitride nanosheet;
According to some specific aspects of the present invention, in step (1), the hydroxylated hexagonal boron nitride is prepared by: mixing hexagonal boron nitride with a sodium hydroxide aqueous solution, and stirring and reacting at the temperature of 90-150 ℃ to prepare the boron nitride-based catalyst.
According to some specific aspects of the present invention, in the step (1), the hexagonal boron nitride is a commercially available product with a purity of 99% or more and a particle size of about 2 to 5 μm.
According to some specific and preferred aspects of the present invention, in the step (1), the temperature is achieved by means of heating by an oil bath.
According to some specific aspects of the invention, in the step (1), after the stirring reaction, a step of washing with distilled water is further included until the washing is neutral, and drying is performed to obtain the hydroxylated hexagonal boron nitride.
According to some preferred aspects of the present invention, in step (2), the freeze-thaw expansion process is operated in the following manner: preparing the hydroxylated hexagonal boron nitride prepared in the step (1) into an aqueous solution, freezing the obtained aqueous solution at a first set temperature, then unfreezing the aqueous solution to a second set temperature, and circularly freezing and unfreezing the aqueous solution for multiple times to prepare the expanded hydroxylated hexagonal boron nitride.
According to some preferred aspects of the present invention, in the step (2), the first set temperature is-50 to-5 ℃ and the second set temperature is 10 to 30 ℃. More preferably, the first set temperature is-45 to-15 ℃, and the second set temperature is 18 to 28 ℃.
According to some preferable aspects of the invention, in the step (2), the mass fraction of the aqueous solution is 5 to 20%.
According to some preferred aspects of the invention, in the step (2), the freezing time is 1-8 h.
According to some preferred aspects of the present invention, in the step (2), the number of the cycles is 4 to 12.
According to some specific and preferred aspects of the present invention, in step (3), R is methyl, ethyl, propyl, butyl or pentyl.
According to some preferred aspects of the present invention, in the step (3), the mixing and stirring are performed at a temperature of 60 to 78 ℃. More preferably, in the step (3), the mixing and stirring are carried out at a temperature of 65 to 75 ℃. In some embodiments of the present invention, the mixing and stirring may be performed by using ultrasonic waves, and the mixing and stirring may be performed under water bath heating to control the temperature.
According to some preferred aspects of the present invention, in the step (3), the reaction occurring in the second solvent is performed at a temperature of 80 to 120 ℃. More preferably, in the step (3), the reaction in the second solvent is performed at a temperature of 85 to 115 ℃.
According to some preferred aspects of the present invention, in step (3), the reaction occurring in the second solvent is carried out in the presence of an inert gas. The inert gas includes nitrogen, argon, and the like.
According to some preferred aspects of the present invention, in the step (3), the mixing and stirring are controlled to be performed in an anhydrous environment. In some embodiments of the present invention, the raw materials and the moisture in the environment can be separated by refluxing and water separation, so that the mixing and stirring can be carried out in a water-free environment.
According to some preferred aspects of the invention, in the step (3), the feeding mass ratio of the compound shown in the formula (I) to the expanded hydroxylated hexagonal boron nitride is 6-12: 1.
According to some preferred aspects of the invention, in the step (3), the feeding mass ratio of the unsaturated acid and/or unsaturated acid anhydride to the expanded hydroxylated hexagonal boron nitride is 0.05-0.5: 1.
According to some specific and preferred aspects of the present invention, in step (3), the first solvent is cyclohexane and the second solvent is ethyl acetate.
According to some specific and preferred aspects of the present invention, in the step (3), the unsaturated acid is linoleic acid and/or methacrylic acid, and the unsaturated acid anhydride is itaconic anhydride and/or maleic anhydride.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the preparation method, hydroxylated hexagonal boron nitride is subjected to freeze-thaw expansion treatment, and then the catalysis of stripping and esterification modification of boron nitride by combining a specific compound of formula (I) is performed, so that on one hand, stripping and hydrophobic modification are performed by a one-pot method without separating an intermediate, and meanwhile, the compound of formula (I) can be reused, so that the cost is greatly saved, on the other hand, the yield of the hydrophobic hexagonal boron nitride nanosheet is more than 57%, and further, industrial batch production can be realized, and therefore, the preparation method is favorable for application in the fields of high-thermal-conductivity glue, high-thermal-conductivity resin, high-thermal-conductivity insulating materials, high-thermal-conductivity plastics and the like.
Drawings
Fig. 1 is a Transmission Electron Micrograph (TEM) of hydrophobic hexagonal boron nitride nanoplates prepared in example 3, wherein the left and right are at different magnifications;
FIG. 2 is an Atomic Force Microscope (AFM) image of hydrophobic hexagonal boron nitride nanoplates prepared in example 3
Fig. 3 is an XRD spectrum of the hydrophobic hexagonal boron nitride nanosheet prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these examples are for the purpose of illustrating the general principles, essential features and advantages of the present invention, and the present invention is not limited by the following examples. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. The raw materials used in the examples are all commercially available commercial products.
In the following examples, all starting materials are essentially obtained commercially or prepared by conventional methods in the art, unless otherwise specified.
Example 1
Preparation of a compound of formula (Ia) (i.e. R is propyl in formula (I)): 15.8g (0.073mo1) of N-butylpyridinium bromide ([ bpy ] was weighed out]Br) and 8g (0.073mo1) (sodium tetrafluoroborate) NaBF4Adding 100mL acetone as solvent into a plastic washing bottle, magnetically stirring, condensing and refluxing at room temperature, reacting for 12h, standing, vacuum filtering, discardingRemoving white solid NaBr to obtain light yellow clear filtrate, adding 100mL dichloromethane into the light yellow clear filtrate, precipitating white precipitate, vacuum filtering, concentrating the filtrate by rotary evaporation to remove acetone and dichloromethane, and vacuum drying the obtained yellow oily liquid at 60 deg.C for 8 hr to obtain the product [ bpy ] shown in formula (Ia)]BF413.8g, yield 85.2%;
example 2
Preparation of a compound of formula (Ib) (i.e. R in formula (I) is methyl): 28.2g (0.15mol) of bromo-N-ethylpyridine were added to a Erlenmeyer flask containing 50mL of acetone, and 16.5g (0.15mol) of NaBF was added4Magnetically stirring for 10h at room temperature, filtering, performing rotary evaporation, removing volatile acetone, and vacuum drying to obtain white solid compound represented by formula (Ib) 25.16g, yield 86.5%, m.p.53.2-53.6 deg.C;
example 3
The embodiment provides a preparation method of a hydrophobic hexagonal boron nitride nanosheet, which comprises the following steps:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows:
preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of the compound shown in the formula (Ia) prepared in the example 1, putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 12g of linoleic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 100 ℃ for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 14.4g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs with a yield of 57.3%;
the yield is calculated as follows:
：mM-BNNSsthe obtained hydrophobic hexagonal boron nitride nanosheet (M-BNNSs) containing vinyl has the mass g; : wP-BNOHIs the mass g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH); n isP-BNOH: the surface hydroxyl content of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is mmol/g; mma: molecular weight of modifier (unsaturated acid or unsaturated anhydride), in this case linoleic acid: 280.44g/mol, calculated in the same manner as in the examples below.
The TEM image of the measured product is shown in FIGS. 1(a) (b) (c), a TEM image of single peeled M-BNNSs can be seen on a porous carbon grid, the transparent effect of single-layer M-BNNSs is shown, the transverse dimension of 2-3 mu M is shown, a coiling superposition image of side few-layer M-BNNSs is measured by adopting HRTEM (high definition transmission electron microscope) shown in FIG. 1(d), the coiling is caused by a 200KV electron microscope testing environment, the number of layers of the coiling of BNNS is clearly visible to be 7, and the single-layer or few-layer hydrophobic hexagonal boron nitride nanosheets M-BNNSs are proved to be obtained by the invention. As shown in fig. 2: a typical Atomic Force Microscope (AFM) image of M-BNNSs deposited on a mica substrate from an ethanol/water dispersion is shown, showing a flake height of 3nm, which also reveals the nature of the exfoliated M-BNNSs. The XRD pattern is measured to be the comparison pattern of the XRD of the original hexagonal boron nitride and the M-BNNSs, the diffraction peaks (002), (100), (101), (102), (004), (104), (110) and (112) shown in the figure are consistent with the XRD standard peaks of the hexagonal boron nitride, and the obtained hydrophobic hexagonal boron nitride nanosheet is proved to be free of other impurities. In addition, we can see from the figure that the (002) peak is shifted to a small angle direction and the peak is relatively enhanced, which all indicate that the modified hexagonal boron nitride (002) face after exfoliation is more exposed and the face spacing becomes larger, indicating that boron nitride has been well exfoliated.
Cooling the filtrate subjected to vacuum filtration to below 25 ℃, standing and layering for 4h, and performing simple rotary evaporation treatment on the lower layer liquid (namely the compound shown in the formula (Ia)), so that the lower layer liquid can be used as a stripping agent and a catalyst for the next cycle again, thereby being repeatedly used; the upper layer after standing and layering is a mixed solvent and can be recycled after vacuum distillation treatment.
Example 4
The embodiment provides a preparation method of a hydrophobic hexagonal boron nitride nanosheet, which comprises the following steps:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.4g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows:
preparing a 15% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.0g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be about 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) and the cyclohexane into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 218g of the compound shown in the formula (Ib) prepared in the example 2, putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 68 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 12g of linoleic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to 105 ℃ for 5 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering, adding the mixture into 500mL of the toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 14.5g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs with a yield of 57.7%.
Filtering under reduced pressure, cooling the filtrate to below 25 deg.C, standing for layering for 4 hr, and subjecting the lower layer liquid (i.e. compound shown in formula (Ib)) to simple rotary evaporation treatment to obtain stripping tablet and catalyst for the next cycle for reuse; the upper layer after standing and layering is a mixed solvent and can be recycled after vacuum distillation treatment.
Example 5
The embodiment provides a preparation method of a hydrophobic hexagonal boron nitride nanosheet, which comprises the following steps:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 120 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.8g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows:
preparing a 15% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.3g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of a self-made ionic liquid compound shown as a formula (Ia), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 4g of methacrylic acid and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to about 100 ℃, carrying out reflux reaction for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering, adding the mixture into 500mL of the toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 14.3g of the hydrophobic hexagonal boron nitride nanosheet M-BNNSs with a yield of 57.1%;
filtering under reduced pressure, cooling the filtrate to below 25 deg.C, standing for layering for 4h, and subjecting the lower layer liquid (i.e. compound shown in formula (Ia)) to simple rotary evaporation treatment to obtain intercalation agent and catalyst for the next cycle for reuse; the upper layer after standing and layering is a mixed solvent and can be recycled after vacuum distillation treatment.
Example 6
The embodiment provides a preparation method of a hydrophobic hexagonal boron nitride nanosheet, which comprises the following steps:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows:
preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 218g of a self-made ionic liquid compound shown as a formula (Ib), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 5g of itaconic anhydride and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to about 100 ℃, carrying out reflux reaction for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at 8000r/min, collecting the upper suspension, filtering, and oven drying (140 deg.C) to obtain 14.7g of hydrophobic hexagonal boron nitride nanosheet M-BNNSs with yield of 58.7%.
Filtering under reduced pressure, cooling the filtrate to below 25 deg.C, standing for layering for 4h, and subjecting the lower layer liquid (i.e. compound shown in formula (Ib)) to simple rotary evaporation treatment to obtain intercalation agent and catalyst for the next cycle for reuse; the upper layer after standing and layering is a mixed solvent and can be recycled after vacuum distillation treatment.
Example 7
The embodiment provides a preparation method of a hydrophobic hexagonal boron nitride nanosheet, which comprises the following steps:
(1) the method for preparing the hydroxylated hexagonal boron nitride by carrying out surface hydroxylation modification on the hexagonal boron nitride comprises the following specific implementation modes: adding 50g of hexagonal boron nitride (hBN with the purity of more than or equal to 99 percent and the particle size of 2-5 microns) into a 1000ml three-mouth reaction bottle, then adding the hexagonal boron nitride into a prepared 5mol/L sodium hydroxide aqueous solution, mechanically stirring for 10 hours under the oil bath heating condition at about 100 ℃, washing the obtained mixture with distilled water for multiple times until the filtrate is neutral, and drying to obtain 49.5g of hydroxylated hexagonal boron nitride (hBN-OH);
(2) performing freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride prepared in the step (1) to prepare expanded hydroxylated hexagonal boron nitride, wherein the specific implementation mode is as follows:
preparing a 10% distilled water solution from the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in the step (1), freezing the distilled water solution in a freezer at the temperature of about-25 ℃ for 5 hours, then unfreezing the distilled water solution to room temperature, and performing freeze-thaw cycle for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH), wherein the surface hydroxyl number of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) is determined to be 0.0209 mmol/g;
(3) taking 25g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2) and 250mL of cyclohexane, putting the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) into 1000mL of three-neck flask with a stirrer and a reflux water separator, heating the three-neck flask to reflux, gradually removing water in a system by a refluxing solvent, cooling the temperature to 80 ℃ when no water is evaporated in the reflux water separator, adding 237g of a self-made ionic liquid compound shown as a formula (Ia), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24 hours, then adding 4.5g of maleic anhydride and 50mL of ethyl acetate, introducing nitrogen, heating the mixture to about 100 ℃, carrying out reflux reaction for 4 hours, cooling the mixture to 65 ℃, carrying out vacuum filtration, cleaning a filter cake twice by using a toluene/acetone (1:1 volume ratio) mixed solution, then filtering the mixture, adding the mixture into 500mL of toluene/isopropanol mixed solution to form a micro-nano dispersion solution, centrifuging at 8000r/min, collecting the upper suspension, filtering, and oven drying (140 deg.C) to obtain 14.8g of hydrophobic hexagonal boron nitride nanosheet M-BNNSs with yield of 59.1%.
Filtering under reduced pressure, cooling the filtrate to below 25 deg.C, standing for layering for 4h, and subjecting the lower layer liquid (i.e. compound shown in formula (Ib)) to simple rotary evaporation treatment to obtain intercalation agent and catalyst for the next cycle for reuse; the upper layer after standing and layering is a mixed solvent and can be recycled after vacuum distillation treatment.
Comparative example 1
The steps (1) and (2) are the same as the embodiment 3, but the difference is that the step (3) is modified to be modified and stripped by adopting the conventional stripping agent polyethylene glycol, but the modified and stripped polyethylene glycol cannot be used as a catalyst in esterification hydrophobic modification, so that an intermediate hexagonal boron nitride nanosheet needs to be separated first, and then esterification hydrophobic modification is carried out with linoleic acid, specifically:
(3) taking 25g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in the step (2), adding 250mL of mixed solvent (toluene/cyclohexane is 1:1) into 1000mL of three-neck flask with a stirrer, heating to reflux, gradually removing water in the system from the refluxed solvent, cooling to 80 ℃ when no water is evaporated in a reflux water separator, adding 86g of polyethylene glycol (Mn is 400), putting the reactor into an ultrasonic cleaner, controlling the water temperature to be about 70 ℃, carrying out ultrasonic stirring reaction for 24h, cooling to 65 ℃, precipitating for 30min, and removing the solvent under reduced pressure;
(4) then adding 12g of linoleic acid into the obtained precipitate, adding 100mL of mixed solvent (toluene/cyclohexane is 1:1), introducing nitrogen, heating to about 120 ℃, carrying out reflux reaction for 8h, cooling to 65 ℃, carrying out vacuum filtration under reduced pressure, washing a filter cake twice by using toluene/acetone (1:1 volume ratio) mixed solution, then filtering, adding the filter cake into 500mL of toluene/isopropanol mixed solution to form micro-nano dispersion, carrying out centrifugal treatment at a rotating speed of 8000r/min, taking the upper suspension, filtering and drying (140 ℃) to obtain 9.0g of hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) (formula (IV-4)), wherein the yield is 35.8%.
The difference between the comparative example 1 and the invention is that the compound shown in the formula (I) of the invention is not used for stripping and esterification, so that two steps are needed for reaction and the synthesis time is doubled, and the obtained hydrophobic hexagonal boron nitride nanosheet not only has low yield, but also contains unmodified hexagonal boron nitride nanosheets in the product and is not easy to separate.
The above embodiments are merely illustrative of the technical concept 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 implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A method for preparing hydrophobic hexagonal boron nitride nanosheets, the method comprising the steps of:
(a) carrying out freeze-thaw expansion treatment on the hydroxylated hexagonal boron nitride to prepare expanded hydroxylated hexagonal boron nitride;
(b) mixing and stirring the expanded hydroxylated hexagonal boron nitride prepared in the step (a) and a compound shown as a formula (I) in a first solvent in an anhydrous environment at the temperature of 60-78 ℃ to obtain a first mixed solution, then adding an unsaturated acid and/or an unsaturated anhydride and a second solvent into the obtained first mixed solution, and reacting at the temperature of 85-115 ℃ to prepare the hydrophobic hexagonal boron nitride nanosheet;
2. A method of making hydrophobic hexagonal boron nitride nanoplates as described in claim 1, wherein the hydroxylated hexagonal boron nitride is made by the method of: mixing hexagonal boron nitride with a sodium hydroxide aqueous solution, and stirring and reacting at the temperature of 90-150 ℃ to prepare the boron nitride-based catalyst.
3. A method for preparing hydrophobic hexagonal boron nitride nanoplates as claimed in claim 1, wherein in step (a), the freeze-thaw expansion process is operated in the following manner: preparing hydroxylated hexagonal boron nitride into an aqueous solution, freezing the obtained aqueous solution at a first set temperature, then unfreezing the aqueous solution to a second set temperature, and circularly freezing and unfreezing the aqueous solution for multiple times to prepare the expanded hydroxylated hexagonal boron nitride.
4. A method for preparing hydrophobic hexagonal boron nitride nanosheets according to claim 3, wherein the first set temperature is in the range of-50 ℃ to-5 ℃ and the second set temperature is in the range of 10 ℃ to 30 ℃.
5. The method for preparing hydrophobic hexagonal boron nitride nanosheets according to claim 3, wherein the aqueous solution comprises 5-20% by mass, the freezing treatment time is 1-8 h, and the number of cycles is 4-12.
6. A method for preparing hydrophobic hexagonal boron nitride nanosheets according to claim 1, wherein in step (b) R is methyl, ethyl, propyl, butyl or pentyl.
7. A method for preparing hydrophobic hexagonal boron nitride nanoplates as claimed in claim 1, wherein in step (b), the reaction occurring in the second solvent is carried out in the presence of an inert gas.
8. A method for preparing hydrophobic hexagonal boron nitride nanosheets according to claim 1, wherein in step (b), the compound of formula (i) and the expanded hydroxylated hexagonal boron nitride are dosed in a mass ratio of 6-12: 1, and the unsaturated acid and/or unsaturated anhydride and the expanded hydroxylated hexagonal boron nitride are dosed in a mass ratio of 0.05-0.5: 1.
9. The method for preparing hydrophobic hexagonal boron nitride nanosheets according to claim 1, wherein in step (b), the mixing and stirring are carried out ultrasonically, and the anhydrous environment separates the raw materials and the moisture in the environment by way of refluxing and water splitting.
10. A method of making hydrophobic hexagonal boron nitride nanoplates as in claim 1, wherein in step (b), the first solvent is cyclohexane, the second solvent is ethyl acetate, the unsaturated acid is linoleic acid and/or methacrylic acid, and the unsaturated anhydride is itaconic anhydride and/or maleic anhydride.
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