CN113416334B - Hydroxyethyl cellulose/boron nitride nano composite film and preparation method thereof - Google Patents
Hydroxyethyl cellulose/boron nitride nano composite film and preparation method thereof Download PDFInfo
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- CN113416334B CN113416334B CN202110780173.XA CN202110780173A CN113416334B CN 113416334 B CN113416334 B CN 113416334B CN 202110780173 A CN202110780173 A CN 202110780173A CN 113416334 B CN113416334 B CN 113416334B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a hydroxyethyl cellulose/boron nitride nano composite film and a preparation method thereof, wherein the method comprises the following steps: carrying out liquid phase ball milling on hydroxyethyl cellulose solution and boron nitride, wherein the mass ratio of the hydroxyethyl cellulose to the boron nitride in the hydroxyethyl cellulose solution is (0.6-2.5): (1-5) obtaining a hydroxyethyl cellulose/boron nitride composite solution; the hydroxyethyl cellulose/boron nitride composite solution is dried to obtain the hydroxyethyl cellulose/boron nitride nano composite film, the hydroxyethyl cellulose which is low in price, biodegradable and water-soluble is selected as a stripping agent, the structural integrity of the boron nitride nano sheet is protected by the high viscosity of the hydroxyethyl cellulose, so that BNNs can be protected in liquid phase ball milling, the BNNs can also be used as a substrate of a composite material, the time is short, an organic solvent is not used, and the composite film has high mechanical property and strong heat conductivity.
Description
Technical Field
The invention relates to the technical field of preparation of sheet nano materials, in particular to a hydroxyethyl cellulose/boron nitride nano composite film and a preparation method thereof.
Background
Boron Nitride Nanosheets (BNNS) have excellent heat conduction, high temperature resistance, friction reduction, wear resistance and other properties, and are widely applied to the fields of material science, electronic devices and the like as reinforcing agents, heat-conducting fillers and electric conduction agents.
The preparation method of the boron nitride nanosheet mainly comprises a chemical vapor deposition method, a hydrothermal method and a mechanical auxiliary stripping method, wherein the BNNS prepared by the vapor deposition method has high cost, harsh preparation conditions and low yield; the strong cavitation of ultrasound in the mechanical auxiliary stripping method can cause defects on the surface layer of the boron nitride nanosheet, and the boron nitride nanosheet prepared by the method has fewer surface functional groups and is easy to agglomerate when directly compounded with a polymer. Therefore, the finding of an efficient, environment-friendly and energy-saving BNNS preparation method is of great significance.
At present, researchers grow melamine molecular chains in boron nitride lamella, increase the distance between layers, reduce the Van der Waals force between layers, and then strip the layers by using liquid phase ball milling, so that the melamine modified boron nitride nanosheet can be prepared. The obtained BNNS can be compounded with a polymer to prepare a high-thermal-conductivity composite material, but an organic solvent with higher cost is used in the preparation process, the preparation period is longer, and the industrial application of the modified boron nitride nanosheet is influenced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the hydroxyethyl cellulose/boron nitride nano composite film and the preparation method thereof, which have the advantages of short time, no use of organic solvent, high mechanical property and strong heat conductivity.
The invention is realized by the following technical scheme:
a preparation method of hydroxyethyl cellulose/boron nitride nano composite film comprises the following steps:
carrying out liquid phase ball milling on a hydroxyethyl cellulose solution and boron nitride, wherein the mass ratio of the hydroxyethyl cellulose to the boron nitride in the hydroxyethyl cellulose solution is (0.6-2.5): (1-5) obtaining a hydroxyethyl cellulose/boron nitride composite solution;
and drying the hydroxyethyl cellulose/boron nitride composite solution to obtain the hydroxyethyl cellulose/boron nitride nano composite film.
Preferably, the mass fraction of the hydroxyethyl cellulose solution is 3-5%.
Further, the hydroxyethyl cellulose solution is obtained by the following process:
firstly, swelling hydroxyethyl cellulose in deionized water for 1-12 h, and then stirring the obtained mixed system to obtain the hydroxyethyl cellulose solution.
And further, stirring for 1-5 hours.
Further, the hydroxyethyl cellulose solution and the boron nitride are subjected to liquid phase ball milling through grinding beads, and the mass ratio of the hydroxyethyl cellulose solution to the grinding beads is 1 (30-50).
Further, the liquid phase ball milling is carried out for 6-36 hours under the condition of 300-500 revolutions per minute.
Preferably, the boron nitride is hexagonal boron nitride.
Preferably, the hydroxyethyl cellulose/boron nitride composite solution is dried for 12-24 hours at the temperature of 40-60 ℃.
A hydroxyethyl cellulose/boron nitride nano composite film obtained by the preparation method of the hydroxyethyl cellulose/boron nitride nano composite film.
Further, the hydroxyethyl cellulose/boron nitride nano composite film is formed by stacking boron nitride together, wherein the distance between every two adjacent boron nitride is 3-5 nm, and the longitudinal dimension is 3-5 nm.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a hydroxyethyl cellulose/boron nitride nano composite film, which selects low-cost, biodegradable and water-soluble hydroxyethyl cellulose as a stripping agent, and utilizes the high viscosity of the hydroxyethyl cellulose to protect the structural integrity of boron nitride nano sheets, so that BNNs can be protected in liquid phase ball milling and can also be used as a substrate of a composite material; in the process of stripping boron nitride, hydroxyethyl cellulose molecules are inserted between boron nitride nanosheets, hydroxyethyl cellulose is adsorbed to the surface layers of the boron nitride nanosheets through the van der Waals force and the action of hydrogen bonds to form the hydroxyethyl cellulose modified boron nitride nanosheets, then the modified boron nitride nanosheets and the hydroxyethyl cellulose are fully compounded through the action of the hydrogen bonds, and then the HEC/BNNS composite film is prepared by utilizing a template pouring method, so that the time required for preparing the composite material is shortened, an organic solvent is not used, and the environment-friendly requirement is met. The hydroxyethyl cellulose which is low in price, biodegradable and water-soluble is selected.
Drawings
FIG. 1 is an SEM image of BNNs stripped with HEC assistance in example 1 of the invention.
FIG. 2 is an SEM image of HEC/BNNs composite material of example 1.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method of a hydroxyethyl cellulose/boron nitride nano composite film, which comprises the following specific steps:
(1) dissolving hydroxyethyl cellulose (HEC) in deionized water, standing and swelling for 1-12 h to ensure that water molecules fully enter the hydroxyethyl cellulose to ensure that the hydroxyethyl cellulose is well dispersed, and stirring for 1-5 h to prepare a hydroxyethyl cellulose solution with the mass fraction of 3-5%;
(2) placing 20 g-50 g of the hydroxyethyl cellulose solution obtained in the step (1) into a 100ml, 200ml or 500ml agate, corundum or stainless steel grinding tank, adding grinding beads, wherein the mass ratio of the hydroxyethyl cellulose solution to the grinding beads is 1 (30-50), adding 1 g-5 g of boron nitride, performing liquid phase ball milling for 6 h-36 h under the condition of 300-500 r/min, and performing auxiliary stripping on the boron nitride by using the hydroxyethyl cellulose, wherein the hexagonal boron nitride is selected in the embodiment;
(3) and (3) introducing 10 g-20 g of the hydroxyethyl cellulose/boron nitride composite solution in the preparation step (2) into a polytetrafluoroethylene or organic glass grinding tool with the diameter of 8 cm-10 cm, and drying in an oven at 40-60 ℃ for 12-24 h to obtain the hydroxyethyl cellulose/boron nitride composite film.
As shown in figure 1, a TEM image of BNNs is obtained, the hydroxyethyl cellulose/boron nitride composite film is centrifuged for multiple times to separate the BNNs at the bottom layer, a freeze drying or vacuum drying method is adopted to obtain the BNNs, the collected solid powder is used as SEM, the BNNs with few layers are observed to be stacked together, the transverse dimension is about 200nm, and the longitudinal dimension is 3-5 nm.
As shown in fig. 2, which is a fracture surface SEM image of the hydroxyethyl cellulose/boron nitride nanocomposite film, BNNs are uniformly distributed in the mixed system.
The hydroxyethyl cellulose/boron nitride composite film prepared by one-step forming has high mechanical property and strong heat conduction property, the tensile strength is 10-50 MPa, the heat conduction coefficient is as high as 3W/(m.K) -7W/(m.K), the tensile strength adopts national standard GB/T1040.3-2006, a sample is cut into strips of 10mm x 40mm, the strips are stretched at the speed of 5mm/min at room temperature, and the heat conduction coefficient adopts a hot-disk method.
Example 1
The invention relates to a preparation method of a hydroxyethyl cellulose/boron nitride nano composite film, which comprises the following specific steps:
(1) dissolving hydroxyethyl cellulose in deionized water, standing, wetting and swelling for 1h, and stirring for 5h to prepare a 3% solution;
(2) putting 20g of the hydroxyethyl cellulose solution obtained in the step (1) into a 100ml agate grinding tank, adding grinding beads in a mass ratio of 1:30, and then adding 1g of hexagonal boron nitride to perform liquid phase ball milling for 6 hours under the condition of 300 revolutions per minute;
(3) and (3) introducing 10g of the hydroxyethyl cellulose/boron nitride composite solution in the preparation step (2) into a polytetrafluoroethylene grinding tool with the diameter of 8cm, and placing the polytetrafluoroethylene grinding tool in an oven to dry for 12 hours at 40 ℃ to successfully prepare the composite film.
The hydroxyethyl cellulose/boron nitride composite material prepared by one-step molding has high mechanical property and heat conductivity, the tensile strength is 11MPa, and the heat conductivity coefficient is as high as 3W/(m.K).
Example 2
The invention relates to a preparation method of a hydroxyethyl cellulose/boron nitride nano composite film, which comprises the following specific steps:
(1) dissolving hydroxyethyl cellulose in deionized water, standing, moistening and swelling for 4 hours, and stirring for 4 hours to prepare a 3% solution;
(2) putting 30g of hydroxyethyl cellulose solution obtained in the step (1) into a 200ml corundum grinding tank, adding grinding beads in a mass ratio of 1:40, and then adding 2g of hexagonal boron nitride to perform liquid phase ball milling for 12 hours under the condition of 400 revolutions per minute;
(3) and (3) introducing 10g of the hydroxyethyl cellulose/boron nitride composite solution obtained in the preparation step (2) into a polytetrafluoroethylene grinding tool with the diameter of 8cm, and drying the polytetrafluoroethylene grinding tool in an oven at 45 ℃ for 18 hours to successfully prepare the composite film.
The hydroxyethyl cellulose/boron nitride composite material prepared by one-step molding has high mechanical property and heat conductivity, the tensile strength is 20MPa, and the heat conductivity coefficient is up to 4W/(m.K).
Example 3
The invention relates to a preparation method of a hydroxyethyl cellulose/boron nitride nano composite film, which comprises the following specific steps:
(1) dissolving hydroxyethyl cellulose in deionized water, standing, wetting and swelling for 8h, and stirring for 3h to prepare a 5% solution;
(2) putting 50g of hydroxyethyl cellulose solution obtained in the step (1) into a 500ml stainless steel grinding tank, adding grinding beads in a mass ratio of 1:50, and then adding 4g of hexagonal boron nitride to perform liquid phase ball milling for 24 hours under the condition of 500 revolutions per minute;
(3) and (3) introducing 20g of the hydroxyethyl cellulose/boron nitride composite solution obtained in the preparation step (2) into an organic glass grinding tool with the diameter of 10cm, placing the organic glass grinding tool in an oven, and drying for 24 hours at the temperature of 60 ℃ to successfully prepare the composite film.
The hydroxyethyl cellulose/boron nitride composite material prepared by one-step molding has high mechanical property and heat conductivity, the tensile strength is 40MPa, and the heat conductivity coefficient is up to 6W/(m.K).
Example 4
The invention relates to a preparation method of a hydroxyethyl cellulose/boron nitride nano composite film, which comprises the following specific steps:
(1) dissolving hydroxyethyl cellulose in deionized water, standing, wetting and swelling for 12h, and stirring for 1h to prepare a 5% solution;
(2) putting 40g of hydroxyethyl cellulose solution obtained in the step (1) into a 100ml agate grinding tank, adding grinding beads in a mass ratio of 1:50, and then adding 5g of hexagonal boron nitride to perform liquid phase ball milling for 36 hours under the condition of 500 revolutions per minute;
(3) and (3) introducing 20g of the hydroxyethyl cellulose/boron nitride composite solution in the preparation step (2) into a polytetrafluoroethylene grinding tool with the diameter of 10cm, and placing the polytetrafluoroethylene grinding tool in an oven to dry for 24 hours at 55 ℃ to successfully prepare the composite film.
The hydroxyethyl cellulose/boron nitride composite material prepared by one-step molding has high mechanical property and heat conductivity, the tensile strength is 50MPa, and the heat conductivity coefficient is as high as 7W/(m.K).
Claims (4)
1. A preparation method of hydroxyethyl cellulose/boron nitride nano composite film is characterized by comprising the following steps:
firstly, swelling hydroxyethyl cellulose in deionized water for 1-12 h, then stirring the obtained mixed system to obtain a hydroxyethyl cellulose solution, carrying out liquid-phase ball milling on 3-5% by mass of the hydroxyethyl cellulose solution and hexagonal boron nitride for 6-36 h by grinding beads under the condition of 300-500 rpm, wherein the mass ratio of the hydroxyethyl cellulose solution to the grinding beads is 1 (30-50), and the mass ratio of the hydroxyethyl cellulose to the hexagonal boron nitride in the hydroxyethyl cellulose solution is (0.6-2.5): (1-5) obtaining a hydroxyethyl cellulose/boron nitride composite solution;
and drying the hydroxyethyl cellulose/boron nitride composite solution at the temperature of 40-60 ℃ for 12-24 h to obtain the hydroxyethyl cellulose/boron nitride nano composite film.
2. The method for preparing the hydroxyethyl cellulose/boron nitride nano composite film according to claim 1, wherein the stirring is performed for 1-5 hours.
3. A hydroxyethyl cellulose/boron nitride nanocomposite film obtained by the method for producing a hydroxyethyl cellulose/boron nitride nanocomposite film according to any one of claims 1 to 2.
4. The hydroxyethyl cellulose/boron nitride nanocomposite film according to claim 3, wherein the hydroxyethyl cellulose/boron nitride nanocomposite film comprises stacked boron nitrides, wherein the distance between the boron nitrides is 3 to 5nm and the longitudinal dimension is 3 to 5 nm.
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| CN114575186B (en) * | 2022-03-01 | 2023-01-24 | 四川大学 | Cellulose-based composite barrier film and preparation method thereof |
| CN114773686B (en) * | 2022-05-31 | 2023-10-27 | 陕西科技大学 | HEC/BNNS/AgNWs composite film and preparation method thereof |
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