CN115028894A - Preparation method of composite slurry for preparing two-dimensional mica composite membrane, two-dimensional mica composite membrane and preparation method of two-dimensional mica composite membrane - Google Patents
Preparation method of composite slurry for preparing two-dimensional mica composite membrane, two-dimensional mica composite membrane and preparation method of two-dimensional mica composite membrane Download PDFInfo
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- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08K3/34—Silicon-containing compounds
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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
- C08K7/00—Use of ingredients characterised by shape
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Polymers & Plastics (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The application provides a preparation method of composite slurry for preparing a two-dimensional mica composite membrane, which comprises the following steps: mixing two-dimensional mica nanosheet powder with a silane coupling agent solution to obtain a two-dimensional mica nanosheet dispersion liquid; filtering and drying the two-dimensional mica nanosheet dispersion liquid to obtain modified two-dimensional mica nanosheets; and adding the modified two-dimensional mica nanosheet into polymethyl methacrylate dispersion liquid to obtain the composite slurry. The application also provides a preparation method of the two-dimensional mica composite membrane and the two-dimensional mica composite membrane. The two-dimensional mica composite film provided by the application not only has higher visible light transmission, but also has higher ultraviolet light barrier property, and excellent mechanical property and water vapor barrier property.
Description
Technical Field
The application relates to the technical field of two-dimensional materials, in particular to a preparation method of composite slurry for preparing a two-dimensional mica composite membrane, the two-dimensional mica composite membrane and a preparation method of the two-dimensional mica composite membrane.
Background
Mica is a common phyllosilicate mineral, and is widely applied to the electronic and electrical industries due to excellent electrical insulation, heat resistance, water resistance and other properties. In mica ore, the effective crystal area is not less than 4cm 2 The mica flake has high industrial value. However, more than 85% of the mica ore becomes scrap mica during mining and processing of the lepidolite ore, and the application fields of the scrap mica are limited. In addition, the crushed mica also originates from the mining of crushed mica ores. Compared with the lepidolite ore, China has more abundant broken mica resources. Therefore, the intensive research on the muscovite and the widening of the application field of the muscovite not only meet the requirement of green recycling economy, but also are beneficial to fully utilizing the muscovite resources of China.
Mica belongs to phyllosilicate, has good cleavage property and is an excellent source of two-dimensional nano materials. Because the two-dimensional material has higher diameter-thickness ratio and larger specific surface area, when the two-dimensional material is compounded with the polymer to prepare the composite membrane, more stable interaction can be generated, so that the composite membrane has more excellent performance. However, mica has high surface energy, and when it is compounded with a polymer, the compatibility between mica and the polymer is poor due to the mismatch of the surface energy of mica and the polymer, which results in poor performance of the prepared composite membrane.
Disclosure of Invention
In view of the above, the present application provides a preparation method of a composite slurry for preparing a two-dimensional mica composite film, a two-dimensional mica composite film and a preparation method thereof.
In order to achieve the above objects, the present application provides a method for preparing a composite slurry for a two-dimensional mica composite membrane, the method comprising: mixing two-dimensional mica nanosheet powder with a silane coupling agent solution to obtain a two-dimensional mica nanosheet dispersion liquid; filtering and drying the two-dimensional mica nanosheet dispersion liquid to obtain modified two-dimensional mica nanosheets; and adding the modified two-dimensional mica nanosheets into polymethyl methacrylate dispersion liquid to obtain the composite slurry.
In some possible implementations, the mass ratio of the silane coupling agent solution to the two-dimensional mica nanoplate powder is 50% to 60%.
In some possible implementations, the silane coupling agent solution includes a silane coupling agent including one or more of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or gamma-aminopropyltrimethoxysilane, and an organic solvent, which is one or more of ethanol, methanol, propanol, or acetone.
In some possible implementations, the polymethyl methacrylate dispersion has a solid content of 20 to 40 wt%.
In some possible implementation manners, the two-dimensional mica nanosheet is obtained by calcining natural mica powder at a calcining temperature of 750-850 ℃ for 1-2h in air to obtain a calcined substance, treating the calcined substance with a surfactant, and performing ultrasonic treatment, mechanical treatment, sanding, ball milling, microwave treatment or microfluidization, wherein the diameter of the two-dimensional mica nanosheet is 0.3-1.5 μm.
In some possible implementations, mixing the two-dimensional mica nanosheet powder with the silane coupling agent solution further includes adjusting the pH of the silane coupling agent solution to 3-4.
The application also provides a preparation method of the two-dimensional mica composite membrane, which comprises the following steps: providing said composite slurry; and carrying out blade coating treatment on the composite slurry, and standing to obtain the two-dimensional mica composite film, wherein the two-dimensional mica composite film comprises polymethyl methacrylate and modified two-dimensional mica nanosheets distributed in the polymethyl methacrylate, and the modified two-dimensional mica nanosheets are arranged in an ordered parallel layer.
In some possible implementation manners, when the composite slurry is subjected to blade coating treatment, the blade coating speed of the blade coating treatment is 30-50 mm/s, the gap between a blade coating rod and a substrate is 0.25-1 mm, the blade coating temperature is 20-26 ℃, and the solvent evaporation time is 5-20 min.
The application also provides a two-dimensional mica composite film prepared by the preparation method of the two-dimensional mica composite film, wherein the two-dimensional mica composite film comprises polymethyl methacrylate and modified two-dimensional mica nano sheets distributed in the polymethyl methacrylate, the modified two-dimensional mica nano sheets are arranged in a layered mode, and a plurality of layers of the modified two-dimensional mica nano sheets are arranged in parallel.
In some possible implementation modes, the thickness of the two-dimensional mica composite membrane is 0.02-0.08 mm.
In some possible implementation manners, the ratio of the modified two-dimensional mica nanosheet in the two-dimensional mica composite film is 3-40 wt%.
In the preparation method provided by the application, the two-dimensional mica nanosheet and the silane coupling agent solution are mixed, so that the silane coupling agent in the silane coupling agent solution is grafted to the surface of the two-dimensional mica nanosheet through a chemical bond, and the surface of the two-dimensional mica nanosheet is modified to obtain the modified two-dimensional mica nanosheet, so that the surface energy of the two-dimensional mica nanosheet can be reduced, the subsequent modified two-dimensional mica nanosheet has better compatibility with polymethyl methacrylate, the mixing uniformity and dispersibility of the modified two-dimensional mica nanosheet and polymethyl methacrylate are improved, and the binding capacity of the modified two-dimensional mica nanosheet and polymethyl methacrylate is improved.
Meanwhile, the modified two-dimensional mica nanosheets in the composite slurry are subjected to blade coating treatment, and tangential acting force is applied to the modified two-dimensional mica nanosheets, so that the two-dimensional mica nanosheets are orderly arranged in parallel layers, and the two-dimensional mica composite film with high visible light transmittance is obtained. Meanwhile, the two-dimensional mica nanosheets are orderly arranged in the polymethyl methacrylate in a parallel layered manner, so that the ultraviolet light shielding capability of the polymethyl methacrylate can be further enhanced, and the two-dimensional mica composite film also has high barrier property (such as water vapor and oxygen isolation), tensile strength and tensile modulus.
Drawings
Fig. 1 is a transmission electron microscope image of two-dimensional mica nanosheet powder obtained after peeling of natural mica powder provided in an embodiment of the present application.
Fig. 2 is a scanning electron microscope image of the natural mica composite film provided in comparative example 1 of the present application.
Fig. 3 is a scanning electron microscope photograph of a cross section of the natural mica composite film provided in comparative example 1 of the present application.
Fig. 4 is a scanning electron microscope image of a two-dimensional mica composite film provided in comparative example 2 of the present application.
Fig. 5 is a scanning electron microscope image of a cross section of a two-dimensional mica composite membrane provided in comparative example 2 of the present application.
Fig. 6 is a scanning electron microscope image of the two-dimensional mica composite film provided in example 1 of the present application.
Fig. 7 is a scanning electron microscope image of a cross section of a two-dimensional mica composite membrane provided in example 1 of the present application.
Fig. 8 is an infrared spectrum of the natural mica powder provided in comparative example 1 of the present application and the two-dimensional mica nanosheet in example 1.
Fig. 9 is an infrared spectrum of the two-dimensional mica nanosheet and the modified two-dimensional mica nanosheet provided in example 1 of the present application.
Fig. 10 is an infrared spectrum of the two-dimensional mica nanosheets and the modified two-dimensional mica nanosheets provided in example 4 of the present application.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The application provides a preparation method of a two-dimensional mica composite membrane, which comprises the following steps:
step S1: providing natural mica powder with the flake diameter of 20-120 mu m, and sequentially carrying out calcination treatment, cationic surfactant treatment and ultrasonic treatment to peel the natural mica powder into two-dimensional mica nanosheets.
Referring to fig. 1, in some embodiments, the two-dimensional mica nanoplatelets have a platelet diameter of 0.3 to 1.5 μm. As can be seen from fig. 1, two-dimensional mica nanosheets with micrometer-scale plate diameters are distributed.
In the present application, the natural mica powder used is derived from natural muscovite produced by new materials, Inc. of Anguilrui.
When the two-dimensional mica nanosheet is prepared from the natural mica powder, firstly, the natural mica powder is placed in the air atmosphere, the calcining temperature is 750-850 ℃, and the calcining time is 1-2h in the air, so that a calcined substance is obtained. And adding the calcined substance into a 4-5 mol/L nitric acid solution, and stirring for 4-5h at the heating temperature of 80-95 ℃ to obtain a pretreated calcined substance. And then adding the pretreated calcined substance into a sodium chloride saturated solution, heating to 80-95 ℃, and stirring for 12-14h to obtain the calcined substance treated by sodium chloride.
Then putting the calcined substance treated by the sodium chloride into a cationic surfactant, such as Cetyl Trimethyl Ammonium Bromide (CTAB) with the concentration of 30g/L, then washing the calcined substance treated by the CTAB (surfactant) with water, then carrying out ultrasonic treatment on the washed calcined substance for 1-2h, filtering, and drying to obtain the two-dimensional mica nanosheet, wherein the calcining temperature is preferably 800 ℃. The cationic surfactant includes a quaternary ammonium salt.
In the above process, the calcined substance is treated by nitric acid, which can remove impurities (such as iron minerals) from the calcined substance and make the calcined substance have a porous structure, thus facilitating the subsequent combination with the cationic surfactant. Meanwhile, the cationic surfactant can enter the interlayer of the calcined substance more easily through the treatment of sodium chloride, and the reactivity of the calcined substance and the cationic surfactant is improved.
In some embodiments, the calcine treated with the cationic surfactant may also be exfoliated into two-dimensional mica nanoplatelets using any of mechanical methods, sanding, ball milling, microwave, or microfluidizing.
Step S2: preparing a silane coupling agent solution, adding the two-dimensional mica nanosheets obtained in the step S1 into the silane coupling agent solution, and magnetically stirring to obtain a two-dimensional mica nanosheet dispersion liquid. The silane coupling agent is grafted on the surface of the two-dimensional mica nanosheet by forming chemical bonding through condensation reaction of silicon hydroxyl in the silane coupling agent and hydroxyl on the surface of the two-dimensional mica nanosheet.
In the step, the mass ratio of the silane coupling agent solution to the two-dimensional mica nanosheet powder is 50% -60%, and the ratio of the silane coupling agent solution to the two-dimensional mica nanosheet powder is within the range, so that the silane coupling agent solution can be used for fully modifying the surfaces of the two-dimensional mica nanosheets.
In some embodiments, the silane coupling agent solution includes a silane coupling agent including one or more of gamma-methacryloxypropyltrimethoxysilane (KH570), gamma-glycidoxypropyltrimethoxysilane, or gamma-aminopropyltrimethoxysilane, and an organic solvent, which is one or more of ethanol, methanol, isopropanol, or acetone.
When preparing the silane coupling agent solution, the silane coupling agent can be added into the organic solvent under magnetic stirring to be fully mixed and dissolved. For example, KH570 is slowly added dropwise to a 95% ethanol solution.
In some embodiments, in preparing the silane coupling agent solution, oxalic acid or acetic acid may be added to the silane coupling agent and the organic solvent under magnetic stirring to make the pH of the mixed solution 3-4, and stirring is continued at room temperature for 3-4 hours to obtain the oligomer solution of KH 570.
In some embodiments, the two-dimensional mica nanosheet powder of step S1 is added to a silane coupling agent solution, and the silane coupling agent solution containing the two-dimensional mica nanosheet powder can be heated to 70 ℃ and then stirred for 3 hours to obtain a two-dimensional mica nanosheet dispersion.
Step S3: and filtering, cleaning and drying the two-dimensional mica nanosheet dispersion liquid to obtain the modified two-dimensional mica nanosheet.
In some embodiments, the two-dimensional mica nanosheet dispersion is filtered by vacuum filtration, and the filter residue is washed 3-4 times with anhydrous ethanol to remove excess silane coupling agent solution.
In some embodiments, the drying treatment temperature is 60-80 ℃ and the drying treatment time is 12-24 h, so as to obtain the dried modified two-dimensional mica nanosheet.
Step S4: preparing polymethyl methacrylate dispersion liquid, adding the modified two-dimensional mica nanosheets into the polymethyl methacrylate dispersion liquid, and magnetically stirring to obtain the composite slurry.
In some embodiments, the polymethyl methacrylate dispersion has a solids content of 20 to 40 wt%, for example, the polymethyl methacrylate dispersion has a solids content of 20 wt%, 30 wt%, or 40 wt%.
In some embodiments, the polymethyl methacrylate dispersion comprises polymethyl methacrylate and a dispersant, the dispersant being ethyl acetate.
Step S5: and carrying out blade coating treatment on the composite slurry, and standing to obtain a two-dimensional mica composite membrane, wherein the two-dimensional mica composite membrane has selective light transmittance. In particular, the two-dimensional mica composite film may allow visible light to pass therethrough while blocking ultraviolet light. The two-dimensional mica composite film comprises polymethyl methacrylate and modified two-dimensional mica nanosheets distributed in the polymethyl methacrylate, the modified two-dimensional mica nanosheets are orderly arranged in layers in a matrix (namely the polymethyl methacrylate), and the layers are approximately parallel to each other (figure 7).
In some embodiments, before the composite slurry is subjected to the blade coating treatment, the composite slurry needs to be magnetically stirred for 12 hours and kept still for 24 hours for defoaming, so that the polymethyl methacrylate in the composite slurry is fully dissolved. It is understood that the polymethyl methacrylate is further dispersed in the dispersant by the shearing force after the composite slurry is stirred.
In some embodiments, the composite slurry may be knife coated using an automated film coater. The blade coating speed of the blade coating treatment is 30-50 mm/s, the gap between a blade coating rod and a substrate is 0.25-1 mm, and the blade coating temperature is 20-26 ℃. Under the above-mentioned blade coating conditions, the thickness and uniformity of the two-dimensional mica composite film can be further ensured. And (3) after blade coating, evaporating the solvent at room temperature for 5-20 min. Specifically, a stepped temperature rise program is arranged in the automatic film coating machine, the substrate is set to be 20-26 ℃ at first, and then blade coating is carried out, so that the influence on the uniformity of the two-dimensional mica composite film due to temperature change is avoided.
In the preparation method provided by the application, the two-dimensional mica nanosheet and the silane coupling agent solution are mixed, so that the silane coupling agent in the silane coupling agent solution is grafted on the surface of the two-dimensional mica nanosheet through a chemical bond, and the surface of the two-dimensional mica nanosheet is modified to obtain the modified two-dimensional mica nanosheet, so that the surface energy of the two-dimensional mica nanosheet can be reduced, the subsequent modified two-dimensional mica nanosheet has better compatibility with polymethyl methacrylate, the mixing uniformity and dispersibility of the modified two-dimensional mica nanosheet and polymethyl methacrylate are improved, and the binding capacity of the modified two-dimensional mica nanosheet and polymethyl methacrylate is improved.
Meanwhile, the composite slurry is subjected to blade coating treatment, so that tangential acting force is applied to the modified two-dimensional mica nanosheets in the composite slurry, and the modified two-dimensional mica nanosheets are arranged in an ordered layered manner. The two-dimensional mica nanosheet has the advantages of ultraviolet shielding, high insulating property, impermeability, good mechanical property and the like, particularly has high transmittance to visible light above 400nm and has the characteristic of shielding effect to ultraviolet light below 400nm, and an ordered parallel layered arrangement structure is formed in the two-dimensional mica composite film, so that the intrinsic polarization and the interlayer light interference phenomenon between layers of the two-dimensional mica nanosheet are modified, and the two-dimensional mica composite film is endowed with excellent selective light transmittance.
In the application, since the modified two-dimensional mica nanosheets are uniformly dispersed in the two-dimensional mica composite film and form an ordered layered structure, an effective path for blocking outside gas or liquid such as water vapor, oxygen and the like) is increased, so that the outside gas or liquid is difficult to pass through the two-dimensional mica composite film, and the two-dimensional mica composite film has high barrier property.
In addition, the silane coupling agent is bonded between the modified two-dimensional mica nanosheets and the polymethyl methacrylate in a molecular chain form, so that the compatibility and the bonding strength of the modified two-dimensional mica nanosheets and the polymethyl methacrylate are improved, and in addition, the layered structure of the modified two-dimensional mica nanosheets further improves the tensile strength and the tensile modulus of the two-dimensional mica composite film.
Moreover, the preparation method provided by the application is simple, easy to operate and easy to realize large-scale production.
The application also provides a two-dimensional mica composite film prepared by the preparation method, the two-dimensional mica composite film comprises polymethyl methacrylate and modified two-dimensional mica nanosheets distributed in the polymethyl methacrylate, the modified two-dimensional mica nanosheets are arranged in an ordered layered manner, and the layers are approximately parallel to each other. The two-dimensional mica composite membrane has a better compactness (see fig. 7), and several obstacles are formed to hinder gas or liquid from passing through the two-dimensional mica composite membrane. In addition, the two-dimensional mica nanosheet has an intrinsic ultraviolet shielding effect, and the light absorption rate of the two-dimensional mica composite film in an ultraviolet band is improved.
Furthermore, in the two-dimensional mica film, polymethyl methacrylate molecular chains can be distributed between layers of the modified two-dimensional mica nanosheets, so that the two-dimensional mica nanosheets can be effectively combined together.
The composite slurry can be coated on the surfaces of automobile plastics, packages, agricultural films and coatings in a blade mode, and can be applied to the field of ultraviolet protection. When the two-dimensional mica composite film is formed after the composite slurry is blade-coated, the two-dimensional mica composite film can be applied to vehicle window glass, lamps and sun-shading appliances as a coating.
In some embodiments, the two-dimensional mica composite film has a thickness of 0.02 to 0.08mm, for example, 0.02mm, 0.03mm, 0.04mm, 0.06mm, or 0.08 mm.
In some embodiments, the ratio of the modified two-dimensional mica nanosheets in the two-dimensional mica composite film is 3-40 wt%, for example, the ratio of the modified two-dimensional mica nanosheets in the two-dimensional mica composite film can be 3 wt%, 5 wt%, 10 wt%, 20 wt% or 40 wt%. The modified two-dimensional mica nanosheet can play a better role in visible light transmission and ultraviolet shielding under the mass ratio.
The scheme of the invention will be explained with reference to the following examples. It will be appreciated by those skilled in the art that the following examples are illustrative only and are not to be construed as limiting the invention. Unless otherwise handled, reagents, software and equipment not specifically handled in the following examples are conventional commercially available products or open sources.
Example 1
Providing 4g of two-dimensional mica nanosheet powder obtained by performing ultrasonic treatment on natural mica powder, wherein the diameter of the two-dimensional mica nanosheet powder is 0.3-1.5 mu m.
Providing a silane coupling agent solution, wherein the silane coupling agent solution comprises KH570 and an ethanol solution with the concentration of 95%, the concentration of KH570 in the silane coupling agent solution is 20mg/ml, dropwise adding a proper amount of oxalic acid under magnetic stirring to adjust the pH value to be about 3, and continuously stirring at room temperature for 3 hours.
Slowly adding 4g of two-dimensional mica nanosheet powder into 100ml of the silane coupling agent solution, heating to 70 ℃, and magnetically stirring for 3h to obtain a surface-modified two-dimensional mica dispersion liquid, wherein the mass ratio of the silane coupling agent solution to the two-dimensional mica nanosheet powder is 50%. And carrying out vacuum filtration on the surface-modified two-dimensional mica dispersion liquid, washing the surface-modified two-dimensional mica with absolute ethyl alcohol for 3 times, and drying the surface-modified two-dimensional mica in a 60 ℃ drying oven for 24 hours after washing to obtain modified two-dimensional mica nanosheet powder.
Providing a polymethyl methacrylate dispersion liquid with solid content of 20 wt%, adding 2g of modified two-dimensional mica nanosheet powder into 15g of the polymethyl methacrylate dispersion liquid, magnetically stirring for 12h, and standing for 24h to obtain the composite slurry.
And carrying out blade coating treatment on the composite slurry, wherein the moving speed of a blade coating rod is 40mm/s, the height of the blade coating rod from a substrate is 0.25mm, the temperature of the substrate is 25 ℃, and standing for 10min at room temperature to obtain the two-dimensional mica composite membrane with the thickness of 40 mu m. In the two-dimensional mica composite film, the two-dimensional mica nanosheet accounts for 40 wt%.
Example 2
Example 2 differs from example 1 in that: adding the 2g of modified two-dimensional mica nanosheet powder into 40g of the polymethyl methacrylate dispersion liquid. In the two-dimensional mica composite film, the two-dimensional mica nanosheet accounts for 20 wt%. The remaining conditions were the same as in example 1.
Example 3
Example 3 differs from example 1 in that: and adding 1g of modified two-dimensional mica nanosheet powder into 95g of the polymethyl methacrylate dispersion liquid. In the two-dimensional mica composite film, the two-dimensional mica nanosheet accounts for 5 wt%. The remaining conditions were the same as in example 1.
Example 4
Example 4 differs from example 1 in that: slowly adding 4g of two-dimensional mica nanosheet powder into 100ml of the silane coupling agent solution, heating to 70 ℃, and magnetically stirring for 3 hours to obtain the surface-modified two-dimensional mica dispersion liquid. The mass ratio of the silane coupling agent to the two-dimensional mica nanosheet powder is 60%. The remaining conditions were the same as in example 1.
Comparative example 1
Providing a polymethyl methacrylate dispersion liquid with the solid content of 20 wt%, directly adding 2g of natural mica powder into 15g of the polymethyl methacrylate dispersion liquid, magnetically stirring for 12h, and standing for 24h to obtain the composite slurry.
And carrying out blade coating treatment on the composite slurry, wherein the moving speed of a blade coating rod is 40mm/s, the height of the blade coating rod from a substrate is 0.25mm, the temperature of the substrate is 25 ℃, and standing for 10min at room temperature to obtain the natural mica composite membrane with the thickness of 40 mu m. In the natural mica composite film, the natural mica powder accounts for 40 wt%.
Comparative example 2
Comparative example 2 differs from example 1 in that: the silane coupling agent solution was not added, and the remaining conditions were the same as in example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that: the two-dimensional mica nanoplate powder and the silane coupling agent solution were not added, and the remaining conditions were the same as in example 1.
The present application also measured the light transmittance of the two-dimensional mica composite films of examples 1 to 4 and comparative examples 1 to 3 using an ultraviolet-visible spectrophotometer (Cary 5000), and the tensile properties of the two-dimensional mica composite films of examples 1 to 3 and comparative examples 2 to 3 using a universal material testing machine (Instron 5973), and the water vapor transmittance of the two-dimensional mica composite films of examples 1 to 3 and comparative examples 2 to 3 using a water loss method, and the results are shown in table 1.
Table 1 results of performance test of two-dimensional mica composite films in examples 1 to 4 and comparative examples 1 to 3
As can be seen from table 1, in the two-dimensional mica composite films of examples 1 to 3, as the proportion of the two-dimensional mica nanosheets increases, the ultraviolet light shielding rate, the tensile strength, the tensile modulus, and the water vapor barrier property are all significantly improved. When the proportion of the two-dimensional mica nano-sheets is 40 wt%, the two-dimensional mica composite film has the highest ultraviolet shielding rate of 67.4%, the highest tensile strength of 5.9MPa and the highest tensile modulus of 5.8 GPa. And the two-dimensional mica composites with selective light transmission of examples 1-3 maintained high visible light transmission at high loadings of 40%.
In table 1, compared to comparative example 2, after the silane coupling agent solution is added and the two-dimensional mica nanosheets are modified, the visible light transmittance, tensile strength, tensile modulus and water vapor transmittance of the two-dimensional mica composite film are improved.
The natural mica composite film and the two-dimensional mica composite film in comparative examples 1-2 were also tested by scanning electron microscopy, respectively. Referring to fig. 2 and 3, in fig. 2, the natural mica composite membrane of comparative example 1 shows more bubbles (e.g., dotted circles) generated due to poor compatibility between natural mica and polymethylmethacrylate. And natural mica platelets with uneven distribution appear in figure 2. In fig. 3, the natural mica sheet layer in the natural mica composite film is thick (e.g., the natural mica sheet layer in the oval dotted line) and the natural mica sheet layer is not uniformly dispersed, as viewed from the cross section of the natural mica composite film.
In fig. 4, the surface of the two-dimensional mica composite film in comparative example 2 also showed more bubbles (e.g., dotted circle), and in fig. 5, two-dimensional mica nanosheets in the two-dimensional mica composite film were randomly stacked together (e.g., natural mica platelets in the elliptic dotted line) as viewed from the cross section of the two-dimensional mica composite film, and the natural mica platelets were not uniformly dispersed. As can be seen from the data in table 1, compared with example 1, in comparative example 2, due to poor compatibility between the two-dimensional mica nanosheets and the polymethyl methacrylate, the two-dimensional mica nanosheets in the two-dimensional mica composite film are stacked in a disordered manner to form aggregates, which reduces the tensile strength and the tensile modulus. The agglomerated two-dimensional mica nanosheets do not form an effective path for blocking outside water vapor, and the barrier property of the two-dimensional mica composite film is reduced.
Referring to fig. 6 to 7, the present application also performed a scanning electron microscope test on the two-dimensional mica composite film of example 1. As can be seen from fig. 6, the surface of the two-dimensional mica composite membrane was free from bubbles, compared to comparative examples 1 to 2. As seen from fig. 7, the multilayer modified two-dimensional mica nanosheets arranged in parallel are uniformly distributed in the two-dimensional mica composite film, forming an ordered laminated structure. On one hand, the compatibility of the two-dimensional mica nanosheet and polymethyl methacrylate is improved after the two-dimensional mica nanosheet structure is modified by the silane coupling agent solution, and on the other hand, the uniformity of the two-dimensional mica nanosheet dispersed in the polymethyl methacrylate is also shown.
Referring to fig. 8 to 10, the present application also performed infrared spectroscopy tests on natural mica powder, two-dimensional mica nanoplates, modified two-dimensional mica nanoplates of example 1, and modified two-dimensional mica nanoplates of example 4. As seen in FIG. 8, daysThe natural mica powder is subjected to calcination treatment, cationic surfactant treatment and ultrasonic treatment, and compared with the natural mica powder, the two-dimensional mica nanosheet is about 3630cm -1 The intensity of the OH peak at the wavenumber is weakened, and more hydroxyl groups in the natural mica powder undergo dehydration reaction during the calcination treatment, so that the hydroxyl groups are weakened. As can be seen from fig. 9, the modified two-dimensional mica nanosheets in example 1 were at about 3620cm -1 -3630cm -1 The intensity of the OH peak at wavenumbers decreases. As can be seen from fig. 10, the modified two-dimensional mica nanosheet in example 4 was at about 3620cm as compared to the two-dimensional mica nanosheet -1 -3630cm -1 The intensity of the OH peak at wavenumbers also decreases. The hydroxyl groups in the modified two-dimensional mica nanosheets obtained after the silane coupling agent solution treatment are obviously reduced, the surface energy of the two-dimensional mica nanosheets is reduced, and the binding capacity of the modified two-dimensional mica nanosheets and the polymethyl methacrylate is improved.
Although the present invention has been described in detail with reference to the above embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (11)
1. A preparation method of composite slurry for preparing a two-dimensional mica composite membrane is characterized by comprising the following steps:
mixing two-dimensional mica nanosheet powder with a silane coupling agent solution to obtain a two-dimensional mica nanosheet dispersion liquid;
filtering and drying the two-dimensional mica nanosheet dispersion liquid to obtain modified two-dimensional mica nanosheets;
and adding the modified two-dimensional mica nanosheets into polymethyl methacrylate dispersion liquid to obtain the composite slurry.
2. The method for preparing composite slurry according to claim 1, wherein the mass ratio of the silane coupling agent solution to the two-dimensional mica nanosheet powder is 50% to 60%.
3. The method for preparing the composite paste according to claim 1, wherein the silane coupling agent solution comprises a silane coupling agent and an organic solvent, the silane coupling agent comprises one or more of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, or gamma-aminopropyltrimethoxysilane, and the organic solvent is one or more of ethanol, methanol, isopropanol, or acetone.
4. The method for preparing composite slurry according to claim 1, wherein the polymethyl methacrylate dispersion has a solid content of 20 to 40 wt%.
5. The preparation method of the composite slurry according to claim 1, wherein the two-dimensional mica nanosheet is obtained by calcining natural mica powder at a temperature of 750-.
6. The method for preparing composite slurry according to claim 1, further comprising adjusting the pH of the silane coupling agent solution to 3 to 4 after mixing the two-dimensional mica nanoplate powder and the silane coupling agent solution.
7. A preparation method of a two-dimensional mica composite membrane is characterized by comprising the following steps:
providing a composite slurry according to any one of claims 1 to 6;
and carrying out blade coating treatment on the composite slurry, and standing to obtain the two-dimensional mica composite film, wherein the two-dimensional mica composite film comprises polymethyl methacrylate and modified two-dimensional mica nanosheets distributed in the polymethyl methacrylate, and the modified two-dimensional mica nanosheets are arranged in an ordered parallel layer.
8. The method for preparing a two-dimensional mica composite film according to claim 7, wherein when the composite slurry is subjected to blade coating, the blade coating speed of the blade coating is 30-50 mm/s, the gap between a blade coating rod and a substrate is 0.25-1 mm, the blade coating temperature is 20-26 ℃, and the solvent evaporation time is 5-20 min.
9. A two-dimensional mica composite film prepared by the preparation method of the two-dimensional mica composite film as set forth in any one of claims 7 or 8, wherein the two-dimensional mica composite film comprises polymethyl methacrylate and modified two-dimensional mica nano sheets distributed in the polymethyl methacrylate, the modified two-dimensional mica nano sheets are arranged in a layered manner, and a plurality of layers of the modified two-dimensional mica nano sheets are arranged in parallel.
10. A two-dimensional mica composite film according to claim 9, wherein the thickness of the two-dimensional mica composite film is 0.02 to 0.08 mm.
11. The two-dimensional mica composite film according to claim 9, wherein the ratio of the modified two-dimensional mica nanosheets in the two-dimensional mica composite film is 3 to 40 wt%.
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