Montmorillonite material with directional structure and photocuring 3D printing method and application thereof

Abstract

The invention discloses a montmorillonite material with an oriented structure and a photocuring 3D printing method and application of the montmorillonite material, and belongs to the technical field of inorganic mineral material processing. Comprising the following components in percentage by mass: 15-40 wt% of layered montmorillonite, 50-75 wt% of a light-cured resin monomer, 0.5-5 wt% of a photoinitiator, 0.1-5 wt% of a dispersing agent and 0-5 wt% of a glass material, the softening point of the glass material is 300 to 500 DEG C. The photocuring 3D printing process is adopted, accurate construction of a complex three-dimensional structure can be achieved, and the limitation of a traditional forming method on the degree of freedom of configuration is broken through. By combining with the addition of a low-melting-point glass material, densification can be promoted in the heat treatment process, and phase change instability of the layered montmorillonite at high temperature can be effectively inhibited, so that excellent mechanical and thermal stability is obtained while oriented arrangement of nanosheet layers of the layered montmorillonite is kept; and a new path is provided for controllable manufacturing of the anisotropic montmorillonite material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of inorganic mineral material processing, and particularly relates to a directional structure montmorillonite material and a photo-curing 3D printing method and application thereof. BACKGROUND

[0002] Montmorillonite is a kind of sheet-shaped inorganic mineral material, which has good adsorption and ion exchange performance and is widely used in the fields of environmental protection, medicine, composite materials and chemical industry. Under specific process conditions, the directional arrangement of the ordered stacking or distribution of the layered crystal structure of montmorillonite in a specific direction can significantly optimize the physical, chemical and mechanical properties of the montmorillonite, thereby improving the reinforcing effect of the montmorillonite in composite materials and the efficiency of the montmorillonite in adsorption and catalysis applications.

[0003] In the prior art, the directional arrangement of montmorillonite is usually realized by using external field assistance such as electric field, magnetic field or mechanical shearing, but these methods have defects such as complex process, high cost and difficulty in accurately controlling the structure form. SUMMARY

[0004] The present application aims to provide a directional structure montmorillonite material and a photo-curing 3D printing method and application thereof, so as to solve the problems in the background.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions.

[0006] A directional structure montmorillonite material is prepared by photo-curing 3D printing, and includes the following components in terms of mass percentage: 15-40wt% of layered montmorillonite, 50-75wt% of photo-curing resin monomer, 0.5-5wt% of photoinitiator, 0.1-5wt% of dispersant and 0-5wt% of glass material; the softening point of the glass material is 300-500 DEG C.

[0007] Further, the directional structure montmorillonite material includes the following components in terms of mass percentage: 23-40wt% of layered montmorillonite, 54-70wt% of photo-curing resin monomer, 2-4.8wt% of photoinitiator, 0.2-0.4wt% of dispersant and 2-4wt% of glass material.

[0008] Further, the layered montmorillonite is single-layer or multi-layer montmorillonite nanosheet treated by layered exfoliation; the method of layered exfoliation treatment is ultrasonic exfoliation, high-speed shearing dispersion or chemical intercalation; the thickness of the layered montmorillonite is 1-100nm, and the diameter-thickness ratio is greater than 50.

[0009] Further, the photocuring resin monomer is one or more of acrylate-based monomer, methacrylate-based monomer, butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate.

[0010] Further, the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.

[0011] Further, the dispersant is one or more of acid group-containing copolymer, macromolecular copolymer alkyl ammonium salt, xylene propylene glycol methyl ether acetate, oleic acid, stearic acid, silane coupling agent.

[0012] Further, the glass material is borosilicate glass or phosphate glass; or the glass material is borosilicate glass or phosphate glass modified by rare earth oxide; the preparation method of the borosilicate glass or phosphate glass modified by rare earth oxide is: mixing borosilicate glass or phosphate glass with rare earth oxide, then heating to 500-600℃, and then quenching and grinding to obtain borosilicate glass or phosphate glass modified by rare earth oxide.

[0013] Another object of the present application is to provide a photocuring 3D printing method for the above-mentioned oriented montmorillonite material, which comprises the following steps:

[0014] According to the mass percentage of each component, the layered montmorillonite, the photocuring resin monomer, the photoinitiator, the dispersant and the glass material are mixed to prepare a slurry;

[0015] The slurry is printed layer by layer to build a green body of a predetermined shape by using a photocuring 3D printing process; during the photocuring 3D printing process, the slurry is leveled by a scraper and then cured by laser; the shear force applied to the slurry during the leveling process by the scraper can make the layered montmorillonite in the slurry uniformly and directionally arranged along the moving direction of the scraper;

[0016] According to the application requirements, the green body is directly used as a resin-based functional material; or the green body is heat treated to obtain an oriented montmorillonite material.

[0017] Further, the photocuring 3D printing process is a digital light processing process or a stereolithography process; the printing parameters are as follows: laser power is 50-200mW, laser wavelength is 355-405nm, printing layer thickness is 10-100μm, and the moving speed of the scraper is 5-20mm / s; the heat treatment conditions are as follows: heating to 400-600℃ at a heating rate of 1-5℃ / min, holding for 1-3h, and then cooling at a rate of 1-3℃ / min.

[0018] Another object of the present application is to provide an application of the above-mentioned oriented structured montmorillonite material in gas separation, catalytic carrier, adsorption filtration or functional resin device.

[0019] The present application provides an oriented structured montmorillonite material prepared by a photocuring 3D printing process, which can realize accurate construction of complex three-dimensional structures, break through the limitations of traditional forming methods in the degree of freedom of construction, thereby improving the adsorption, ion exchange and mechanical properties of the montmorillonite material, and expanding its application in functional devices and the like. In combination with the addition of a low-melting-point glass material, the densification is promoted and the phase transition instability of the layered montmorillonite at high temperatures is effectively inhibited during the heat treatment, so as to maintain the oriented arrangement of the nanosheet layers of the layered montmorillonite while obtaining excellent mechanical and thermal stability, thereby providing a new path for the controllable construction of anisotropic montmorillonite material. The method not only realizes the ordered regulation of the layered montmorillonite on a macroscopic scale, but also effectively passivates the active sites on the edges of the sheet layers through in-situ coating of the low-melting-point glass material, thereby inhibiting the reconstruction behavior of the aluminum-oxygen tetrahedron at high temperatures, and further improving the thermal stability and environmental resistance of the montmorillonite material. At the same time, the continuous amorphous network formed between the sheet layers of the layered montmorillonite by the low-melting-point glass material can effectively block the external water and oxygen erosion, and significantly enhance the structural stability and long-term durability of the montmorillonite material in a humid environment. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0021] In an embodiment of the present application, an oriented structured montmorillonite material is provided, which is prepared by photocuring 3D printing, and includes the following components in terms of mass percentage: 15-40wt% of layered montmorillonite, 50-75wt% of photocuring resin monomer, 0.5-5wt% of photoinitiator, 0.1-5wt% of dispersant, and 0-5wt% of glass material.

[0022] Specifically, the photocuring 3D printing method of the oriented structured montmorillonite material includes the following steps:

[0023] The layered montmorillonite, photocuring resin monomer, photoinitiator, dispersant and glass material are mixed in terms of mass percentage to prepare a slurry;

[0024] The slurry is printed layer by layer to build a green body of a predetermined shape by using a light-curing 3D printing process; during the light-curing 3D printing process, the slurry is thinned and leveled by a scraper and then cured by laser; the shearing force applied to the slurry by the scraper during the leveling process can make the layered smectite in the slurry uniformly and directionally arranged along the moving direction of the scraper, significantly improving the anisotropic performance of the smectite material, which cannot be achieved by other 3D printing processes.

[0025] According to application requirements, the green body is directly used as a resin-based functional material; or the green body is heat treated to obtain a high-purity directional structure smectite material.

[0026] Preferably, the light-curing 3D printing process is a digital light processing (DLP) process or a stereolithography (SLA) process; the printing parameters are as follows: laser power is 50-200 mW, laser wavelength is 355-405 nm, printing layer thickness is 10-100 μm, and the moving speed of the scraper is 5-20 mm / s, so as to ensure that the layered smectite is directionally arranged before being cured in each layer.

[0027] Preferably, the heat treatment conditions are as follows: the temperature is raised to 400-600 ℃ at a rate of 1-5 ℃ / min in air, vacuum or inert atmosphere, and then cooled to room temperature at a rate of 1-3 ℃ / min, so that the layered smectite maintains ordered orientation under the wrapping of low-melting-point glass material, avoiding collapse and disordered re-stacking at high temperature. In addition, by controlling the process parameters of heat treatment, the organic residues can be removed while the orientation of the layered smectite is retained, obtaining a pure inorganic material with controllable porosity and stable structure, which is suitable for high-performance adsorption membranes, catalytic carriers or composite reinforcing phases, etc.

[0028] Preferably, the directional structure smectite material comprises the following components in terms of mass percentage: 23-40 wt% of layered smectite, 54-70 wt% of light-curing resin monomer, 2-4.8 wt% of photoinitiator, 0.2-0.4 wt% of dispersant, and 2-4 wt% of glass material.

[0029] Preferably, the layered smectite is a single-layer or multi-layer smectite nanosheet subjected to layered exfoliation treatment; the method of layered exfoliation treatment is ultrasonic exfoliation, high-speed shearing dispersion or chemical intercalation; the thickness of the layered smectite is 1-100 nm, and the diameter-thickness ratio is greater than 50.

[0030] Preferably, the photo-curable resin monomer is one or more of acrylate-based monomer, methacrylate-based monomer, butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and other photo-curable monomers with single functional group, double functional group or multiple functional group, and low-viscosity single functional group photo-curable resin monomers are mainly used.

[0031] Preferably, the photo-initiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.

[0032] Preferably, the dispersant is one or more of acid group-containing copolymer, high-molecular copolymer alkyl ammonium salt, xylene propylene glycol methyl ether acetate, oleic acid, stearic acid, silane coupling agent. The viscosity of the slurry is controlled at 50-100 Pa·s (25℃); the amount of dispersant is adjusted according to the viscosity of the system (50-100 Pa·s).

[0033] Preferably, the softening point of the glass material is 300-500℃; during the heat treatment, the glass material can form an amorphous network structure in situ between the layers of the layered montmorillonite, promoting densification and inhibiting high-temperature phase transition of the montmorillonite. It should be noted that if the heat treatment temperature is high enough or no heat treatment is performed, the glass material can also not be added, and the layered montmorillonite can still maintain the oriented structure and certain mechanical integrity due to the particle boundary effect after removing the organic matter at high temperature.

[0034] Preferably, the glass material is borosilicate glass or phosphate glass; or the glass material is borosilicate glass or phosphate glass modified by rare earth oxide; the preparation method of the borosilicate glass or phosphate glass modified by rare earth oxide is: mixing borosilicate glass or phosphate glass with rare earth oxide in a mass ratio of (0.05-0.2):1, then heating to 500-600℃ at a heating rate of 1-5℃ / min, holding for 1-3h, and then quenching and grinding to obtain the borosilicate glass or phosphate glass modified by rare earth oxide. The rare earth oxide is one or more of cerium oxide, yttrium oxide and lanthanum oxide; the rare earth ions can enter the glass network and have a synergistic effect with the glass material; specifically, the introduction of rare earth ions can break part of the B-O or P-O network, reduce the melting temperature and viscosity of the glass material, and enable it to better wet and wrap the layers of the layered montmorillonite; moreover, the rare earth ions themselves occupy the network gap and are combined with non-bridging oxygen bonds, playing a role in reinforcing the glass network, which can significantly improve the thermal stability, chemical durability and mechanical strength of the glass phase, effectively inhibit the crystallization tendency of the glass phase during heat treatment and cooling, maintain a uniform amorphous state, avoid internal stress concentration and structural cracking caused by local crystallization, and make it more stable during heat treatment and subsequent use; moreover, by using rare earth oxides such as cerium oxide with redox catalytic activity, the adsorption and catalytic capacity of the montmorillonite material can be further improved.

[0035] According to the application scenario requirements of the prepared material, it can be selected whether to need to be heat treated. The material without heat treatment is a resin-based functional material filled with montmorillonite in a directional arrangement, which has very high forming precision and good anisotropy characteristics, and is suitable for functional resin devices with low requirements for thermal stability; the material after heat treatment forms an inorganic material mainly composed of montmorillonite, which has excellent high-temperature stability and mechanical strength, and can form products with different pore structures according to different heat treatment processes, and the layered structure of montmorillonite can endow the material with application potential in the fields of high-temperature gas separation, catalytic carrier or thermal insulation. By adjusting the heat treatment atmosphere and cooling rate, the network connectivity of the residual glass phase in the product can be further optimized, thereby synergistically controlling the thermal conductivity and fracture toughness of the material to realize structure-function integrated construction.

[0036] If it is a resin-based functional material without heat treatment, the tensile strength in the x-axis direction is 1.5-2.0 times that in the z-axis direction, and the oxygen permeability in the z-axis direction is 50%-70% of that in the x-axis direction; if it is a directional structured montmorillonite material after heat treatment, the bulk density is 1.5-1.9g / cm 3 The adsorption amount of CO2 is 40-50mg / g, the adsorption amount of Cu 2+ and NH4 +The adsorption capacity is greater than or equal to 120 mg / g, the thermal conductivity is less than or equal to 0.35 W / (m*K), and the adsorption performance retention rate is greater than or equal to 95% after 30 adsorption and desorption cycles.

[0037] The resin-based functional material without heat treatment can be used for a functional resin device with low heat stability requirement; and the heat-treated oriented structure montmorillonite material can be used for high-temperature gas separation, a catalyst carrier, a heat insulation material or a high-temperature filtration and adsorption integrated scene.

[0038] In the embodiment of the application, the layered montmorillonite is uniformly dispersed in a photocuring resin monomer system, and a digital light processing or stereolithography light curing 3D printing technology is combined to realize layer-by-layer precise construction of the montmorillonite material with a directional arrangement microstructure; the layered montmorillonite is induced to be arranged in a set direction in the resin matrix by regulating the printing direction and the ultraviolet light irradiation path, and a three-dimensional porous or dense body with controllable structure is formed after light curing. The method breaks through the technical limitation of traditional external field assisted orientation, realizes programmed arrangement of the montmorillonite sheet under a complex geometric shape, and significantly improves the anisotropic performance of the montmorillonite material. By regulating the content and dispersion stability of the layered montmorillonite in the resin formula and combining printing parameter optimization, the microstructure orientation and density distribution can be precisely controlled, and the method is suitable for customized preparation of high-performance montmorillonite materials, adsorption devices and catalyst carriers. The method is simple to operate and has high forming precision, breaks through the bottleneck of directional construction of the montmorillonite material at the microscale, can realize stable and precise construction of millimeter to micrometer scale structures, is suitable for batch customized montmorillonite-based materials with directional functional characteristics, and does not need complex external field equipment support, and significantly reduces the process cost.

[0039] The following examples are some specific implementation cases of the application in actual application, but are not limited thereto.

[0040] It should be noted that in the following examples, the layered montmorillonite used is obtained by high-speed shearing and flaking, has an average aspect ratio of about 35, a D50 of 0.7 μm, a maximum particle size of not more than 5 μm, and a thickness of 1-100 nm. The photocuring resin monomer, the photoinitiator and the dispersant are all commercial industrial-grade materials. The glass material is selected from a borosilicate system, has a softening point of 400 DEG C, is purchased from Qichen New Material, and has a model of D400.

[0041] Example 1: The embodiment provides a directional structure montmorillonite material, and a preparation method thereof includes the following steps:

[0042] After 54 g of acrylate, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 0.2 g of oleic acid, 0.2 g of dimethyl isophthalate, and 0.2 g of xylene propylene glycol methyl ether acetate are uniformly mixed, 40 g of layered montmorillonite, 3.6 g of low-melting glass material D400 are added, and the mixture is dispersed by a high-speed disperser for 60 minutes to obtain a slurry with a uniform dispersion and a viscosity of 82 mPa·s (25°C). The slurry is then subjected to 3D printing molding in a photocuring ceramic 3D printer with a wavelength of 405 nm to obtain a green body with a three-dimensional structure. The printer parameters are set as follows: laser power is 100 mW, printing layer thickness is 50 μm, and squeegee moving speed is 10 mm / s. The green body with a three-dimensional structure obtained by printing is dried at 80°C under vacuum for 2 h, and then heated to 500°C at a rate of 5°C / min under a nitrogen atmosphere, and held for 2 h. The furnace is then cooled to obtain a porous lightweight directional structure montmorillonite material. The bulk density of the directional structure montmorillonite material is 1.7 g / cm 3 The adsorption capacity for carbon dioxide can reach 50 mg / g, and the adsorption performance remains above 95% after 30 adsorption-desorption cycles.

[0043] Example 2: The example provides a directional structure montmorillonite material, and the preparation method thereof comprises the following steps:

[0044] After 60 g of acrylate, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1 g of 1-hydroxycyclohexyl phenyl ketone, 0.1 g of oleic acid, and 0.2 g of acrylate / acrylonitrile copolymer ammonium salt (CAS No. 37809-64-6) are uniformly mixed, 36.7 g of layered montmorillonite and 3 g of low-melting glass material D400 are added, and the mixture is dispersed by a high-speed disperser for 60 minutes to obtain a slurry with a uniform dispersion and a viscosity of 80 mPa·s (25°C). The slurry is then subjected to 3D printing molding in a photocuring ceramic 3D printer with a wavelength of 405 nm to obtain a green body with a three-dimensional structure. The printer parameters are set as follows: laser power is 100 mW, printing layer thickness is 30 μm, and squeegee moving speed is 10 mm / s. The green body with a three-dimensional structure obtained by printing is dried at 80°C under vacuum for 2 h, and then heated to 500°C at a rate of 5°C / min under a nitrogen atmosphere, and held for 2 h. The furnace is then cooled to obtain a porous lightweight directional structure montmorillonite material. The bulk density of the directional structure montmorillonite material is 1.9 g / cm 3 The adsorption capacity for carbon dioxide can reach 42 mg / g, and the adsorption performance remains above 95% after 30 adsorption-desorption cycles.

[0045] Example 3: The example provides a directional structure montmorillonite material, and the preparation method thereof comprises the following steps:

[0046] After 40 g of butyl acrylate, 30 g of methyl methacrylate, 4.8 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 0.1 g of oleic acid, 0.1 g of dimethyl isophthalate glycol methyl ether acetate are uniformly mixed, 23 g of layered montmorillonite, 2 g of low-melting glass material D400 are added, and dispersed by a high-speed disperser for 60 minutes to obtain a slurry with uniform dispersion and a viscosity of 87 mPa·s (25°C); then the slurry is placed in a photocuring ceramic 3D printer with a wavelength of 405 nm for 3D printing forming to obtain a green body with a three-dimensional structure. The printer parameters are set as follows: laser power is 100 mW, printing layer thickness is 20 μm, and squeegee moving speed is 10 mm / s. The three-dimensional structure green body obtained by printing is dried at 80°C for 2 h under vacuum, and then heated to 600°C at a rate of 3°C / min under a nitrogen atmosphere, and held for 1.5 h to obtain a porous lightweight directional structure montmorillonite material. The bulk density of the directional structure montmorillonite material is 1.5 g / cm 3 , the thermal conductivity is as low as 0.32 W / (m·K), and the cation adsorption capacity for Cu 2+ and NH4 + is up to 120 mg / g, which is suitable for high-temperature filtration and adsorption integrated scenarios.

[0047] Example 4: The example provides a directional structure montmorillonite material, and the preparation method thereof comprises the following steps:

[0048] After 40 g of butyl acrylate, 30 g of methyl methacrylate, 5 g of pentaerythritol triacrylate, 5 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 0.1 g of oleic acid are uniformly mixed, 19.8 g of layered montmorillonite is added, and dispersed by a high-speed disperser for 30 minutes to obtain a slurry with uniform dispersion and a viscosity of 85 mPa·s (25°C); then the slurry is placed in a photocuring ceramic 3D printer with a wavelength of 405 nm for 3D printing forming to obtain a directional structure montmorillonite material. The printer parameters are set as follows: laser power is 100 mW, printing layer thickness is 20 μm, and squeegee moving speed is 10 mm / s. Although the directional structure montmorillonite material has a slight decrease in performance such as thermal stability and adsorption capacity compared with Examples 1-3, the tensile strength in the x-axis direction is 1.8 times that in the z-axis direction, and the oxygen permeability in the z-axis direction is 60% of that in the x-axis direction, showing significant anisotropic mechanical properties. The mechanical properties of the directional structure montmorillonite material are also greatly improved compared with the product without layered montmorillonite (i.e., the difference between Example 4 and the product without layered montmorillonite is only that no layered montmorillonite is added, and the other conditions are the same), wherein the tensile strength in the x-axis direction is 2.1 times that of the product without layered montmorillonite, reaching 68.5 MPa.

[0049] Example 5: The example provides a directional structure montmorillonite material, and the preparation method thereof comprises the following steps:

[0050] S1, the low-melting point glass material D400 is mixed with cerium oxide at a mass ratio of 0.1:1, then heated to 550℃ at a heating rate of 2℃ / min, and kept for 2h, and then quenched and ground to obtain a cerium oxide modified low-melting point glass material D400.

[0051] S2, 54g of acrylate, 2g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 0.2g of oleic acid, 0.2g of dimethylphenylpropanediol methyl ether acetate are mixed uniformly, then 40g of layered montmorillonite, 3.6g of cerium oxide modified low-melting point glass material D400 are added, and dispersed by a high-speed disperser for 60 minutes to obtain a slurry with uniform dispersion and a viscosity of 82mPa·s (25℃); then the slurry is placed in a photocuring ceramic 3D printer with a wavelength of 405nm for 3D printing to form a green body with a three-dimensional structure. The printer parameters are set as follows: laser power is 100mW, printing layer thickness is 50μm, and squeegee moving speed is 10mm / s. The three-dimensional structure green body obtained by printing is dried at 80℃ under vacuum for 2h, then heated to 500℃ at a rate of 5℃ / min under nitrogen atmosphere, kept for 2h, and cooled in the furnace to obtain a porous lightweight directional structure montmorillonite material. Compared with Example 1, the directional structure montmorillonite material prepared in Example 5 has a linear shrinkage rate after 600℃ heat preservation reduced by 23%, better structural integrity, and an adsorption capacity of carbon dioxide increased by 11%, and the tensile strength in the x-axis direction increased by 13%.

[0052] Based on the above ideal embodiments according to the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the contents of the specification.

Claims

1. A directionally structured smectite material, characterized in that, The oriented structure montmorillonite material is prepared by photocuring 3D printing, and comprises the following components in percentage by mass: 15-40wt% of layered montmorillonite, 50-75wt% of photocuring resin monomer, 0.5-5wt% of photoinitiator, 0.1-5wt% of dispersant, and 0-5wt% of glass material; the softening point of the glass material is 300-500℃.

2. The oriented constructed smectite material of claim 1, wherein, The oriented structure montmorillonite material comprises the following components in percentage by mass: 23-40wt% of layered montmorillonite, 54-70wt% of photocuring resin monomer, 2-4.8wt% of photoinitiator, 0.2-0.4wt% of dispersant, and 2-4wt% of glass material.

3. The oriented constructed smectite material of claim 1 or 2, wherein, The layered montmorillonite is single-layer or multi-layer montmorillonite nanosheet after layered exfoliation treatment; the method of layered exfoliation treatment is ultrasonic exfoliation, high-speed shearing dispersion or chemical intercalation; the thickness of the layered montmorillonite is 1-100nm, and the ratio of diameter to thickness is greater than 50.

4. The oriented constructed smectite material of claim 1 or 2, wherein, The photocuring resin monomer is one or more of acrylate-based monomer, methacrylate-based monomer, butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate.

5. The oriented constructed smectite material of claim 1 or 2, wherein, The photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide.

6. The oriented constructed smectite material of claim 1 or 2, wherein, The dispersant is one or more of acid group-containing copolymer, macromolecular copolymer alkyl ammonium salt, xylene propylene glycol methyl ether acetate, oleic acid, stearic acid, and silane coupling agent.

7. The oriented constructed smectite material of claim 1 or 2, wherein, The glass material is borosilicate glass or phosphate glass; or the glass material is borosilicate glass or phosphate glass modified by rare earth oxide; the preparation method of the borosilicate glass or phosphate glass modified by rare earth oxide is: mixing borosilicate glass or phosphate glass with rare earth oxide, then heating to 500-600℃, and then quenching and grinding to obtain borosilicate glass or phosphate glass modified by rare earth oxide.

8. A photocured 3D printing method for the directed construction of montmorillonite materials according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: Mixing layered montmorillonite, photocuring resin monomer, photoinitiator, dispersant, and glass material according to the mass percentage of each component to prepare slurry; Printing the slurry layer by layer to build a green body with a predetermined shape by using photocuring 3D printing process; during photocuring 3D printing, the slurry is flattened by a scraper and then cured by laser; the shear force applied to the slurry during the flattening process by the scraper can make the layered montmorillonite in the slurry uniformly and directionally arranged along the moving direction of the scraper; According to application requirements, the green body is directly used as a resin-based functional material; or the green body is heat treated to obtain an oriented structure montmorillonite material.

9. The photocured 3D printing method of orienting a smectite material according to claim 8, wherein, The light-curing 3D printing process is a digital light processing process or a stereolithography process; the printing parameters are as follows: the laser power is 50-200 mW, the laser wavelength is 355-405 nm, the printing layer thickness is 10-100 μm, and the scraper moving speed is 5-20 mm / s; the heat treatment conditions are as follows: the temperature is raised to 400-600 ℃ at a temperature raising rate of 1-5 ℃ / min, the temperature is kept for 1-3 h, and then the temperature is cooled at a rate of 1-3 ℃ / min.

10. Use of the oriented structure montmorillonite material according to any one of claims 1-7 in gas separation, catalytic carrier, adsorptive filtration or functional resin devices.