Porous functional ceramic material with high plasticity as well as preparation method and application of porous functional ceramic material

Abstract

The invention discloses a porous functional ceramic material with high plasticity as well as a preparation method and application thereof, and belongs to the technical field of ceramic preparation, the ceramic material is prepared by treating and firing ceramic slurry, and the ceramic slurry comprises the following components in parts by mass: 1-10 parts of a binder and 1-10 parts of a binder. Comprising the following components in parts by weight: 2090 to 2190 parts of red pottery clay, 1100 to 1200 parts of feldspar powder, 2580 to 2680 parts of kaolin, 1000 to 1100 parts of white sandy soil, 1300 to 1400 parts of flower soil, 540 to 640 parts of red pottery clay, 10 to 15 parts of manganese dioxide, 100 to 140 parts of plasticizer and 3600 to 4000 parts of water. The modified bentonite is used as a plasticizer of the ceramic, the surface layer of the bentonite is modified with a water-absorbing organic polymer structure, so that the water retention capacity of the bentonite is enhanced, non-uniform shrinkage of a green body caused by too fast water evaporation of the bentonite is prevented, and the hydroxyl and carboxyl structures on the surface can enhance the combination between soil bodies and can effectively prevent cracking; the organic polymer structure releases certain gas in the calcining process to obtain ceramic with a porous structure; organic molecular structures with different thermal stability are adopted to modify the surface of bentonite, so that gas is slowly released, and the ceramic material with uniform pores is obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramic preparation, and particularly relates to a porous functional ceramic material with high plasticity, a preparation method thereof, and an application thereof. Background Art

[0002] Ceramic articles are made from clay as raw materials through high-temperature firing, and have both practicality and artistry. Ceramic clay billet raw materials are essential raw materials in ceramic production. The plasticity of ceramic raw materials is a key technology in ceramic production, and the quality of plasticity directly affects subsequent production, such as forming, grouting, firing, and the production quality of products. Plasticizers are usually a class of chemical substances used to increase the flexibility, ductility, and processing performance of materials.

[0003] Bentonite is a natural clay mineral mainly composed of montmorillonite, and has the following characteristics: (1) high water absorption, bentonite can absorb water and expand to form a colloidal structure; (2) high plasticity, with good flexibility and viscosity when containing water and becoming hard after drying; (3) suspension and lubricity, which can increase the fluidity of the system after being dispersed in water. Bentonite is often added to the formula of clay or kaolin, especially to the billets of porcelain and pottery. Its main function is to enhance plasticity, make the mud easier to form, and reduce cracking. However, bentonite also has the following disadvantages: after absorbing water and expanding, it is prone to cracking during the drying stage. The main reason for cracking is the different evaporation rates inside and outside, resulting in a water gradient inside the soil body. The greater the water gradient, the more uneven the shrinkage of the billet. When the shrinkage force of the soil body exceeds its tensile strength, the soil body will crack. Organic plasticizers, such as carboxymethyl cellulose and polyvinyl alcohol, have good plasticizing and bonding properties, and can improve the plasticity of clay mud, making it easier to form. However, organic molecules may decompose prematurely during the calcination process, resulting in too rapid gas evolution. If the gas cannot be discharged in time, cracks may form in the billet, affecting the quality of the finished product. Summary of the Invention

[0004] In order to overcome the deficiencies of the above-mentioned prior art, the present invention provides a porous functional ceramic material with high plasticity, using modified bentonite as a plasticizer for ceramics. By modifying the surface layer of bentonite with a water-absorbing organic polymer structure, its water retention ability is enhanced, preventing the rapid evaporation of water, resulting in uneven shrinkage of the billet. Moreover, the hydroxyl and carboxyl structures on the surface can enhance the bonding between soil bodies, effectively preventing cracking; during the calcination process of the organic polymer structure, a certain amount of gas is released to obtain a ceramic with a porous structure; different thermally stable organic molecular structures are used to modify the surface of bentonite, so that the gas is slowly released, thereby obtaining a ceramic material with uniform pores.

[0005] The technical solution for achieving the purpose of the present invention is as follows: A porous functional ceramic material with high plasticity, which is fired after the ceramic slurry is processed. The ceramic slurry, by mass, includes 2090 - 2190 parts of terra cotta clay, 1100 - 1200 parts of feldspar powder, 2580 - 2680 parts of kaolin, 1000 - 1100 parts of white sand soil, 1300 - 1400 parts of flower soil, 540 - 640 parts of red clay, 10 - 15 parts of manganese dioxide, 100 - 140 parts of plasticizer, and 3600 - 4000 parts of water; The preparation method of the plasticizer is as follows: S1. Bentonite purification: Wet purification is adopted, followed by drying, pulverizing, and screening. S2. Silane modification of bentonite: Bentonite is modified with a silane coupling agent with epoxy groups. S3. Initiator modification of bentonite: The epoxy groups in the silane - modified bentonite react with the amino groups in the initiator to introduce an initiating group. S4. Polymer modification: Under an inert gas atmosphere, 3 - 6 parts of tert - butyl acrylate monomer, 24 - 48 parts of the initiator - modified bentonite, 0.004 - 0.008 parts of cuprous bromide, and 40 - 50 parts of anhydrous N,N - dimethylformamide are added to a reaction kettle, followed by freeze - thaw degassing. Then, 0.04 - 0.08 parts of N,N,N',N'',N'' - pentamethyldiethylenetriamine are added, and the mixture is stirred at 50 - 80 °C for 10 - 24 h. Then, 3 - 6 parts of hydroxyethyl acrylate monomer and 0.004 - 0.008 parts of cuprous bromide are added and stirred for another 10 - 24 h. After the reaction is completed, oxygen is introduced to terminate the reaction. The reaction solution is centrifuged to separate the precipitate, which is washed at least twice with deionized water and alcohol. The precipitate is dispersed in a mixed solvent of dichloromethane and trifluoroacetic acid, and stirred at room temperature for 16 - 24 h. After removing the organic solvent, the pH is adjusted to 9 - 11, and the precipitate is centrifuged, washed, and dried to obtain the polymer - modified bentonite. The initiator has the following molecular structure formula: .

[0006] Preferably, the purification steps in step S1 are as follows: Bentonite and water are stirred at a mass ratio of 1:(5 - 7) for 1 - 2 h, and left standing for 16 - 24 h to remove the lower - layer sandy soil; After stirring for 10 - 30 min, water is added to prepare a slurry with a mass ratio of bentonite ore powder to water of 1:(9 - 12), stirred for 20 - 30 min, left standing for 5 - 6 h, and then the supernatant is recovered. The upper - layer refined soil is taken out from the sediment, the lower - layer sandy soil is discarded, the upper - layer refined soil is suction - filtered, put into an electro - thermal constant - temperature drying oven for drying, pulverized, and screened with a 200 - mesh sieve.

[0007] Preferably, the detailed steps of the silane-modified bentonite in step S2 are as follows: Disperse the bentonite obtained in step S1 in a mixed solvent of alcohol and water, then add a silane coupling agent containing an epoxy group, stir at a temperature of 40-60 °C for 8-12 h, centrifuge the reaction solution to separate the precipitate, wash and dry to obtain silane-modified bentonite; the mass ratio of the bentonite, silane coupling agent and mixed solvent is (4-6):(0.5-1):(30-50); the volume ratio of the alcohol and water is (1-10):1; the alcohol is at least one of methanol and ethanol; the silane coupling agent with an epoxy group is at least one of 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.

[0008] Preferably, the detailed steps of the initiator-modified bentonite in step S3 are as follows: Add 4-6 parts of the silane-modified bentonite obtained in step S2 and disperse it in 30-50 parts of dry tetrahydrofuran. Under a nitrogen atmosphere, add 0.5-1 part of the initiator, heat up to 50-60 °C, react for 10-16 h, centrifuge the reaction solution to separate the precipitate, wash and vacuum dry to obtain the initiator-modified bentonite.

[0009] Preferably, in step S4, the tert-butyl acrylate monomer is at least one of tert-butyl acrylate and tert-butyl methacrylate; the hydroxy acrylate monomer is at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; the pH adjustment is carried out using an aqueous solution prepared with one or several of sodium hydroxide, sodium carbonate and sodium bicarbonate.

[0010] Preferably, the bentonite is at least one of sodium-based bentonite and calcium-based bentonite.

[0011] A preparation method of a highly plastic porous functional ceramic material includes the following steps: Making mud, forming, watering, bisque firing, glazing, kiln glazing firing, colored porcelain; The making of mud is as follows: grind the ceramic slurry into mixed mud by a ball mill, filter the particulate matter through a vibrating filter screen device, extrude the excess water through a mud pressing bed device, and finally add a clay kneader to further remove the air in the mud to finally form a mud strip; The forming is to select roll forming or slip casting to obtain a green body; The watering is to polish the burrs and particles of the green body with a wet sponge; The final temperature of the biscuit firing is 600~1000 °C, and the steps are as follows: heating from room temperature to 200 °C at a heating rate of 50~100 °C / h; from 200~600 °C at a heating rate of 30~60 °C / h; from 600~1000 °C at a heating rate of 90~110 °C / h; after heating to the final temperature, keep warm for 1~2 h; The final temperature of the glaze firing in the kiln is 900~1200 °C, and the steps are as follows: heating from room temperature to 500 °C at a heating rate of 100~150 °C / h; from 500~900 °C at a heating rate of 50~100 °C / h; from 900~1200 °C at a heating rate of 50~80 °C / h; after heating to the final temperature, keep warm for 1~2 h; then cool down at a cooling rate of 50~100 °C / h until it reaches 600 °C and then cool naturally; The colored porcelain is at least one of the powder spraying process or the painting process; the ceramic material is the above-mentioned ceramic material.

[0012] The present invention also protects the application of the ceramic material obtained by the preparation method of a highly plastic porous functional ceramic material in a ceramic flower pot. A rolling forming or slip casting mold in the shape of a flower pot is selected to obtain a flower pot for soil cultivation. Beneficial effects

[0013] The present invention has the following beneficial effects: 1. Using polymer-modified bentonite as a plasticizer for ceramic slurry makes the ceramic slurry have good plasticity. By modifying the water-absorbing organic polymer structure on the surface of bentonite, the rapid evaporation of water during the drying stage is reduced, resulting in uneven shrinkage of the green body. The hydrogen bond structure enhances the bonding between the soil bodies and further prevents cracking; the organic polymer is a block copolymer. The inner layer close to bentonite is a carboxylate structure, and the outer layer is a hydroxyester structure, with different thermal stabilities. The thermal stability of the inner layer is higher than that of the outer layer. During calcination, the decomposition temperature ranges of the outer layer and the inner layer are different, so that the gas is slowly released, preventing cracks caused by the too-fast escape of gas, and thus obtaining a ceramic material with uniform pores; both the carboxylate in the inner layer and the hydroxyl group in the outer layer are hydrophilic groups. The organic polymer is a dendritic structure, which has more excellent water retention and better lubrication performance compared with the linear structure; it enables the modified bentonite to form a more uniform hydration film after absorbing water, enhancing the flexibility of the mud and playing an excellent plasticizing role.

[0014] During the calcination process of the organic polymer structure, certain gases are released to obtain a ceramic flowerpot with a porous structure. This porous structure enables the flowerpot to have good air permeability, and at the same time is conducive to the discharge and evaporation of excess water in the flowerpot. The porous ceramic has a certain hygroscopicity and moisture retention. When the air humidity is high, the flowerpot can absorb and store the moisture in the air. When the air is dry, it can release the stored moisture, playing a certain role in regulating the soil humidity in the flowerpot and creating a relatively stable humidity environment for plant growth. The porous structure can bring a unique appearance effect to the ceramic flowerpot, increasing its aesthetic and artistic sense, reducing the weight of the flowerpot. At the same time, the good air permeability and water permeability make the soil environment in the flowerpot healthier and not conducive to the growth and reproduction of harmful microorganisms.

[0015] Organic molecular structures with different thermal stabilities are used to modify the surface of bentonite, enabling the slow release of gases, thereby obtaining a ceramic flowerpot with uniform pores. The uniform pores allow the soil in all parts of the flowerpot to conduct sufficient and balanced gas exchange with the outside air. At the same time, it can make the structure of the flowerpot more stable, with a more consistent performance when bearing external forces in all parts, avoiding stress concentration phenomena, so that the overall strength of the flowerpot is more uniform and reducing the risk of cracks or breakage. During the firing process, the uniform pores are conducive to the uniform transfer of heat, making all parts of the flowerpot receive the same heat, thereby ensuring the uniform color of the final product, reducing color differences caused by local overheating or overcooling, and improving the appearance quality and commercial value of the flowerpot. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a schematic diagram of the synthesis, structure and mechanism of the plasticizer of the present invention; Figure 2 It is an XRD spectrum of the calcium-based bentonite and plasticizer 3 used in the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0017] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0018] In the embodiments, unless otherwise specified, the experimental methods used are all conventional methods, and the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0019] Now, the raw materials and equipment used in the examples and comparative examples are described as follows: Red clay: LingShou County DeZhou Mineral Products Processing Factory; Feldspar powder: LingShou County DeZhou Mineral Products Processing Factory; Kaolin: LingShou DeZhou Mineral Products Processing Factory; White sand soil: LingShou DeZhou Mineral Products Processing Factory; Flower soil: LingShou DeZhou Mineral Products Processing Factory; Red pottery clay: LingShou DeZhou Mineral Products Processing Factory; Manganese dioxide: Nantong Runfeng Petrochemical Co., Ltd.; Calcium-based bentonite: Liangyou Bentonite Processing Factory; Glycidoxypropyltriethoxysilane: Guangdong Wengjiang Chemical Reagent Co., Ltd.; tert-Butyl acrylate: Shanghai Macklin; 2-Hydroxyethyl acrylate: Shanghai Macklin; (2-Hydroxy-1,1-bis(hydroxymethyl)ethyl)carbamic acid tert-butyl ester: Bidepharm; Bromo isobutyryl bromide: Shanghai Macklin; (tert-Butoxycarbonyl)ethanolamine: Shanghai Macklin; Poly(2-hydroxyethyl methacrylate): average molecular weight 20000, Guangdong Wengjiang Chemical Reagent; Sodium polymethacrylate: obtained by treating poly(methacrylic acid) (Shaanxi Didu Pharmaceutical Chemical Industry) with an average molecular weight of 20000 with sodium hydroxide; Initiator 1 Cool 1 eq of (2-Hydroxy-1,1-bis(hydroxymethyl)ethyl)carbamic acid tert-butyl ester and 5 eq of triethylamine in an ice bath, and dropwise add 3.2 eq of 2-bromo isobutyryl bromide. Stir the mixture at low temperature for 3 h, then dropwise add 1.5 eq of 2-bromo isobutyryl bromide, continue stirring for 1 h, filter the reactants, wash the precipitate with a small amount of dichloromethane, combine the organic phases, wash the combined organic matter with saturated sodium bicarbonate, then dry with sodium sulfate, filter and concentrate to obtain a residue. After column chromatography, recrystallize in n-hexane, filter and dry to obtain Product 1; Disperse 1 eq of Product 1 in 15 eq of dichloromethane solvent, add an equal volume of trifluoroacetic acid solution, stir at room temperature for 2 h, add 20 eq of dichloromethane, wash the organic phase with saturated sodium bicarbonate, combine the organic phases, remove the solvent, and dry under vacuum to obtain Initiator 1.

[0020] Initiator 2 Compared with the preparation method of Initiator 1, the difference is that (2-Hydroxy-1,1-bis(hydroxymethyl)ethyl)carbamic acid tert-butyl ester is replaced by (tert-Butoxycarbonyl)ethanolamine.

[0021] Plasticizer 1 S1. Bentonite purification: Stir the bentonite ore powder and water at a mass ratio of 1:6 for 1 h, let it stand for 18 h to remove the lower-layer sandy soil; continue to stir for 20 min, then add water to prepare a slurry with a mass ratio of bentonite ore powder to water of 1:10, stir for 30 min, let it stand for 6 h, then recover the supernatant. Take out the upper-layer refined soil from the sediment, discard the lower-layer sandy soil, filter the upper-layer refined soil by suction, put it into an electrothermal constant-temperature drying oven for drying, pulverize it, and screen it with a 200-mesh sieve; S2. Silane-modified bentonite: Disperse 5 parts of the bentonite obtained in step S1 in a mixed solvent of 30 parts of methanol and 10 parts of water, then add 0.6 part of 3-glycidoxypropyltriethoxysilane, stir at 60 °C for 10 h, centrifuge the reaction solution to separate out the precipitate, wash and dry to obtain silane-modified bentonite; S3. Initiator-modified bentonite: Add 5 parts of the silane-modified bentonite obtained in step S2 and disperse it in 40 parts of dry tetrahydrofuran. Under a nitrogen atmosphere, add 1 part of initiator 1, heat up to 60 °C, react for 14 h, centrifuge the reaction solution to separate out the precipitate, wash and dry it under vacuum to obtain initiator-modified bentonite; S4. Polymer modification: Under an inert gas atmosphere, add 3 parts of tert-butyl acrylate monomer, 24 parts of initiator-modified bentonite, 0.006 part of cuprous bromide, and 50 parts of anhydrous N,N-dimethylformamide to the reaction kettle, perform freeze-thaw degassing, then add 0.06 part of N,N,N',N'',N''-pentamethyldiethylenetriamine, stir at 80 °C for 24 h, add 3 parts of hydroxyethyl acrylate monomer and 0.06 part of cuprous bromide and continue to stir for 24 h. After the reaction is completed, introduce oxygen to terminate the reaction. Centrifuge the reaction solution to separate out the precipitate, wash it twice with deionized water and alcohol. Disperse the precipitate in a mixed solvent of dichloromethane and trifluoroacetic acid, stir and react at room temperature for 22 h. After removing the organic solvent, add saturated sodium chloride solution to sodium hydroxide to prepare a saturated sodium chloride solution of 1 mol / L sodium hydroxide, adjust the pH to 10, centrifuge to separate out the precipitate, wash and dry to obtain polymer-modified bentonite.

[0022] Plasticizer 2 Compared with the preparation method of plasticizer 1, the difference is that in step S4, "3 parts of tert-butyl acrylate monomer, 24 parts of initiator-modified bentonite,....... 3 parts of hydroxyethyl acrylate monomer" is replaced by "6 parts of tert-butyl acrylate monomer, 48 parts of initiator-modified bentonite,....... 6 parts of hydroxyethyl acrylate monomer".

[0023] Plasticizer 3 Compared with the preparation method of plasticizer 1, the difference lies in that "24 parts of initiator-modified bentonite" in step S4 is replaced with "30 parts of initiator-modified bentonite".

[0024] Plasticizer 4 Compared with the preparation method of plasticizer 3, the difference lies in that "3 parts of tert-butyl acrylate monomer,....... 3 parts of hydroxy acrylate monomer" in step S4 is replaced with "5 parts of tert-butyl acrylate monomer...... 5 parts of hydroxy acrylate monomer".

[0025] Plasticizer 5 Compared with the preparation method of plasticizer 3, the difference lies in that "3 parts of tert-butyl acrylate monomer" in step S4 is replaced with "3 parts of hydroxy acrylate monomer".

[0026] Plasticizer 6 Compared with the preparation method of plasticizer 3, the difference lies in that "3 parts of hydroxy acrylate monomer" in step S4 is replaced with "3 parts of tert-butyl acrylate monomer".

[0027] Plasticizer 7 Compared with the preparation method of plasticizer 3, the difference lies in that in step S4, 3 parts of hydroxy acrylate monomer and 3 parts of tert-butyl acrylate monomer are added together at the beginning, and the rest of the operations remain unchanged.

[0028] Plasticizer 8 Compared with the preparation method of plasticizer 3, the difference lies in that in step S3, 1 part of initiator 1 is replaced with initiator 2.

[0029] Plasticizer 9 Compared with the preparation method of plasticizer 3, the difference lies in that only steps S1 and S2 are carried out.

[0030] Plasticizer 10 Compared with the preparation method of plasticizer 3, the difference lies in that only step S1 is carried out.

[0031] The following are the test methods for the performance parameters involved in the present invention: Water retention performance: Prepare a core sample with a diameter of 60 mm and a height of 40 mm, place it in a PVC pipe cap with good heat insulation, and only keep the upper surface exposed to the air. Then place it in an oven at the same time, and evaporate and dry it at a certain temperature. Randomly take out the sample every 6 h, and take an appropriate amount of the soil layer at the upper and middle parts of the sample to measure the water content at 0 h, 6 h, and 12 h. The water retention performance is obtained by the following formula: Water retention performance Water retention performance , where the water content n is the water content after 6 h and 12 h of evaporation drying, and the water content 0 is the initial water content.

[0032] Thermal stability test: Using a thermogravimetric analyzer, in an air atmosphere, poly(2-hydroxyethyl methacrylate) and sodium polymethacrylate with the same molecular weight were heated from room temperature to 700 °C at a heating rate of 10 °C / min.

[0033] Porosity test: After the earthenware was fired, the sample to be tested was ultrasonically cleaned for 0.5 h, then taken out and dried to a constant weight at 110 °C. The dry weight of the sample was weighed as M1 with an electronic balance. The impregnating liquid was injected under a vacuum of less than 20 Torr so that the sample was completely immersed; the sample was hung on the hook of the balance immersed in the impregnating liquid, and the mass of the sample in the impregnating liquid M2, that is, the apparent mass M2 of the sample, was measured. Distilled water was used as the impregnating liquid with a density of D L ; Bulk density D b (g / cm 3 ) is calculated as shown in formula 1:

[0034] Pore size distribution test: For the mercury intrusion test sample, after being processed according to the formula to prepare the slurry, it was injected into a cube grid with a side length of 1 cm. After the earthenware was fired, the sample was taken out and the porosity was tested with a mercury intrusion porosimeter.

[0035] A preparation method of a porous functional ceramic material with high plasticity includes the following steps: The ceramic slurry was ground into mixed clay by a ball mill, filtered through a vibrating sieve device to remove particulate matter, excess water was squeezed out by a mud pressing bed device, and finally the air in the clay was further removed by a clay kneading machine to finally form a clay strip, which was injection molded to obtain an earthenware. The rough edges and particles of the earthenware were polished clean with a wet sponge, and then subjected to biscuit firing. The temperature was raised from room temperature to 200 °C at a heating rate of 60 °C / h; from 200 to 600 °C, the heating rate was 45 °C / h; from 600 to 900 °C, the heating rate was 100 °C / h; after heating to the final temperature of 900 °C, it was held for 1 h; after glazing, it was subjected to kiln glazing firing. The temperature was raised from room temperature to 500 °C at a heating rate of 120 °C / h; from 500 to 900 °C, the heating rate was 70 °C / h; from 900 to 1100 °C, the heating rate was 70 °C / h; after heating to the final temperature of 1100 °C, it was held for 2 h; the temperature was decreased at a rate of 80 °C / h until it reached 600 °C and then naturally cooled; color porcelain operation was carried out through the colored drawing process.

[0036] It can be seen from Figure 2 that the interlayer spacing decreases after modification, which is due to the fact that the ionic radius of Na + itself is larger than that of Ca 2+Small. Hydrogen bonding occurred between the carboxyl and hydroxyl groups in the polymer and the groups between the bentonite layers, making the plasticizer structure more compact and regular, thus reducing the layer spacing.

[0037] Table 1 Thermal Stability Test

[0038] Table 2 Ceramic Slurry Formulations of Examples 1 - 6 (kg)

[0039] Table 3 Ceramic Slurry Formulations of Comparative Examples 1 - 6 (kg)

[0040] Table 4 Performance Tests of Materials Prepared from the Formulations of Examples and Comparative Examples

[0041] From the data in Table 4, it can be seen that for the plasticizer prepared by the present invention, within a reasonable range, a ceramic material with uniform volatilization of embryo moisture and uniform porosity distribution can be obtained. And by adjusting the content of volatile organic compounds, the porosity of the flowerpot can be controlled to be greater than 10%, meeting the definition of porous ceramics.

[0042] From the data of Examples 1 - 6, it can be seen that after the ceramic is formed and dried, the water retention performance on the surface and inside has little difference, showing good water retention performance, which can effectively prevent cracks caused by uneven shrinkage of the green body during the drying stage; when the obtained green body is calcined, the gas is discharged at a uniform speed, and the obtained pore size distribution is uniform. From the data of Comparative Examples 1 - 2, it can be seen that for the plasticizers 5 - 6 obtained by modifying the ceramic surface with acrylate or 2 - hydroxyethyl acrylate alone, the water retention performance of the obtained embryo is little different from that in the examples, but after sintering, its porosity is low and the pore size distribution is wide. This is because the gas escapes too fast, resulting in the merger of some pores and the formation of larger pores. From the data of Comparative Example 3, it can be seen that for the plasticizer 7 using an alternating copolymer to modify bentonite, its performance effect is not as good as that of the block copolymers used in the plasticizers 1 - 4 of the examples. The polyacrylate hydroxy ester with poor external thermal stability in the block copolymer decomposes first, and then the sodium acrylate with good internal thermal stability decomposes, achieving a step - by - step decomposition process. From the data of Comparative Example 4, it can be seen that for the plasticizer 8 using a modified linear polymer to modify bentonite, its effect is not as good as that of modifying bentonite with a dendritic structure, and its water retention and pore size distribution effects are not as good as those in the examples. From the data of Comparative Examples 5 - 6, it can be seen that using bentonite modified only by silane or unmodified as plasticizers 9 and 10, their effects are not as good as those of the plasticizers 1 - 4 used in Examples 1 - 6.

[0043] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A porous functional ceramic material with high plasticity, characterized in that, The ceramic material is fired after being processed from ceramic slurry. The ceramic slurry, by mass, comprises 2090 - 2190 parts of terra cotta clay, 1100 - 1200 parts of feldspar powder, 2580 - 2680 parts of kaolin, 1000 - 1100 parts of white sand soil, 1300 - 1400 parts of flower soil, 540 - 640 parts of red pottery clay, 10 - 15 parts of manganese dioxide, 100 - 140 parts of plasticizer, and 3600 - 4000 parts of water; The preparation method of the plasticizer is as follows: S1. Bentonite purification: Wet purification is adopted, and then it is dried, pulverized and sieved; S2. Silane modification of bentonite: Bentonite is modified with a silane coupling agent with epoxy groups; S3. Initiator modification of bentonite: The epoxy groups in the silane - modified bentonite react with the amino groups in the initiator to introduce initiating groups; S4. Polymer modification: Under an inert gas atmosphere, 3 - 6 parts of tert - butyl acrylate monomer, 24 - 48 parts of initiator - modified bentonite, 0.004 - 0.008 parts of cuprous bromide, and 40 - 50 parts of anhydrous N,N - dimethylformamide are added to a reaction kettle, and freeze - thaw degassing is carried out. Then 0.04 - 0.08 parts of N,N,N',N'',N'' - pentamethyldiethylenetriamine are added, and it is stirred at 50 - 80 °C for 10 - 24 h. Then 3 - 6 parts of hydroxyethyl acrylate monomer and 0.004 - 0.008 parts of cuprous bromide are added and stirred for another 10 - 24 h. After the reaction is completed, oxygen is introduced to terminate the reaction. The reaction solution is centrifuged to separate out the precipitate, which is washed at least twice with deionized water and alcohol. The precipitate is dispersed in a mixed solvent of dichloromethane and trifluoroacetic acid, and stirred at room temperature for 16 - 24 h. After removing the organic solvent, the pH is adjusted to 9 - 11, and the precipitate is centrifuged, washed and dried to obtain polymer - modified bentonite; The initiator has the following molecular structure formula: 。 2. The porous functional ceramic material with high plasticity as described in claim 1, characterized in that, The purification steps in step S1 are as follows: Bentonite and water are stirred at a mass ratio of 1:(5 - 7) for 1 - 2 h, and left to stand for 16 - 24 h to remove the lower - layer sandy soil; After stirring for 10 - 30 min, water is added to prepare a liquid mixture with a mass ratio of bentonite ore powder to water of 1:(9 - 12), stirred for 20 - 30 min, left to stand for 5 - 6 h, and then the supernatant is recovered. The upper - layer fine soil is taken out from the sediment, the lower - layer sandy soil is discarded, the upper - layer fine soil is suction - filtered, put into an electro - thermal constant - temperature drying oven for drying, pulverized, and sieved with a 200 - mesh sieve.

3. A porous functional ceramic material with high plasticity as described in claim 1, characterized in that, The detailed steps of the silane modification of bentonite in step S2 are as follows: Disperse the bentonite obtained in step S1 in a mixed solvent of alcohol and water, then add a silane coupling agent containing an epoxy group, stir at a temperature of 40 - 60 °C for 8 - 12 h, centrifuge the reaction solution to separate out the precipitate, wash and dry to obtain silane-modified bentonite; the mass ratio of the bentonite, silane coupling agent and mixed solvent is (4 - 6):(0.5 - 1):(30 - 50); the volume ratio of the alcohol and water is (1 - 10):1; the alcohol is at least one of methanol and ethanol; the silane coupling agent with an epoxy group is at least one of 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.

4. A highly plastic porous functional ceramic material as described in claim 1, characterized in that, The detailed steps of the initiator-modified bentonite in step S3 are as follows: Add 4 - 6 parts of the silane-modified bentonite obtained in step S2 and disperse it in 30 - 50 parts of dry tetrahydrofuran. Under a nitrogen atmosphere, add 0.5 - 1 part of the initiator, heat up to 50 - 60 °C, react for 10 - 16 h, centrifuge the reaction solution to separate out the precipitate, wash and vacuum dry to obtain initiator-modified bentonite.

5. A porous functional ceramic material with high plasticity as described in claim 1, characterized in that, In step S4, the tert-butyl acrylate monomer is at least one of tert-butyl acrylate and tert-butyl methacrylate; the hydroxy acrylate monomer is at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; the pH adjustment is carried out using an aqueous solution prepared with one or several of sodium hydroxide, sodium carbonate and sodium bicarbonate.

6. A highly plastic porous functional ceramic material according to claim 1, characterized in that, The bentonite is at least one of sodium-based bentonite and calcium-based bentonite.

7. A preparation method of a highly plastic porous functional ceramic material, comprising the following steps: Making mud, shaping, watering, bisque firing, glazing, kiln glazing firing, colored porcelain; The making of mud is as follows: Grind the ceramic slurry into mixed mud by a ball mill, filter the particulate matter through a vibrating filter screen device, extrude the excess water through a mud pressing bed device, and finally add a clay kneading machine to further remove the air in the mud to finally form a mud strip; The shaping is to select rolling shaping or slip casting to obtain a green body; The watering is to polish the rough edges and particles of the green body with a wet sponge; The final temperature of the bisque firing is 600 - 1000 °C, and the steps are: heating from room temperature to 200 °C with a heating rate of 50 - 100 °C / h; 200 - 600 °C with a heating rate of 30 - 60 °C / h; 600 - 1000 °C with a heating rate of 90 - 110 °C / h; after heating to the final temperature, keep warm for 1 - 2 h; The final temperature of the kiln glazing firing is 900 - 1200 °C, and the steps are: heating from room temperature to 500 °C with a heating rate of 100 - 150 °C / h; 500 - 900 °C with a heating rate of 50 - 100 °C / h; 900 - 1200 °C with a heating rate of 50 - 80 °C / h; after heating to the final temperature, keep warm for 1 - 2 h; adopt a cooling rate of 50 - 100 °C / h, and after cooling to 600 °C, cool naturally; The colored porcelain is at least one of powder spraying process and painting process; the ceramic material is the ceramic material according to any one of claims 1 - 7.

8. Application of the ceramic material obtained by the preparation method of a highly plastic porous functional ceramic material as described in claim 8 in a ceramic flowerpot.

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