Antibacterial flame-retardant artificial board and preparation method thereof

Abstract

The invention discloses an antibacterial flame-retardant artificial board which comprises the following raw materials in parts by weight: 100 parts of inorganic filler, 10-50 parts of high-molecular prepolymer, 0.1-5 parts of curing agent, 1-20 parts of antibacterial agent and 1-20 parts of flame retardant, and the antibacterial agent is hydrophobic biological ceramic powder; the flame retardant is hydrophobic zirconium phosphate. The preparation method of the antibacterial flame-retardant artificial board comprises the following steps: uniformly mixing an inorganic filler, a high-molecular prepolymer and a flame retardant in advance to obtain an intermediate material; the preparation method comprises the following steps: firstly, adding an antibacterial agent and a curing agent, considering that the antibacterial agent (hydrophobic biological ceramic powder) has certain humidity sensitivity, in the preparation process of the forming material, performing material mixing treatment by adopting a damp-proof condition, and finally, in the material distribution and die casting process of the artificial board, performing material distribution, die casting and curing by adopting a conventional preparation technology of the artificial board. The antibacterial flame-retardant artificial board is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of building materials, and in particular to an antibacterial flame-retardant artificial board and a preparation method thereof. Background Art

[0002] As a new type of polymer material, artificial board, such as artificial quartz stone board, has unique advantages such as non-toxic, pollution-free and rich colors, and is widely used in kitchen and bathroom countertops, dining table countertops, coffee table tops and other decorations as well as the home furnishing industry. Due to the long-term use of artificial board materials without special treatment in high humidity, high temperature, multiple objects and multiple dead corners, a large number of bacteria are easily bred on its surface, resulting in odor, discoloration and a large number of colored microorganisms, which seriously affect the appearance of the board material and threaten human health.

[0003] In addition, since the raw materials for preparing artificial boards contain polymer resin materials, artificial quartz stone boards have a certain degree of flammability, which limits the application scope of artificial quartz stone boards. As consumers' awareness of health and fire safety increases, the development of artificial boards that are both healthy, antibacterial, and highly flame-retardant will become an inevitable trend in the development of the industry.

[0004] The selection and use of antimicrobial agents play a key role in the preparation and application of antimicrobial artificial boards. At present, artificial boards usually use inorganic antimicrobial agents, including metal nano-antimicrobial materials and photocatalyst antimicrobial materials. The key technology for the preparation of antimicrobial artificial boards lies in the selection and preparation of antimicrobial materials, their microscopic uniform distribution inside the artificial board materials, and the controllable release of antimicrobial active factors. Due to many limitations, the practical application of high-performance antimicrobial and flame-retardant artificial boards has not yet been popularized. The main reasons are that, on the one hand, the surface free energy of inorganic antimicrobial powder materials is high, and their poor compatibility with polymer materials causes a strong tendency to agglomerate, resulting in uneven dispersion and inability to effectively exert antibacterial effects; on the other hand, antimicrobial agents are easy to lose their activity during high-temperature processing of artificial boards, or antimicrobial ions, such as silver ions, have poor release controllability and are easy to precipitate on the surface of the board, which cannot achieve the purpose of long-lasting antibacterial. In addition, the reduction of antibacterial silver ions will also cause the product to discolor and affect the appearance and use value. These problems restrict the practical application of antimicrobial agents in artificial boards. In addition, if metal ion-type nano-antibacterial materials, such as silver ions, copper ions, etc., are introduced into artificial boards, long-term contact with humans may also threaten human health.

[0005] In the flame retardant modification of artificial boards, halogen flame retardants, inorganic flame retardants, phosphorus flame retardants and intumescent flame retardants are usually used. However, there are still defects such as the interface compatibility problem between polar flame retardants and polymer substrates and the release of toxic gases due to high temperature. Summary of the invention

[0006] The purpose of the present invention is to provide an antibacterial and flame-retardant artificial board, in which the antibacterial agent and flame retardant used have good compatibility with the polymer substrate, and the board is a high-performance artificial board with both healthy antibacterial and efficient flame retardancy.

[0007] The present invention also aims to provide a method for preparing the antibacterial and flame-retardant artificial board.

[0008] In order to achieve the above object, the solution of the present invention is:

[0009] An antibacterial flame-retardant artificial board comprises the following raw materials, measured by weight: 100 parts of inorganic filler, 10-50 parts of polymer prepolymer, 0.1-5 parts of curing agent, 1-20 parts of antibacterial agent, and 1-20 parts of flame retardant;

[0010] Among them, the inorganic filler is at least one of quartz powder, glass powder, marble powder, dolomite powder, mullite sand, bentonite, glass fiber powder, spodumene powder, attapulgite, halloysite and barite powder, the polymer prepolymer is at least one of unsaturated polyester resin, epoxy resin, polyurethane prepolymer and phenolic resin, the curing agent is at least one of methyl ethyl ketone peroxide, liquid Moka curing agent, polyether amine D230, the antibacterial agent is hydrophobic bioceramic powder; the flame retardant is hydrophobic zirconium phosphate.

[0011] The method for preparing the hydrophobic bioceramic powder comprises the following steps:

[0012] Step 1, collecting abalone shells, first washing the abalone shells with water and drying them;

[0013] Step 2, then calcining the abalone shell at high temperature to obtain a calcined product, wherein the temperature of the high temperature calcination is 1100-1250° C., and the time of the high temperature calcination is 2-24 hours;

[0014] Step 3, then under sealed conditions, grinding and screening the calcined product obtained in step 2 to obtain a bioceramic powder with a particle size range of 1 to 200 μm;

[0015] Step 4: Finally, the bioceramic powder is mixed with the hydrophobically modified silane, and hydrophobically modified at 150 to 250° C. for 2 to 12 hours to obtain a hydrophobic bioceramic powder.

[0016] The hydrophobically modified silane is at least one of methyltriethoxysilane and methyltrimethoxysilane.

[0017] The method for preparing the hydrophobic zirconium phosphate comprises the following steps:

[0018] Step 1: first, under stirring at room temperature, sequentially add an aqueous solution of a zirconium source, an aqueous solution of a template agent, and an aqueous solution of a phosphorus source into a reaction kettle to obtain a reaction solution;

[0019] The zirconium source is zirconium oxychloride octahydrate;

[0020] The phosphorus source is at least one of sodium dihydrogen phosphate and sodium dihydrogen phosphate dihydrate;

[0021] The template agent is at least one of malonic acid, oxalic acid and acetic acid;

[0022] Step 2, then adjust the pH value of the reaction solution to 0.5-2, raise the temperature to 80-105°C, and keep the reaction for 8-24 hours;

[0023] Step 3, then cool to 10-50°C, add a hydrophobic modifier to the reaction solution, stir and keep warm for 0.5-12h;

[0024] Step 4: Finally, after purification and drying, hydrophobic zirconium phosphate is obtained.

[0025] In step 1, the molar ratio of the zirconium source, the phosphorus source and the template is 1:1-3:0.3-3, and the concentrations of the aqueous solution of the zirconium source, the aqueous solution of the template and the aqueous solution of the phosphorus source are 3wt%-80wt% respectively.

[0026] In step 2, the pH value of the reaction solution is adjusted using a 1wt% to 5wt% hydrochloric acid solution. In step 4, the purification is performed by a combination of centrifugal separation and water washing or a combination of plate pressure filtration and water washing. The drying temperature is 60 to 200° C. and the drying time is 0.5 to 5 hours.

[0027] In step 3, the hydrophobic modifier is at least one of methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and ethyltrimethoxysilane, and the added concentration of the hydrophobic modifier is 0.1wt% to 10wt%.

[0028] A method for preparing an antibacterial flame-retardant artificial board comprises the following steps:

[0029] Step 1, firstly, 100 parts of inorganic filler, 10-50 parts of polymer prepolymer, and 1-20 parts of flame retardant are mixed evenly to obtain an intermediate material;

[0030] Step 2, then under moisture-proof conditions, 0.1 to 5 parts of curing agent, 1 to 20 parts of antibacterial agent and the intermediate material are mixed evenly to obtain a molding material;

[0031] Step 3: Finally, the molding material is subjected to fabrication, die-casting, curing and polishing treatments in sequence to obtain the antibacterial and flame-retardant artificial board.

[0032] In step 2, the moisture-proof condition refers to controlling the ambient humidity to be 0% to 20%.

[0033] After adopting the above technical solution, the components of the antibacterial flame-retardant artificial board of the present invention include:

[0034] Taking inorganic filler as the main filler, the particle size and dosage of the inorganic filler are adjusted according to the actual application and conventional preparation experience, wherein the particle size of the inorganic filler can be selected from 10 to 500 meshes;

[0035] In the components, hydrophobic bioceramic powder is added as an antibacterial agent to improve the wettability, dispersibility, and interface bonding strength between the bioceramic powder and the polymer / organic molecules, and to improve the compatibility of the bioceramic powder with the polymer prepolymer, thereby achieving uniform dispersion of the bioceramic powder inside the substrate and avoiding powder agglomeration. In this way, a better antibacterial effect can be achieved under the condition of a smaller amount of antibacterial agent added, thereby improving the comprehensive performance of the material and the added value of the product.

[0036] Hydrophobic zirconium phosphate is added as a flame retardant in the components to improve the wettability, dispersibility and interface bonding strength between zirconium phosphate and polymer / organic molecules, and to improve the compatibility between zirconium phosphate and polymer prepolymers, thereby achieving uniform dispersion of zirconium phosphate inside the substrate and avoiding powder agglomeration. In this way, better flame retardant effects can be achieved with less flame retardant addition, thereby improving the comprehensive performance of the material and the added value of the product.

[0037] In addition, the present invention introduces layered hydrophobic zirconium phosphate into the substrate of the artificial board. The layered hydrophobic zirconium phosphate and the polymer substrate can form a "brick-mortar" bionic layered microstructure similar to the nacre in natural shells, thereby improving the strength and toughness of the artificial board.

[0038] Furthermore, the bioceramic powder was hydrophobically modified. Specifically, natural abalone shells were used and the bioceramic powder was prepared by high-temperature calcination. The bioceramic powder has a natural and efficient antibacterial and anti-mildew effect. The calcination temperature used was 1100°C to 1250°C (higher than the calcination temperature of conventional shellfish, and the final chemical composition is porous calcium oxide). The calcined bioceramic powder was then hydrophobically modified to improve its compatibility in the polymer prepolymer, so that the bioceramic powder can be better dispersed in the polymer / organic medium.

[0039] Furthermore, the zirconium phosphate is hydrophobically modified. The existing zirconium phosphate on the market is usually hydrophilic. After the hydrophobic modification, the zirconium phosphate can have good compatibility with the polymer substrate. The hydrophobic modification process of zirconium phosphate in the present invention is highly innovative. The hydrophobic modification method adopted, on the one hand, utilizes the acidic conditions of the zirconium phosphate solution to achieve the hydrolysis of the hydrophobic modifier, and further achieves the surface modification of the zirconium phosphate; on the other hand, the hydrophobic modifier used can be dissolved in the aqueous environment after acidic hydrolysis to achieve surface hydrophobic modification under aqueous conditions. The entire hydrophobic modification process, with the help of the front-end synthesis environment of zirconium phosphate, does not add new processes and energy consumption, and is low-cost, simple and fast. The prepared hydrophobic zirconium phosphate is layered and can be well dispersed in the polymer / organic medium, giving the material excellent flame retardancy and improving the mechanical properties of the material.

[0040] The invention discloses a method for preparing an antibacterial flame-retardant artificial board. The method comprises the following steps: uniformly mixing an inorganic filler, a polymer prepolymer and a flame retardant in advance to obtain an intermediate material; then adding an antibacterial agent and a curing agent. Considering that the antibacterial agent (hydrophobic bioceramic powder) has certain moisture sensitivity, the invention adopts moisture-proof conditions to carry out mixing treatment in the process of preparing the molding material. Finally, in the process of laying and die-casting the artificial board, conventional preparation technology of the artificial board can be adopted to carry out laying, die-casting and curing to obtain the antibacterial flame-retardant artificial board. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is the XRD pattern of the hydrophobic bioceramic powder prepared in Example 1;

[0042] Figure 2 This is a hydrophobicity test graph of the hydrophobic bioceramic powder prepared in Example 1;

[0043] Figure 3 This is the XRD pattern of the hydrophobic zirconium phosphate prepared in Example 3;

[0044] Figure 4 This is a SEM image of the hydrophobic zirconium phosphate prepared in Example 3;

[0045] Figure 5 It is the hydrophobicity test graph of the products prepared in Comparative Example 3 and Example 3. DETAILED DESCRIPTION

[0046] In order to further explain the technical solution of the present invention, the present invention is described in detail below through specific embodiments.

[0047] 1. Preparation of hydrophobic bioceramic powder

[0048] Example 1

[0049] A method for preparing a hydrophobic bioceramic powder comprises the following steps:

[0050] Step 1, collecting abalone shells, first washing the abalone shells with water and drying them;

[0051] Step 2, then calcining the abalone shell at high temperature, heating the temperature to 1220° C. at a heating rate of 2° C. / min, calcining for 3 hours, and then cooling to room temperature in the furnace to obtain a calcined product;

[0052] Step 3, then under sealed conditions, grinding and screening the calcined product obtained in step 2 to obtain a bioceramic powder with a particle size range of 1 to 10 μm;

[0053] Step 4: Finally, the bioceramic powder is mixed with methyltrimethoxysilane and subjected to hydrophobic modification at 200° C. for 12 h to obtain a hydrophobic bioceramic powder.

[0054] Example 2

[0055] A method for preparing a hydrophobic bioceramic powder comprises the following steps:

[0056] Step 1, collecting abalone shells, first washing the abalone shells with water and drying them;

[0057] Step 2, then calcining the abalone shell at high temperature, heating the temperature to 1250° C. at a heating rate of 2° C. / min, calcining for 2 hours, and then cooling to room temperature in the furnace to obtain a calcined product;

[0058] Step 3, then under sealed conditions, grinding and screening the calcined product obtained in step 2 to obtain a bioceramic powder with a particle size range of 10 to 50 μm;

[0059] Step 4: Finally, the bioceramic powder is mixed with methyltriethoxysilane and subjected to hydrophobic modification at 250° C. for 6 h to obtain a hydrophobic bioceramic powder.

[0060] Comparative Example 1

[0061] The preparation method of the bioceramic powder is substantially the same as the preparation method of Example 1, except that step 4 is not performed, that is, the hydrophobic modification of the bioceramic powder is not performed, and a bioceramic powder that is not hydrophobically modified is obtained.

[0062] Comparative Example 2

[0063] A method for preparing a hydrophobic bioceramic powder comprises the following steps:

[0064] Step 1, collecting abalone shells, first washing the abalone shells with water and drying them;

[0065] Step 2, then calcining the abalone shell at high temperature, heating the temperature to 800° C. at a heating rate of 2° C. / min, keeping the temperature for calcination for 6 hours, and then cooling the temperature to room temperature to obtain a calcined product;

[0066] Step 3, then under sealed conditions, grinding and screening the calcined product obtained in step 2 to obtain a bioceramic powder with a particle size range of 1 to 10 μm;

[0067] Step 4: Finally, the bioceramic powder is mixed with methyltrimethoxysilane and subjected to hydrophobic modification at 200° C. for 12 h to obtain a hydrophobic bioceramic powder.

[0068] 2. Preparation of hydrophobic zirconium phosphate

[0069] Example 3

[0070] A method for preparing hydrophobic zirconium phosphate comprises the following steps:

[0071] Step 1, first, under stirring at room temperature, add a 20wt% aqueous zirconium oxychloride octahydrate solution, an 8wt% aqueous malonic acid solution, and a 30wt% aqueous sodium dihydrogen phosphate dihydrate solution in a reaction kettle to obtain a reaction solution, wherein the molar ratio of zirconium oxychloride octahydrate, sodium dihydrogen phosphate dihydrate and malonic acid is 1:1.8:0.8;

[0072] Step 2, then using 2wt% hydrochloric acid solution to adjust the pH value of the reaction solution to 1.0, raising the temperature to 95°C, and keeping the temperature for reaction for 24h;

[0073] Step 3, then cool to 30°C, add methyltrimethoxysilane to the reaction solution, control the concentration of methyltrimethoxysilane to be 1wt%, stir and keep warm for 6h;

[0074] Step 4: Finally, filter by plate pressure and wash with water, repeat three times, and then dry at 150° C. for 2 hours to obtain hydrophobic zirconium phosphate.

[0075] Example 4

[0076] A method for preparing hydrophobic zirconium phosphate comprises the following steps:

[0077] Step 1, first, under stirring at room temperature, add a 30wt% aqueous zirconium oxychloride octahydrate solution, a 3wt% aqueous oxalic acid solution, and a 10wt% aqueous sodium dihydrogen phosphate solution in a reaction kettle to obtain a reaction solution, wherein the molar ratio of zirconium oxychloride octahydrate, sodium dihydrogen phosphate and oxalic acid is 1:1:3;

[0078] Step 2, then using 2wt% hydrochloric acid solution to adjust the pH value of the reaction solution to 2.0, heating to 80°C, and keeping the temperature for reaction for 12h;

[0079] Step 3, then cool to 50°C, add methyltriethoxysilane to the reaction solution, control the concentration of methyltriethoxysilane to 10wt%, stir and keep warm for 0.5h;

[0080] Step 4: Finally, centrifugal separation and water washing are repeated 8 times, and then dried at 60° C. for 5 hours to obtain hydrophobic zirconium phosphate.

[0081] Example 5

[0082] A method for preparing hydrophobic zirconium phosphate comprises the following steps:

[0083] Step 1, first, under stirring at room temperature, add a 10wt% aqueous zirconium oxychloride octahydrate solution, an 8wt% aqueous acetic acid solution, and a 30wt% aqueous sodium dihydrogen phosphate dihydrate solution into a reaction kettle to obtain a reaction solution, wherein the molar ratio of zirconium oxychloride octahydrate, sodium dihydrogen phosphate dihydrate and malonic acid is 1:3:0.3;

[0084] Step 2, then using 2wt% hydrochloric acid solution to adjust the pH value of the reaction solution to 0.5, heating to 105°C, and keeping the temperature for 8h;

[0085] Step 3, then cool to 10°C, add methyltrimethoxysilane to the reaction solution, control the concentration of methyltrimethoxysilane to 0.1wt%, stir and keep warm for 12h;

[0086] Step 4: Finally, filter by plate pressure and wash with water, repeat three times, and then dry at 200° C. for 0.5 h to obtain hydrophobic zirconium phosphate.

[0087] Comparative Example 3

[0088] The preparation method of the zirconium phosphate is substantially the same as that of Example 3, except that: in step 3, no hydrophobic modifier is added, and the zirconium phosphate is directly purified and dried after cooling to obtain zirconium phosphate that is not hydrophobically modified.

[0089] 3. Preparation of antibacterial flame retardant artificial board

[0090] Example 6

[0091] A method for preparing an antibacterial flame-retardant artificial board comprises the following steps:

[0092] Step 1: First, 100 parts of quartz powder, 20 parts of unsaturated polyester resin (brand name: Fuli FL-680B), and 2 parts of hydrophobic zirconium phosphate prepared in Example 3 are mixed, and dispersed evenly by a high-speed shearing machine to obtain an intermediate material;

[0093] Step 2, then under moisture-proof conditions (ambient humidity is about 10%), 0.2 parts of methyl ethyl ketone peroxide and 1 part of the hydrophobic bioceramic powder prepared in Example 1 are mixed evenly with the intermediate material to obtain a molding material;

[0094] Step 3: Finally, the molding material is subjected to fabrication, vacuum die-casting for 100 seconds (vacuum degree is -0.1 MPa, vibration frequency is 40 Hz), curing at 150°C, and polishing to obtain an antibacterial and flame-retardant artificial board.

[0095] Example 7

[0096] A method for preparing an antibacterial flame-retardant artificial board comprises the following steps:

[0097] Step 1, firstly mix 80 parts of quartz powder, 20 parts of glass powder, 20 parts of unsaturated polyester resin (brand name is Fuli FL-680B), and 4 parts of hydrophobic zirconium phosphate prepared in Example 4, and disperse them evenly using a high-speed shearing machine to obtain an intermediate material;

[0098] Step 2: Then, under moisture-proof conditions (ambient humidity is about 5%), 0.2 parts of methyl ethyl ketone peroxide and 2 parts of the hydrophobic bioceramic powder prepared in Example 2 are mixed evenly with the intermediate material to obtain a molding material;

[0099] Step 3: Finally, the molding material is subjected to fabrication, vacuum die-casting for 180 seconds (vacuum degree is -0.1 MPa, vibration frequency is 20 Hz), curing at 150°C, and polishing treatment in sequence to obtain an antibacterial and flame-retardant artificial board.

[0100] Example 8

[0101] A method for preparing an antibacterial flame-retardant artificial board comprises the following steps:

[0102] Step 1: First, 100 parts of quartz powder, 40 parts of polyurethane prepolymer (grade HC-1590N), and 2 parts of the hydrophobic zirconium phosphate prepared in Example 5 are mixed, and dispersed evenly by a high-speed shearing machine to obtain an intermediate material;

[0103] Step 2, then under moisture-proof conditions (ambient humidity is about 5%), 5 parts of liquid Moka curing agent, 5 parts of the hydrophobic bioceramic powder prepared in Example 1 and the intermediate material are evenly mixed to obtain a molding material;

[0104] Step 3: Finally, the molding material is subjected to fabrication, vacuum die-casting for 180 seconds (vacuum degree is -0.1 MPa, vibration frequency is 10 Hz), curing at 150°C, and polishing to obtain an antibacterial and flame-retardant artificial board.

[0105] Example 9

[0106] A method for preparing an antibacterial flame-retardant artificial board comprises the following steps:

[0107] Step 1: First, 100 parts of marble powder, 50 parts of epoxy resin (brand E-51), and 6 parts of the hydrophobic zirconium phosphate prepared in Example 3 are mixed, and dispersed evenly by a high-speed shearing machine to obtain an intermediate material;

[0108] Step 2, then under moisture-proof conditions (ambient humidity is about 5%), 5 parts of polyetheramine D230, 3 parts of the hydrophobic bioceramic powder prepared in Example 1 and the intermediate material are evenly mixed to obtain a molding material;

[0109] Step 3: Finally, the molding material is subjected to fabrication, vacuum die-casting for 30 seconds (vacuum degree is -0.1 MPa, vibration frequency is 50 Hz), curing at 150°C, and polishing to obtain an antibacterial and flame-retardant artificial board.

[0110] Comparative Example 4

[0111] The preparation method of the artificial board is substantially the same as the preparation method of Example 6, except that: the hydrophobic zirconium phosphate prepared in Example 3 is not added in step 1, and the hydrophobic bioceramic powder prepared in Example 1 is not added in step 2, to obtain an ordinary artificial board.

[0112] Comparative Example 5

[0113] The preparation method of the antibacterial artificial board is substantially the same as the preparation method of Example 6, except that: in step 1, the hydrophobic zirconium phosphate prepared in Example 3 is not added to obtain the antibacterial artificial board.

[0114] Comparative Example 6

[0115] The preparation method of the flame-retardant artificial board is substantially the same as the preparation method of Example 6, except that: in step 2, the hydrophobic bioceramic powder prepared in Example 1 is not added to obtain the flame-retardant artificial board.

[0116] Comparative Example 7

[0117] The preparation method of the antibacterial artificial board is substantially the same as the preparation method of Example 6, except that: hydrophobic zirconium phosphate is not added in step 1, and the non-hydrophobically modified bioceramic powder prepared in Comparative Example 1 is added in step 2 to obtain the antibacterial artificial board.

[0118] Comparative Example 8

[0119] The preparation method of the flame-retardant artificial board is substantially the same as the preparation method of Example 6, except that: in step 1, the zirconium phosphate prepared in Comparative Example 3 without hydrophobic modification is added, and in step 2, no hydrophobic bioceramic powder is added to obtain the flame-retardant artificial board.

[0120] Comparative Example 9

[0121] The preparation method of the antibacterial flame-retardant artificial board is substantially the same as the preparation method of Example 6, except that: in step 1, the non-hydrophobically modified zirconium phosphate prepared in Comparative Example 3 is added, and in step 2, the hydrophobic bioceramic powder prepared in Example 1 is added to obtain the antibacterial flame-retardant artificial board.

[0122] Comparative Example 10

[0123] The preparation method of the antibacterial flame-retardant artificial board is substantially the same as the preparation method of Example 6, except that the hydrophobic zirconium phosphate prepared in Example 3 is added in step 1, and the non-hydrophobically modified bioceramic powder prepared in Comparative Example 1 is added in step 2 to obtain the antibacterial flame-retardant artificial board.

[0124] Comparative Example 11

[0125] The preparation method of the antibacterial flame-retardant artificial board is substantially the same as the preparation method of Example 6, except that: in step 1, the non-hydrophobically modified zirconium phosphate prepared in comparative example 3 is added, and in step 2, the non-hydrophobically modified bioceramic powder prepared in comparative example 1 is added to obtain the antibacterial flame-retardant artificial board.

[0126] Comparative Example 12

[0127] The preparation method of the antibacterial flame-retardant artificial board is substantially the same as the preparation method of Example 6, except that the hydrophobic zirconium phosphate prepared in Example 3 is added in step 1, and the hydrophobic bioceramic powder prepared in Comparative Example 2 is added in step 2 to obtain the antibacterial flame-retardant artificial board.

[0128] In each embodiment and comparative example, methyltrimethoxysilane and methyltriethoxysilane were provided by Nanjing Nengde New Material Technology Co., Ltd.; liquid Moka curing agent was provided by Shandong Jiaying Chemical Technology Co., Ltd.; polyetheramine D230 was provided by Dongguan Taiying Composite Materials Co., Ltd.

[0129] 4. Characterization of hydrophobic bioceramic powder

[0130] from Figure 1 From the XRD characterization, it can be seen that the spectrum shows crystal plane peaks such as (111)(200)(220)(311)(222) belonging to calcium oxide, which shows that the main component of the hydrophobic bioceramic powder prepared in Example 1 is calcium oxide.

[0131] Figure 2 The water drop wettability of the surface of the hydrophobic bioceramic powder prepared in Example 1 is that the obtained hydrophobic bioceramic powder is spread on the double-sided tape, water drops are dropped on it, and its hydrophobic effect is quickly observed. Figure 2It can be seen that the prepared hydrophobic bioceramic powder exhibits a high hydrophobic state and is not easy to react chemically with water.

[0132] 5. Characterization of hydrophobic zirconium phosphate

[0133] from Figure 3 It can be seen that, compared with the standard spectrum of zirconium phosphate, the spectrum of the hydrophobic zirconium phosphate prepared in Example 3 is consistent with the standard spectrum, which shows that the product obtained by the preparation method of the present invention is zirconium phosphate.

[0134] from Figure 4 It can be seen that the prepared zirconium phosphate has a layered structure of stacked sheets.

[0135] Figure 5 The water drop wettability of the surface of the product prepared in Comparative Example 3 (left) and Example 3 (right), that is, the product was spread on the double-sided tape, water droplets were dropped on it, and its hydrophobic effect was observed. Figure 5 It can be seen that the non-hydrophobically modified zirconium phosphate prepared in Comparative Example 3 has a hydrophilic surface and is in an open state, showing a certain hydrophilicity; the hydrophobic zirconium phosphate prepared in Example 3 is in a super-hydrophobic state.

[0136] 6. Performance test of wood-based panels

[0137] The performance tests of the artificial boards prepared in Examples 6 to 9 and Comparative Examples 4 to 12 were carried out using standard methods commonly used in the art, such as JC / T 908-2013, JG / T 463-2014, JC / T 2534-2019, GB / T2570-1995, GB / T2571-1995, GB / T 2568-1995, GB / T17657-2013, GB / T 8626, and GB / T 2406, including tensile strength, crack strength, flexural strength, impact toughness, oxygen index, antibacterial properties, etc.

[0138] The oxygen index refers to the minimum oxygen concentration required for a material to burn in an oxygen-nitrogen mixed gas flow. A high oxygen index means that the material is not easy to burn, and a low oxygen index means that the material is easy to burn.

[0139] Table 1 Performance parameters of the wood-based panels in various embodiments and comparative examples

[0140]

[0141] It can be seen from Table 1 that the antibacterial and flame-retardant artificial panels prepared in Examples 6 to 9 have good flame retardancy, antibacterial properties, as well as tensile strength, dry flexural strength, bending strength and fracture toughness.

[0142] It can be seen from Table 1 that zirconium phosphate was not added in the preparation methods of Comparative Examples 4, 5 and 7, and the oxygen index and mechanical properties of the artificial boards were greatly reduced, which shows that adding zirconium phosphate to the boards can effectively improve the flame retardancy of the boards; after testing, the combustion grade of the artificial boards with the addition of hydrophobic zirconium phosphate reached A, while the combustion grade of the boards without zirconium phosphate was B2.

[0143] The addition of zirconium phosphate can also improve the strength and toughness of the plate at the same time; compared with the non-hydrophobically modified zirconium phosphate (Comparative Example 9), the strength and toughness of the plate are better after adding the hydrophobically modified zirconium phosphate (Example 6). However, the strength and toughness of the plate after adding the non-hydrophobically modified zirconium phosphate are inferior, which may be due to the poor compatibility of the non-hydrophobically modified zirconium phosphate in the plate and the poor dispersion effect, which affects the mechanical properties of the plate.

[0144] As can be seen from Table 1, in Comparative Examples 4, 6 and 8, no bioceramic powder was added, and the boards had no antibacterial properties. When the bioceramic powder prepared by the present invention was added to the boards, the boards had obvious antibacterial properties. Compared with the bioceramic powder prepared at low temperature (Comparative Example 12), the antibacterial properties of the boards prepared by the bioceramic powder prepared at high temperature (Example 6) were better. Compared with the bioceramic powder not hydrophobically modified (Comparative Examples 7 / 10 / 11), the boards prepared by the hydrophobically modified bioceramic powder (Example 6 and Comparative Example 5) had better antibacterial properties.

[0145] The following rules can be summarized from Table 1:

[0146] 1. Adding zirconium phosphate to the raw materials can improve the flame retardancy, strength and toughness of the board;

[0147] 2. Adding hydrophobic zirconium phosphate to the raw materials has better strength and toughness than non-hydrophobically modified zirconium phosphate;

[0148] 3. Add bioceramic powder to the raw materials, and the materials have antibacterial properties;

[0149] 4. Adding hydrophobic bioceramic powder to the raw materials has better antibacterial properties than the non-hydrophobically modified bioceramic powder.

[0150] 5. Add bioceramics prepared by high-temperature calcination to the raw materials.

[0151] Therefore, the antibacterial and flame-retardant artificial board of the present invention has good compatibility between the antibacterial agent and the flame retardant and the polymer substrate, and is a high-performance artificial board with both healthy antibacterial and efficient flame retardancy.

[0152] The above embodiments and drawings do not limit the product form and style of the present invention. Any appropriate changes or modifications made by ordinary technicians in the relevant technical field should be deemed to be within the patent scope of the present invention.

Claims

1. An antibacterial flame-retardant artificial board, characterized in that: The composition comprises the following raw materials in parts by weight: 100 parts of inorganic filler, 10 to 50 parts of polymer prepolymer, 0.1 to 5 parts of curing agent, 1 to 20 parts of antibacterial agent, and 1 to 20 parts of flame retardant; Among them, the inorganic filler is at least one of quartz powder, glass powder, marble powder, dolomite powder, mullite sand, bentonite, glass fiber powder, spodumene powder, attapulgite, halloysite and barite powder, the polymer prepolymer is at least one of unsaturated polyester resin, epoxy resin, polyurethane prepolymer and phenolic resin, the curing agent is at least one of methyl ethyl ketone peroxide, liquid Moka curing agent, polyether amine D230, the antibacterial agent is hydrophobic bioceramic powder; the flame retardant is hydrophobic zirconium phosphate.

2. The antibacterial flame-retardant artificial board according to claim 1, characterized in that: The method for preparing the hydrophobic bioceramic powder comprises the following steps: Step 1, collecting abalone shells, first washing the abalone shells with water and drying them; Step 2, then calcining the abalone shell at high temperature to obtain a calcined product, wherein the temperature of the high temperature calcination is 1100-1250° C., and the time of the high temperature calcination is 2-24 hours; Step 3, then under sealed conditions, grinding and screening the calcined product obtained in step 2 to obtain a bioceramic powder with a particle size range of 1 to 200 μm; Step 4: Finally, the bioceramic powder is mixed with the hydrophobically modified silane, and hydrophobically modified at 150 to 250° C. for 2 to 12 hours to obtain a hydrophobic bioceramic powder.

3. The antibacterial flame-retardant artificial board according to claim 2, characterized in that: The hydrophobically modified silane is at least one of methyltriethoxysilane and methyltrimethoxysilane.

4. The antibacterial flame-retardant artificial board according to claim 1, characterized in that: The preparation method of the hydrophobic zirconium phosphate comprises the following steps: Step 1: first, under stirring at room temperature, sequentially add an aqueous solution of a zirconium source, an aqueous solution of a template agent, and an aqueous solution of a phosphorus source into a reaction kettle to obtain a reaction solution; The zirconium source is zirconium oxychloride octahydrate; The phosphorus source is at least one of sodium dihydrogen phosphate and sodium dihydrogen phosphate dihydrate; The template agent is at least one of malonic acid, oxalic acid and acetic acid; Step 2, then adjust the pH value of the reaction solution to 0.5-2, raise the temperature to 80-105°C, and keep the reaction for 8-24 hours; Step 3, then cool to 10-50°C, add a hydrophobic modifier to the reaction solution, stir and keep warm for 0.5-12h; Step 4: Finally, after purification and drying, hydrophobic zirconium phosphate is obtained.

5. The antibacterial flame-retardant artificial board according to claim 4, characterized in that: In step 1, the molar ratio of the zirconium source, the phosphorus source and the template is 1:1-3:0.3-3, and the concentrations of the aqueous solution of the zirconium source, the aqueous solution of the template and the aqueous solution of the phosphorus source are 3wt%-80wt% respectively.

6. The antibacterial flame-retardant artificial board according to claim 4, characterized in that: In step 2, the pH value of the reaction solution is adjusted using a 1wt% to 5wt% hydrochloric acid solution. In step 4, the purification is performed by a combination of centrifugal separation and water washing or a combination of plate pressure filtration and water washing. The drying temperature is 60 to 200° C. and the drying time is 0.5 to 5 hours.

7. The antibacterial flame-retardant artificial board according to claim 4, characterized in that: In step 3, the hydrophobic modifier is at least one of methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane and ethyltrimethoxysilane, and the added concentration of the hydrophobic modifier is 0.1wt% to 10wt%.

8. A method for preparing an antibacterial flame-retardant artificial board as claimed in claim 1, characterized in that: The following steps are involved: Step 1, firstly, 100 parts of inorganic filler, 10-50 parts of polymer prepolymer, and 1-20 parts of flame retardant are mixed evenly to obtain an intermediate material; Step 2, then under moisture-proof conditions, 0.1 to 5 parts of curing agent, 1 to 20 parts of antibacterial agent and the intermediate material are mixed evenly to obtain a molding material; Step 3: Finally, the molding material is subjected to fabrication, die-casting, curing and polishing treatments in sequence to obtain the antibacterial and flame-retardant artificial board.

9. The method for preparing an antibacterial flame-retardant artificial board according to claim 8, characterized in that: In step 2, the moisture-proof condition refers to controlling the ambient humidity to be 0% to 20%.

Images