Waterproof wear-resistant solid wood floor and preparation method thereof

Abstract

The present application relates to solid wood composite floor field, disclose a kind of waterproof wear-resistant solid wood floor and its preparation method, including solid wood floor and waterproof wear-resistant coating, waterproof wear-resistant coating includes: modified acrylic emulsion, modified additive, auxiliary agent;Modified acrylic emulsion includes: methyl methacrylate, butyl acrylate, modified attapulgite etc.;Modified attapulgite is coated with zinc molybdate after using precipitation method with the modified silane coupling agent prepared by using acrylamide and 3-(2,3-epoxypropoxy) propyl trimethoxysilane reaction Grafting is made;Modified additive is substituted with N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine after using pentaerythritol phosphate ester Substitution continues, then the modified flame-retardant intermediate obtained is modified with tetraethyl orthosilicate and vinyltriethoxysilane, and is made into, the present application is endowed with high hardness and waterproof wear resistance to solid wood floor by waterproof wear-resistant coating, and has excellent flame-retardant effect and ultraviolet aging resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of solid wood composite floor, and particularly relates to a waterproof wear-resistant solid wood floor and a preparation method thereof. BACKGROUND

[0002] Wooden floor is more and more popular with consumers due to its natural texture, beautiful color, energy saving and environmental protection, comfortable foot feeling and other advantages, but wooden material is a flammable material, according to GB 50222-2017 "Fireproof Code for Interior Decoration Design of Buildings", the flame-retardant grade of floor materials of public buildings and ordinary residences should reach B1 level (difficult to burn), and the flame-retardant grade of wooden floor without flame-retardant treatment can only reach B2 level (flammable), since the floor is distributed in every corner of the room, once a fire occurs, it has the effect of promoting the spread of the fire scene, so it is of great significance to take necessary flame-retardant measures for the floor.

[0003] At present, the method of brushing paint on the surface of the board is a convenient and effective method for the flame-retardant treatment of wooden floor, and the acrylic paint has excellent water resistance, alkali resistance and adhesion, and is widely used in the field of paint, but the acrylic paint has poor thermal stability, so it needs to be flame-retardant treated in actual application, the existing technology improves the flame-retardant performance of the paint by adding inorganic flame-retardant agent, but the added flame-retardant paint is prepared by physical mixing between the flame-retardant agent and the adhesive (base resin), so there is a risk of loss of the flame-retardant agent, in addition, in order to obtain high flame-retardant performance, the coating amount of the added flame-retardant paint is often greater than 250g / m 2 , and even as high as 500g / m 2 , such a high coating amount will result in that the pores on the surface of the base material are completely covered, which to some extent destroys the unique mechanism feeling of wood and reduces the aesthetic value of wood, in addition, since the acrylic paint uses water as the solvent, the conventional water-based acrylic resin has defects such as low paint film hardness, poor water resistance, insufficient ultraviolet aging resistance and poor wear resistance, which limits the application of the acrylic paint in wooden floor. SUMMARY

[0004] In order to solve the problems mentioned in the background, the purpose of the present application is to provide a waterproof wear-resistant solid wood floor and a preparation method thereof, by coating waterproof wear-resistant paint on the surface of the solid wood floor, the solid wood floor is endowed with high hardness and waterproof wear resistance, and at the same time has excellent flame-retardant effect and ultraviolet aging resistance.

[0005] The purpose of the present application can be realized by the following technical solutions:

[0006] The waterproof wear-resistant solid wood floor comprises a solid wood floor and a waterproof wear-resistant coating applied on the surface of the solid wood floor, and the waterproof wear-resistant coating comprises the following raw materials in parts by weight: modified acrylic emulsion 55-70 parts, modified additive 3-9 parts, film forming aid 2-6 parts, leveling agent 0.2-0.6 parts, thickening agent 0.2-0.5 parts, defoaming agent 0.1-0.3 parts, and deionized water 10-20 parts.

[0007] The modified acrylic emulsion comprises the following raw materials in parts by weight: methyl methacrylate 40-50 parts, butyl acrylate 20-40 parts, modified attapulgite 5-15 parts, emulsifier 1-3 parts, buffer 0.2-0.6 parts, initiator 0.1-0.5 parts, and deionized water 30-55 parts.

[0008] The modified attapulgite is prepared by coating zinc molybdate onto the surface of attapulgite through a precipitation method and then performing a dehydration condensation reaction with a modified silane coupling agent, wherein the modified silane coupling agent is prepared by performing a ring-opening reaction of acrylamide and 3-(2,3-epoxypropoxy)propyl trimethoxysilane.

[0009] The modified additive is prepared by substituting one chlorine atom in phosphorus oxychloride with pentaerythritol phosphate to obtain a flame-retardant intermediate, then substituting the remaining chlorine atoms in the flame-retardant intermediate with N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine to obtain a modified flame-retardant intermediate, and then modifying the modified flame-retardant intermediate with tetraethyl orthosilicate and vinyltriethoxysilane through a continuous sol-gel method.

[0010] Preferably, the preparation method of the modified acrylic emulsion comprises the following steps: weighing the raw materials according to the weight parts, mixing methyl methacrylate, butyl acrylate, modified attapulgite, emulsifier, buffer, and deionized water, uniformly stirring, and then pre-emulsifying under magnetic stirring at 50-55℃ for 30-40min, then increasing the temperature to 75-80℃, adding one-third of the initiator, waiting for the temperature to stabilize, then adding the remaining initiator within 1h, and increasing the temperature to 85-90℃ for reaction for 2-2.5h, and then cooling and discharging after the reaction is completed to obtain the modified acrylic emulsion.

[0011] Preferably, the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2; the buffer is sodium bicarbonate; and the initiator is one of potassium persulfate or ammonium persulfate.

[0012] Preferably, the preparation method of the modified attapulgite comprises the following steps:

[0013] I. Take attapulgite dispersed in deionized water, then add zinc sulfate heptahydrate, ultrasonic oscillation uniform, then drop the mixed solution of sodium molybdate dihydrate and deionized water, placed in 70~75℃ for 10~12h, after the reaction is completed, take out and cool overnight, washed, filtered, dried, to prepare the zinc molybdate coated attapulgite;

[0014] II. Take acrylamide, acetone, 3-(2,3-epoxypropoxy) propyl trimethoxysilane and sodium ethoxide in the reactor, nitrogen is introduced and stirred at room temperature for 3~4h, then add polymerization inhibitor 4-methoxyphenol, placed in 85~100℃ drop 3-(2,3-epoxypropoxy) propyl trimethoxysilane, reaction 2~2.5h, after the reaction is completed, rotary evaporation to remove unreacted substances, to prepare the modified silane coupling agent;

[0015] III. Take zinc molybdate coated attapulgite ultrasonic dispersion in the mixed solution of anhydrous ethanol and deionized water, then add polymerization inhibitor 4-methoxyphenol and modified silane coupling agent, placed in 55~70℃ for 4~8h, after the reaction is completed, filtered, washed, dried, to prepare the modified attapulgite.

[0016] Preferably, the mass ratio of attapulgite, zinc sulfate heptahydrate and sodium molybdate dihydrate in step I is 1.2~1.5:0.7:0.6.

[0017] Preferably, the preparation method of the modified additive comprises the following steps:

[0018] (1) Take phosphorus oxychloride and acetonitrile in the reactor, at 0℃, by constant pressure funnel, acetonitrile solution containing pentaerythritol phosphate is added dropwise into the reactor within 1h, then placed in 75~85℃ reflux reaction for 7~9h, to prepare the flame retardant intermediate;

[0019] (2) Take N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine, acetonitrile and trimethylamine, stir and mix uniformly, then added to the flame retardant intermediate, placed in 70~80℃ reflux reaction for 16~18h, after the reaction is completed, filtered, washed, dried, to prepare the modified flame retardant intermediate;

[0020] (3) Take the modified flame retardant intermediate, ethanol and deionized water in the reactor, use ammonia water to adjust the pH value of the system to 10, then add emulsifier OP-10, heated to 40~45℃, stir and mix for 10~30min, then add tetraethyl orthosilicate, stir for 3.5~4h, then add vinyl triethoxysilane, heated to 55~65℃, continue to stir for 1~1.5h, after the reaction is completed, filtered, washed, dried, to prepare the modified additive.

[0021] Preferably, the molar ratio of the phosphorus oxychloride, pentaerythritol phosphate and N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine is 1:1:1~1.1.

[0022] Preferably, the mass ratio of the modified flame-retardant intermediate, emulsifier OP-10, ethyl silicate and vinyl triethoxysilane is 5:0.1~0.2:1.2~1.5:0.2~0.3.

[0023] Preferably, the film-forming aid is one of propylene glycol methyl ether or ethylene glycol butyl ether; the leveling agent is sodium polyacrylate; the thickening agent is sodium carboxymethyl cellulose; and the defoaming agent is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether.

[0024] The preparation method of the waterproof wear-resistant solid wood floor as described above comprises the following steps:

[0025] S1, weighing each raw material by weight parts;

[0026] S2, stirring and dispersing the modified acrylic emulsion, the modified additive, the defoaming agent and the deionized water uniformly, then adding the film-forming aid, the leveling agent and the thickening agent, and continuing to stir and disperse to prepare the waterproof wear-resistant coating;

[0027] S3, coating the waterproof wear-resistant coating on the surface of the solid wood floor, and preparing the waterproof wear-resistant solid wood floor after curing and forming.

[0028] The beneficial effects of the present application are as follows:

[0029] The present application coats zinc molybdate to the surface of the attapulgite by the precipitation method, wherein the attapulgite has large output and low price, and has excellent thermal stability and mechanical strength; zinc molybdate is often used as a flame retardant or a smoke suppressant; the use of zinc molybdate coated attapulgite can endow the attapulgite with the ability of flame retardation and smoke suppression, and can improve the wear resistance and weather resistance of the polymer; meanwhile, the amino group in the acrylamide reacts with 3-(2,3-epoxypropoxy) propyl trimethoxysilane to form the -NH- group, and then the -NH- group further reacts with 3-(2,3-epoxypropoxy) propyl trimethoxysilane to form the modified silane coupling agent containing two siloxane chains and a double bond at one end; then, the silicon hydroxyl group in the modified silane coupling agent and the hydroxyl group on the surface of the zinc molybdate coated attapulgite undergo dehydration condensation to prepare the polymerizable modified attapulgite containing high water-resistant and wear-resistant siloxane bonds.

[0030] The modified attapulgite is introduced into methyl methacrylate and butyl acrylate monomers as a polymerization monomer to perform emulsion polymerization, so that the modified attapulgite is firmly fixed on the polyacrylate chain, the modified attapulgite is prevented from migrating out from the surface of the emulsion coating film in a short time to cause the decline of the flame retardation, water resistance, wear resistance and weather resistance, and meanwhile, the dispersion uniformity of the zinc molybdate coated attapulgite in the polymer is improved, and the performance defects caused by the agglomeration phenomenon are avoided.

[0031] The application utilizes the phosphoric acid ester of pentaerythritol to replace one chlorine atom in phosphorus oxychloride to prepare a flame-retardant intermediate, then utilizes the -NH- (CH2) 6-NH- group in the hindered amine light stabilizer N,N'-bis- (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and the remaining two end grafted chlorine atoms in the flame-retardant intermediate to form a polymer to prepare a modified flame-retardant intermediate, then utilizes the continuous sol-gel method to cover the modified flame-retardant intermediate with tetraethyl orthosilicate and vinyltriethoxysilane to prepare a modified additive, wherein the silica layer is attached to the surface of the modified flame-retardant intermediate, the generation of carbon and the compactness are improved, the tetraethyl orthosilicate and the vinyltriethoxysilane are composed of the inorganic skeleton formed by the two-dimensional Si-O short chain and the organic substituent group, the interfacial compatibility of the modified flame-retardant intermediate and the organic material can be improved, thus the ideal dispersion in the matrix can be achieved, the mechanical properties of the material are improved, meanwhile, the emulsion coating film has excellent water resistance and wear resistance, in addition, the flame-retardant phosphorus element, the phosphate group and the hindered amine light stabilizer introduced in the modified additive are beneficial to improving the flame retardation and the ultraviolet aging resistance of the emulsion coating film. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0033] The preparation method of the modified attapulgite in the embodiment 1 comprises the following steps:

[0034] I, 5g of attapulgite is dispersed in 40mL of deionized water, then 2.8g of zinc sulfate heptahydrate is added, ultrasonic oscillation is uniformly performed, then a mixed solution of 2.4g of sodium molybdate dihydrate and 10mL of deionized water is added dropwise, and the reaction is performed at 70℃ for 12h, after the reaction is completed, the product is taken out and cooled overnight, and after washing, suction filtration and drying, the zinc molybdate coated attapulgite is prepared;

[0035] II, take 7.1 g of acrylamide, 100 mL of acetone, 23.6 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane and 0.5% mass fraction of sodium ethoxide in a reactor, nitrogen is introduced and stirred at room temperature for 3 h, then 0.002 g of polymerization inhibitor 4-methoxyphenol is added, and 23.6 g of 3-(2,3-epoxypropoxy) propyl trimethoxysilane is added dropwise at 95°C, and reacted for 2 h. After the reaction is completed, the unreacted substances are removed by rotary evaporation to prepare a modified silane coupling agent;

[0036] III, take 5 g of molybdenum acid zinc coated attapulgite and ultrasonic dispersion in a mixture solution of 90 mL of anhydrous ethanol and 20 mL of deionized water, then add 0.002 g of polymerization inhibitor 4-methoxyphenol and 3.5 g of modified silane coupling agent, and react at 60°C for 5 h. After the reaction is completed, it is filtered, washed and dried to prepare a modified attapulgite.

[0037] The preparation method of the modified additive of example 2 comprises the following steps:

[0038] (1) Take 15.3 g of phosphorus oxychloride and 200 mL of acetonitrile in a reactor, and add 18 g of pentaerythritol phosphate in 20 mL of acetonitrile solution dropwise into the reactor through a constant pressure funnel at 0°C within 1 h, then react at 80°C under reflux for 8 h to prepare a flame retardant intermediate;

[0039] (2) Take 39.5 g of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexanediamine, 100 mL of acetonitrile and 50 mL of trimethylamine, and stir and mix uniformly, then add to the flame retardant intermediate, and react at 75°C under reflux for 16 h. After the reaction is completed, it is filtered, washed and dried to prepare a modified flame retardant intermediate;

[0040] (3) Take 50 g of modified flame retardant intermediate, 100 mL of ethanol and 50 mL of deionized water in a reactor, adjust the pH value of the system to 10 with ammonia water, then add 1 g of emulsifier OP-10, heat to 40°C, stir and mix for 20 min, then add 12.5 g of tetraethyl orthosilicate, stir and react for 4 h, then add 2.5 g of vinyl triethoxysilane, heat to 60°C, and continue to stir and react for 1 h. After the reaction is completed, it is filtered, washed and dried to prepare a modified additive.

[0041] The waterproof and wear-resistant coating of example 3 comprises the following raw materials by weight: 57 parts of modified acrylic emulsion, 3.5 parts of modified additive prepared in example 2, 2.2 parts of film forming aid propylene glycol methyl ether, 0.2 parts of leveling agent polyacrylic acid sodium, 0.2 parts of thickening agent carboxymethyl cellulose sodium, 0.1 parts of defoaming agent fatty alcohol polyoxyethylene ether and 10 parts of deionized water;

[0042] The modified acrylic emulsion includes the following raw materials by weight parts: methyl methacrylate 41 parts, butyl acrylate 20 parts, modified attapulgite prepared in Example 1 5.5 parts, emulsifier 1.2 parts, buffer sodium bicarbonate 0.2 parts, initiator potassium persulfate 0.2 parts, and deionized water 32 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0043] The preparation method of the modified acrylic emulsion includes the following steps: weighing each raw material by weight parts, mixing methyl methacrylate, butyl acrylate, modified attapulgite, emulsifier, buffer, and deionized water, stirring uniformly, and then pre-emulsifying at 50℃ under magnetic stirring for 30min, then warming up to 80℃, adding one-third of the initiator, waiting for the temperature to stabilize, then adding the remaining initiator within 1h, and warming up to 85℃ for 2h of reaction, and then cooling down to discharge the product, thereby preparing the modified acrylic emulsion.

[0044] A preparation method of a waterproof wear-resistant solid wood floor includes the following steps:

[0045] S1, weighing each raw material by weight parts;

[0046] S2, stirring and dispersing the modified acrylic emulsion, modified additive, defoaming agent, and deionized water uniformly, then adding film-forming aid, leveling agent, and thickening agent, and continuing to stir and disperse, thereby preparing the waterproof wear-resistant coating;

[0047] S3, coating the waterproof wear-resistant coating on the surface of the solid wood floor, the substrate thickness is 5mm±0.2mm, the test plate size is 300mm×150mm, and the waterproof wear-resistant solid wood floor is prepared after curing and forming.

[0048] A waterproof wear-resistant coating includes the following raw materials by weight parts: modified acrylic emulsion 62 parts, modified additive prepared in Example 2 5.5 parts, film-forming aid ethylene glycol butyl ether 3.4 parts, leveling agent polyacrylic acid sodium 0.4 parts, thickening agent sodium carboxymethyl cellulose 0.3 parts, defoaming agent alkyl phenol polyoxyethylene ether 0.2 parts, and deionized water 15 parts;

[0049] The modified acrylic emulsion includes the following raw materials by weight parts: methyl methacrylate 44 parts, butyl acrylate 30 parts, modified attapulgite prepared in Example 1 10 parts, emulsifier 2.2 parts, buffer sodium bicarbonate 0.4 parts, initiator potassium persulfate 0.3 parts, and deionized water 40 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0050] The preparation method of the modified acrylic emulsion is the same as that in Example 3.

[0051] The preparation method of a waterproof wear-resistant solid wood floor is the same as that in Example 3.

[0052] A waterproof and wear-resistant coating according to Example 5 comprises the following raw materials by weight: modified acrylic emulsion 68 parts, modified additive prepared in Example 2 8.3 parts, film-forming aid propylene glycol methyl ether 5.5 parts, leveling agent sodium polyacrylate 0.5 parts, thickening agent sodium carboxymethyl cellulose 0.4 parts, defoaming agent fatty alcohol polyoxyethylene ether 0.3 parts, deionized water 17 parts;

[0053] The modified acrylic emulsion comprises the following raw materials by weight: methyl methacrylate 49 parts, butyl acrylate 38 parts, modified attapulgite prepared in Example 1 14 parts, emulsifier 2.8 parts, buffer sodium bicarbonate 0.5 parts, initiator potassium persulfate 0.4 parts, deionized water 50 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0054] The preparation method of the modified acrylic emulsion is the same as that in Example 3.

[0055] The preparation method of the waterproof and wear-resistant solid wood floor is the same as that in Example 3.

[0056] A waterproof and wear-resistant coating according to Comparative Example 1 comprises the following raw materials by weight: modified acrylic emulsion 68 parts, modified additive prepared in Example 2 8.3 parts, film-forming aid propylene glycol methyl ether 5.5 parts, leveling agent sodium polyacrylate 0.5 parts, thickening agent sodium carboxymethyl cellulose 0.4 parts, defoaming agent fatty alcohol polyoxyethylene ether 0.3 parts, deionized water 17 parts;

[0057] The modified acrylic emulsion comprises the following raw materials by weight: methyl methacrylate 49 parts, butyl acrylate 38 parts, zinc molybdate-coated attapulgite prepared in Example 1 14 parts, emulsifier 2.8 parts, buffer sodium bicarbonate 0.5 parts, initiator potassium persulfate 0.4 parts, deionized water 50 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0058] The preparation method of the modified acrylic emulsion is the same as that in Example 3.

[0059] The preparation method of the waterproof and wear-resistant solid wood floor is the same as that in Example 3.

[0060] A waterproof and wear-resistant coating according to Comparative Example 2 comprises the following raw materials by weight: modified acrylic emulsion 68 parts, modified additive prepared in Example 2 8.3 parts, film-forming aid propylene glycol methyl ether 5.5 parts, leveling agent sodium polyacrylate 0.5 parts, thickening agent sodium carboxymethyl cellulose 0.4 parts, defoaming agent fatty alcohol polyoxyethylene ether 0.3 parts, deionized water 17 parts;

[0061] The modified acrylic emulsion comprises the following raw materials by weight parts: methyl methacrylate 49 parts, butyl acrylate 38 parts, attapulgite 14 parts, emulsifier 2.8 parts, buffer sodium bicarbonate 0.5 parts, initiator potassium persulfate 0.4 parts, and deionized water 50 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0062] The preparation method of the modified acrylic emulsion is the same as that in Example 3.

[0063] The preparation method of the waterproof wear-resistant solid wood floor is the same as that in Example 3.

[0064] The waterproof wear-resistant coating of Comparative Example 3 comprises the following raw materials by weight parts: modified acrylic emulsion 68 parts, modified flame-retardant intermediate prepared in Example 2 8.3 parts, film-forming aid propylene glycol methyl ether 5.5 parts, leveling agent polyacrylic acid sodium 0.5 parts, thickening agent sodium carboxymethyl cellulose 0.4 parts, defoaming agent fatty alcohol polyoxyethylene ether 0.3 parts, and deionized water 17 parts.

[0065] The modified acrylic emulsion comprises the following raw materials by weight parts: methyl methacrylate 49 parts, butyl acrylate 38 parts, modified attapulgite prepared in Example 1 14 parts, emulsifier 2.8 parts, buffer sodium bicarbonate 0.5 parts, initiator potassium persulfate 0.4 parts, and deionized water 50 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0066] The preparation method of the modified acrylic emulsion is the same as that in Example 3.

[0067] The preparation method of the waterproof wear-resistant solid wood floor is the same as that in Example 3.

[0068] The waterproof wear-resistant coating of Comparative Example 4 comprises the following raw materials by weight parts: modified acrylic emulsion 68 parts, flame-retardant intermediate prepared in Example 2 8.3 parts, film-forming aid propylene glycol methyl ether 5.5 parts, leveling agent polyacrylic acid sodium 0.5 parts, thickening agent sodium carboxymethyl cellulose 0.4 parts, defoaming agent fatty alcohol polyoxyethylene ether 0.3 parts, and deionized water 17 parts.

[0069] The modified acrylic emulsion comprises the following raw materials by weight parts: methyl methacrylate 49 parts, butyl acrylate 38 parts, modified attapulgite prepared in Example 1 14 parts, emulsifier 2.8 parts, buffer sodium bicarbonate 0.5 parts, initiator potassium persulfate 0.4 parts, and deionized water 50 parts, wherein the emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2;

[0070] The preparation method of the modified acrylic emulsion is the same as that in Example 3.

[0071] The preparation method of the waterproof wear-resistant solid wood floor is the same as that in Example 3.

[0072] Performance test

[0073] The solid wood floor prepared in Examples 3-5 and Comparative Examples 1-4 was subjected to performance test:

[0074] (1) The adhesion was determined by the cross-cut method according to GB / T 9286-2021; the pencil hardness of the coating film was tested according to GB / T 6739-2022, and the data results are shown in Table 1.

[0075] (2) The ultraviolet aging resistance performance test: After the sample was irradiated for 72 h under a 40 W ultraviolet lamp at 60°C, its pencil hardness was tested, the sample was 254 mm away from the lamp tube, and the data results are shown in Table 1.

[0076] (3) The wear resistance performance test: The rubber eraser wiping resistance method was used, and the number of times until the coating film was broken was recorded under the condition of 1 kg weight using a wear resistance testing machine, and the data results are shown in Table 1.

[0077] (4) The flame retardant performance test: The flame retardant performance of the waterproof and wear-resistant coating coated on the surface of the substrate was tested according to GB / T 15442.4-1995, which is the classification and test method for fire performance of decorative fireproof materials - small chamber combustion method, and the data results are shown in Table 1.

[0078] (5) The water resistance test: A clean glass slide was soaked in anhydrous ethanol and then naturally dried, weighed, and recorded as m1; the waterproof and wear-resistant coating prepared in Examples 3-5 and Comparative Examples 1-4 was coated on the glass slide, naturally dried for 7 d, and the edges of the glass slide were trimmed, weighed, and recorded as m2; the paraffin was melted into a liquid state, then the edges of the glass slide were sealed, naturally dried, and weighed, recorded as m3; the glass slide was immersed in fresh water, taken out after 7 d, and the surface was absorbed with filter paper, weighed, and recorded as m4; the water absorption rate of the coating film = (m4-m3) / (m2-m1) x 100%, and the data results are shown in Table 1.

[0079] Table 1 Performance test results of samples

[0080]

[0081] As can be seen from the data results in Table 1, the samples prepared in Examples 3-5 have good adhesion, high pencil hardness, good waterproof and wear resistance, excellent flame retardation and UV aging resistance. In Comparative Example 1, the modified palygorskite is replaced by the zinc molybdate coated palygorskite in equal amount, and in Comparative Example 2, the palygorskite is not modified. The pencil hardness and rubber friction times of Comparative Examples 1-2 are lower than those of Examples 3-5, and the water absorption is higher than that of Examples 3-5, indicating that the grafting of the modified silane coupling agent is beneficial to improving the hardness, wear resistance and water resistance of the material. The mass loss and carbonization volume of Comparative Example 2 are higher than those of Examples 3-5, and the blackening time of the backboard is shorter than that of Examples 3-5, indicating that the coating of zinc molybdate on the palygorskite is beneficial to improving the flame retardation of the material. In Comparative Example 3, the modified additive is replaced by the modified flame-retardant intermediate in equal amount, and in Comparative Example 4, the modified additive is replaced by the flame-retardant intermediate in equal amount. The pencil hardness, rubber friction times and flame retardation of Comparative Examples 3-4 are lower than those of Examples 3-5, and the water absorption is higher than that of Examples 3-5, indicating that the modification of the flame-retardant intermediate with tetraethyl orthosilicate and vinyltriethoxysilane is beneficial to improving the hardness, waterproof and wear resistance and flame retardation of the material. The pencil hardness after UV aging of Comparative Example 4 is significantly lower than that of Example 3-5, which is because the grafting of the hindered amine light stabilizer is beneficial to improving the UV aging resistance of the material.

[0082] In the description of the present specification, the description of the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0083] The basic principles, main features and advantages of the present application are shown and described above. It should be understood by those skilled in the art that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only illustrative of the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A waterproof and wear-resistant solid wood flooring, characterized in that, The invention includes solid wood flooring and a waterproof and wear-resistant coating applied to the surface of solid wood flooring. The waterproof and wear-resistant coating comprises the following raw materials in parts by weight: 55-70 parts modified acrylic emulsion, 3-9 parts modified additives, 2-6 parts film-forming aid, 0.2-0.6 parts leveling agent, 0.2-0.5 parts thickener, 0.1-0.3 parts defoamer, and 10-20 parts deionized water. The modified acrylic emulsion comprises, by weight, the following raw materials: 40-50 parts methyl methacrylate, 20-40 parts butyl acrylate, 5-15 parts modified attapulgite, 1-3 parts emulsifier, 0.2-0.6 parts buffer, 0.1-0.5 parts initiator, and 30-55 parts deionized water. The modified attapulgite is prepared by coating zinc molybdate onto the surface of attapulgite using a precipitation method, followed by a dehydration condensation reaction with a modified silane coupling agent. The modified silane coupling agent is prepared by a ring-opening reaction between acrylamide and 3-(2,3-epoxypropoxy)propyltrimethoxysilane. The modified additive is prepared by replacing one chlorine atom in phosphorus oxychloride with pentaerythritol phosphate to prepare a flame retardant intermediate, and then replacing the remaining chlorine atom in the flame retardant intermediate with N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine to prepare a modified flame retardant intermediate. Subsequently, the modified flame retardant intermediate is modified with tetraethyl orthosilicate and vinyltriethoxysilane using a continuous sol-gel method.

2. The waterproof and wear-resistant solid wood flooring according to claim 1, characterized in that, The preparation method of the modified acrylic emulsion includes the following steps: weigh each raw material according to the weight parts, mix methyl methacrylate, butyl acrylate, modified attapulgite, emulsifier, buffer and deionized water, stir evenly, and then place it at 50~55℃ and magnetically stir for 30~40min for pre-emulsification. Then raise the temperature to 75~80℃, add one-third of the initiator, and after the temperature stabilizes, add the remaining initiator within 1h, and raise the temperature to 85~90℃ to react for 2~2.5h. After the reaction is completed, cool down and discharge the material to prepare the modified acrylic emulsion.

3. The waterproof and wear-resistant solid wood flooring according to claim 2, characterized in that, The emulsifier is a mixture of SDS and OP-10 in a mass ratio of 1:2; the buffer is sodium bicarbonate; and the initiator is either potassium persulfate or ammonium persulfate.

4. The waterproof and wear-resistant solid wood flooring according to claim 1, characterized in that, The method for preparing the modified attapulgite includes the following steps: Ⅰ. Disperse attapulgite in deionized water, then add zinc sulfate heptahydrate, and sonicate until homogeneous. Then add a mixed solution of sodium molybdate dihydrate and deionized water dropwise, and react at 70-75℃ for 10-12 hours. After the reaction is complete, remove and cool overnight. After washing, filtration and drying, zinc molybdate-coated attapulgite is prepared. II. Acrylamide, acetone, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and sodium ethoxide are placed in a reactor. Nitrogen gas is introduced and the mixture is stirred at room temperature for 3-4 hours. Then, the polymerization inhibitor 4-methoxyphenol is added. 3-(2,3-epoxypropoxy)propyltrimethoxysilane is added dropwise at 85-100℃ and the reaction is carried out for 2-2.5 hours. After the reaction is completed, unreacted material is removed by rotary evaporation to prepare the modified silane coupling agent. III. Take zinc molybdate-coated attapulgite and ultrasonically disperse it in a mixed solution of anhydrous ethanol and deionized water. Then add the polymerization inhibitor 4-methoxyphenol and the modified silane coupling agent. React at 55~70℃ for 4~8h. After the reaction is completed, filter, wash and dry to prepare modified attapulgite.

5. The waterproof and wear-resistant solid wood flooring according to claim 4, characterized in that, In step I, the mass ratio of attapulgite, zinc sulfate heptahydrate, and sodium molybdate dihydrate is 1.2~1.5:0.7:0.

6.

6. The waterproof and wear-resistant solid wood flooring according to claim 1, characterized in that, The preparation method of the modified additive includes the following steps: (1) Take phosphorus oxychloride and acetonitrile in a reactor, and add the acetonitrile solution containing pentaerythritol phosphate dropwise to the reactor over 1 hour at 0°C through a constant pressure funnel. Then, reflux the reaction at 75-85°C for 7-9 hours to prepare a flame retardant intermediate. (2) Take N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, acetonitrile and trimethylamine and stir to mix evenly. Then add to the flame retardant intermediate and reflux at 70~80℃ for 16~18h. After the reaction is completed, filter, wash and dry to prepare the modified flame retardant intermediate. (3) Take the modified flame retardant intermediate, ethanol and deionized water into a reactor, adjust the pH of the system to 10 with ammonia water, then add emulsifier OP-10, heat to 40~45℃, stir and mix for 10~30min, then add tetraethyl orthosilicate, stir and react for 3.5~4h, then add vinyltriethoxysilane, heat to 55~65℃, continue stirring and react for 1~1.5h, after the reaction is completed, filter, wash and dry to prepare the modified additive.

7. The waterproof and wear-resistant solid wood flooring according to claim 6, characterized in that, The molar ratio of phosphorus oxychloride, pentaerythritol phosphate and N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine is 1:1:1~1.

1.

8. The waterproof and wear-resistant solid wood flooring according to claim 6, characterized in that, The mass ratio of the modified flame retardant intermediate, emulsifier OP-10, tetraethyl orthosilicate and vinyltriethoxysilane is 5:0.1~0.2:1.2~1.5:0.2~0.

3.

9. The waterproof and wear-resistant solid wood flooring according to claim 1, characterized in that, The film-forming aid is one of propylene glycol methyl ether or ethylene glycol butyl ether; the leveling agent is sodium polyacrylate; the thickener is sodium carboxymethyl cellulose; and the defoamer is one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether.

10. The method for preparing waterproof and wear-resistant solid wood flooring according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1. Weigh each raw material according to its weight parts; S2. The modified acrylic emulsion, modified additives, defoamer and deionized water are stirred and dispersed evenly. Then, film-forming aid, leveling agent and thickener are added, and stirring and dispersion are continued to prepare a waterproof and wear-resistant coating. S3. Apply waterproof and wear-resistant coating to the surface of solid wood flooring, and after curing, prepare waterproof and wear-resistant solid wood flooring.

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