Anti-static floor negative oxygen ion long-acting release process and preparation method thereof

Abstract

The invention relates to the field of air treatment materials, in particular to an anti-static floor negative oxygen ion long-acting release technology and a preparation method thereof.Based on modification of polyurethane and introduction of phosphorus and sulfur elements, the adhesive force and water resistance of a coating are remarkably enhanced, meanwhile, the material is endowed with the flame-retardant characteristic, and the anti-static floor negative oxygen ion long-acting release technology is suitable for being applied to a floor. Silane long chains form a compact network structure through a cross-linking reaction, phosphorus and sulfur synergism can generate a carbonization layer at a high temperature, the combustion process is effectively delayed, stable and long-acting release of negative oxygen ions is achieved through arrangement of microcapsules, a conductive network is formed through nano tin antimony oxide, and the coating has the antistatic characteristic; meanwhile, the low-VOC coalescing agent is matched with the defoaming agent, so that the VOC content of the formula is smaller than 50 g / L, the green building material standard is met, the green chemistry concept is met, and wide application scenes are achieved.

Description

Technical Field

[0001] The present invention relates to the field of air treatment materials, and particularly to an anti-static floor negative oxygen ion long-term release process and its preparation method. Background Art

[0002] An anti-static floor is a special functional floor that, through the conductive or electrostatic dissipation characteristics of the material, quickly conducts the surface static charge into the ground to prevent the accumulation of static electricity from causing equipment damage, dust adsorption, or explosion risks.

[0003] With the rapid development of fields such as the electronics industry, medical facilities, and data centers, the performance requirements for special functional floors are increasing day by day. Although traditional anti-static floors can control the surface resistance through conductive materials, they have a single function. Moreover, most existing negative ion floors simply blend tourmaline or photocatalyst, resulting in problems such as uneven dispersion, low release efficiency, short lifespan, and easy performance interference with anti-static components.

[0004] Therefore, according to the above related technologies, it is urgent to develop an anti-static floor negative oxygen ion long-term release process and its preparation method. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to propose an anti-static floor negative oxygen ion long-term release process and its preparation method to solve the problems of single function, low release efficiency, and short lifespan of anti-static floors in the prior art.

[0006] Based on the above purpose, the present invention provides an anti-static floor negative oxygen ion long-term release process and its preparation method.

[0007] A preparation method for an anti-static floor with long-term negative oxygen ion release, the preparation method is as follows:

[0008] Step S1: Add the modified polyurethane emulsion into a high-speed mixer, heat up to 90 - 110 °C, stir at high speed for 15 - 30 min, add a film-forming aid (Texanol), a leveling agent (H-140), and an antifoaming agent (W-0506), stir for 5 - 10 min, then add modified tourmaline microcapsules, nano-antimony tin oxide, and titanium dioxide, stir at high speed for 20 - 30 min, and mix evenly to obtain an anti-static negative oxygen ion coating.

[0009] Step S2: Grind the surface of the floor substrate, with Ra ≤ 1 μm, brush the anti-static negative oxygen ion coating, heat up to 70 - 90 °C, and cure for 10 - 20 min to obtain an anti-static negative oxygen ion floor.

[0010] Preferably, the antistatic negative oxygen ion coating described in step S1 comprises the following raw materials in parts by mass: 40-50 parts of modified polyurethane emulsion, 2-3 parts of film-forming aid, 0.5-1 part of leveling agent, 0.3-0.5 part of defoaming agent, 8-12 parts of modified tourmaline microcapsule, 2-4 parts of nano antimony tin oxide, and 5-8 parts of titanium dioxide.

[0011] Preferably, the preparation method of the modified polyurethane emulsion is as follows:

[0012] Step SS1: Under a nitrogen atmosphere, add 3-(chloromethyl)-2-(hydroxymethyl)phenol and trimethylolphosphine to a butyl acetate solution, heat up to 100-120 °C, and react for 8-10 h. After the reaction is completed, intermediate 1 is obtained.

[0013] Step SS2: Add paraformaldehyde to a chloroform solvent, add calcium hydride, heat up to 20-30 °C, and react for 20-40 min. Then heat up to 50-70 °C, add 11-aminoundecyltrimethoxysilane, heat up to 70-90 °C, add intermediate 1, and react for 50-90 min. After the reaction is completed, intermediate 2 is obtained.

[0014] Step SS3: Under a nitrogen atmosphere, add intermediate 2 and 1-thiophospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane (SPEPA) to a butyl acetate solvent, heat up to 90-110 °C, and fractionally distill and react for 1-3 h. Then heat up to 120-140 °C, and fractionally distill and react for 4-6 h. After the reaction is completed, intermediate 3 is obtained.

[0015] Step SS4: Add intermediate 3 and hexamethylene diisocyanate to a butyl acetate solvent, add the catalyst dibutyltin dilaurate (DBTDL), heat up to 70-90 °C, and react for 2-4 h to obtain a modified polyisocyanate.

[0016] Step SS5: Under a nitrogen atmosphere, add the modified polyisocyanate and polyethylene glycol 400 (PEG400) to a three-necked flask, stir and mix evenly, heat up to 80-90 °C, and react for 2-4 h. Cool down to 35-55 °C, add dimethylolpropionic acid (DMPA) and 1,4-butanediol (BDO), heat up to 70-90 °C, and react for 30-90 min. Cool down to 35-50 °C, add the catalyst dibutyltin dilaurate (DBTDL) and stannous octoate, and then heat up to 60-80 °C, and react for 3-5 h. After the reaction is completed, a modified polyurethane emulsion is obtained.

[0017] Preferably, the molar ratio of 3-(chloromethyl)-2-(hydroxymethyl)phenol to trimethylolphosphine described in step SS1 is 2.8-3.2:1.

[0018] Preferably, the molar ratio of paraformaldehyde, calcium hydride, 11-aminoundecyltrimethoxysilane, and intermediate in step SS2 is 5.5-7:4-5:3-3.5:1.

[0019] Preferably, the molar ratio of intermediate 2 to SPEPA in step SS3 is 1:8-10.

[0020] Preferably, the molar ratio of intermediate 3, DBDTDL, and hexamethylene diisocyanate in step SS4 is 1:0.0005-0.0015:3-3.5;

[0021] The molar ratio of the modified polyisocyanate, PEG400, DMPA, DBTDL, BDO, and stannous octoate in step SS5 is 1:0.2-0.25:0.08-0.14:0.14-0.19:0.007-0.01:0.13-0.18:0.013-0.018.

[0022] Preferably, the preparation method of the modified tourmaline microcapsules is as follows:

[0023] Step A: Add cyanuric chloride, 3-hydroxybenzoyl chloride, sodium hydroxide, and deionized water to an acetone solvent, stir and react for 2-3 h. After the reaction is completed, intermediate 4 is obtained;

[0024] Step B: Add fine tourmaline powder to an N,N-dimethylformamide (DMF) solvent, heat to 30-50 °C, add intermediate 4, and react for 1-3 h to obtain modified tourmaline;

[0025] Step C: Add ethyl cellulose and modified tourmaline to a dichloromethane solvent, stir evenly, add the emulsifier sodium dodecyl sulfate (SDS), stir for 5-15 min, heat to 30-40 °C, and continue to stir and react for 2-4 h. After the reaction is completed, modified tourmaline microcapsules are obtained.

[0026] Preferably, the molar ratio of cyanuric chloride, 3-hydroxybenzoyl chloride, sodium hydroxide, and deionized water in step A is 1:4.3-4.7:5.8-6.2:58-60;

[0027] The dosage ratio of tourmaline to intermediate 4 in step B is 1 g:0.0028-0.0032 mol;

[0028] The mass ratio of modified tourmaline, ethyl cellulose, and SDS in step C is 1:1.8-2.2:0.14-0.16.

[0029] Preferably, for an antistatic floor with long-term negative oxygen ion release process, the negative oxygen ion activation process is as follows:

[0030] Ultraviolet excitation: Irradiate with UV-C band (254 nm) for 20 - 40 min to activate the photocatalytic activity of TiO2;

[0031] Hydrothermal treatment: Heat up to 50 - 70 °C, with humidity of 80 - 90%, and place for 22 - 26 h to promote the polarization of tourmaline.

[0032] Advantages of the present invention:

[0033] The present invention provides a preparation method for long-term release of negative oxygen ions on an anti-static floor. The coating prepared by the present invention combines a low-volatile organic compound (VOC) film-forming agent with an anti-foaming agent, making the VOC content meet the green building material standard, achieving environmental protection and conforming to the concept of green chemistry.

[0034] The present invention uses a polyurethane emulsion modified with a silane long chain, combined with the introduction of phosphorus and sulfur elements, significantly enhancing the adhesion and water resistance of the coating, while endowing the material with flame retardant properties. The silane long chain forms a dense network structure through cross-linking reactions, and the synergistic effect of phosphorus and sulfur can generate a carbonized layer at high temperatures, effectively delaying the combustion process.

[0035] Through the molecular design of modified tourmaline microcapsules, the present invention realizes the mechanical stability of the microcapsule wall, maintains the spontaneous polarization characteristics of tourmaline, and at the same time, the microcapsule structure can continuously release negative ions, and the ultraviolet absorption ability of triazine groups extends the functional time effect.

[0036] Based on the modification of polyurethane, the present invention realizes high adhesion and high-efficiency flame retardancy of the coating. Through the setting of microcapsules, it realizes the stable and long-term release of negative oxygen ions. Through the formation of a conductive network by nano-antimony tin oxide, the coating has anti-static characteristics. At the same time, through the cooperation of a low-VOC film-forming aid and an anti-foaming agent, the VOC content of the formula is < 50 g / L, meeting the green building material standard, conforming to the concept of green chemistry, and having broad application scenarios. Description of the Drawings

[0037] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only those of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0038] Figure 1 It is the synthesis route diagram of intermediate 3 of the present invention;

[0039] Figure 2 It is the synthesis route diagram of modified tourmaline of the present invention. Detailed Embodiments

[0040] To make the objectives, technical solutions, and advantages of the present invention more clear and understandable, the following further elaborates on the present invention in detail with reference to specific embodiments.

[0041] Example 1: A preparation method for long-term release of negative oxygen ions from an anti-static floor

[0042] Step (1): Under a nitrogen atmosphere, add 280 mmol of 3-(chloromethyl)-2-(hydroxymethyl)phenol and 100 mmol of trimethylolphosphine to 100 mL of butyl acetate solution, heat to 120 °C, react for 8 h. After the reaction is completed, cool and precipitate, and perform vacuum distillation to obtain Intermediate 1.

[0043] Step (2): Add 550 mmol of paraformaldehyde to 150 mL of chloroform solvent, add 400 mmol of calcium hydride, heat to 30 °C, react for 20 min, then heat to 50 °C, add 300 mmol of 11-aminoundecyltrimethoxysilane, heat to 90 °C, add 100 mmol of Intermediate 1, react for 50 min. After the reaction is completed, filter, perform column chromatography separation, and perform low-pressure distillation to obtain Intermediate 2.

[0044] Step (3): Under a nitrogen atmosphere, add 100 mmol of Intermediate 2 and 800 mmol of 1-thiophospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane (SPEPA) to 150 mL of butyl acetate solvent, heat to 90 °C, perform fractional distillation reaction for 3 h, then heat to 120 °C, perform fractional distillation reaction for 4 h. After the reaction is completed, cool down, stir and disperse with absolute ethanol, filter by suction, and dry to obtain Intermediate 3.

[0045] Step (4): Add 100 mmol of Intermediate 3 and 300 mmol of hexamethylene diisocyanate to 100 mL of butyl acetate solvent, add 0.05 mmol of the catalyst dibutyltin dilaurate (DBTDL), heat to 70 °C, react for 4 h. After the reaction is completed, cool down, and perform low-pressure distillation to obtain a modified polyisocyanate.

[0046] Step (5): Under a nitrogen atmosphere, add 100 mmol of the modified polyisocyanate and 20 mmol of polyethylene glycol 400 (PEG400) to a three-necked flask, stir and mix evenly, heat to 80 °C, react for 4 h, cool down to 35 °C, add 8 mmol of dimethylolpropionic acid (DMPA) and 13 mmol of 1,4-butanediol (BDO), heat to 90 °C, react for 30 min, cool down to 50 °C, add 7 mmol of the catalyst dibutyltin dilaurate (DBTDL) and 1.3 mmol of stannous octoate, then heat to 60 °C, react for 5 h. After the reaction is completed, obtain a modified polyurethane emulsion.

[0047] Step (6): Add 100 mmol of cyanuric chloride, 430 mmol of 3-hydroxybenzoyl chloride, 580 mmol of sodium hydroxide, and 5.8 mol of deionized water into 150 mL of acetone solvent, stir and react for 3 h. After the reaction is completed, intermediate 4 is obtained.

[0048] Step (7): Add 100 g of fine tourmaline powder into 200 mL of N,N-dimethylformamide (DMF) solvent, heat up to 50 °C, add 0.28 mol of intermediate 4, and react for 3 h to obtain modified tourmaline.

[0049] Step (8): Add 180 g of ethyl cellulose and 100 g of modified tourmaline into 300 mL of dichloromethane solvent, stir evenly, add 14 g of emulsifier sodium dodecyl sulfate (SDS), stir for 5 min, heat up to 30 °C, and continue to stir and react for 4 h. After the reaction is completed, modified tourmaline microcapsules are obtained.

[0050] Step (9): Add 40 parts by weight of modified polyurethane emulsion into a high-speed mixer, heat up to 110 °C, stir at high speed for 15 min, add 2 parts by weight of film-forming aid (Texanol), 0.5 part by weight of leveling agent (H-140), 0.3 part by weight of defoaming agent (W-0506), stir for 10 min, then add 8 parts by weight of modified tourmaline microcapsules, 2 parts by weight of nano-antimony tin oxide, and 5 parts by weight of titanium dioxide, stir at high speed for 20 - 30 min, and mix evenly to obtain an antistatic negative oxygen ion coating.

[0051] Step (10): Polish the surface of the floor substrate so that Ra ≤ 1 μm, brush the antistatic negative oxygen ion coating, heat up to 90 °C, and cure for 20 min to obtain an antistatic negative oxygen ion floor.

[0052] Example 2: A preparation method for long-term release of negative oxygen ions from an antistatic floor

[0053] Step (1): Under a nitrogen atmosphere, add 300 mmol of 3-(chloromethyl)-2-(hydroxymethyl)phenol and 100 mmol of trimethylolphosphine into 100 mL of butyl acetate solution, heat up to 120 °C, react for 8 h. After the reaction is completed, cool and precipitate, and perform vacuum distillation to obtain intermediate 1.

[0054] Step (2): Add 600 mmol of paraformaldehyde into 150 mL of chloroform solvent, add 450 mmol of calcium hydride, heat up to 25 °C, react for 30 min, then heat up to 60 °C, add 320 mmol of 11-aminoundecyltrimethoxysilane, heat up to 80 °C, add 100 mmol of intermediate 1, and react for 70 min. After the reaction is completed, intermediate 2 is obtained.

[0055] Step (3): Under a nitrogen atmosphere, 100 mmol of intermediate 2 and 900 mmol of SPEPA were added to 150 mL of butyl acetate solvent. The temperature was raised to 100 °C and fractionation reaction was carried out for 2 h. Then the temperature was raised to 130 °C and fractionation reaction was carried out for 5 h. After the reaction was completed, the temperature was lowered. It was stirred and dispersed with absolute ethanol, filtered by suction, and dried to obtain intermediate 3;

[0056] Step (4): 100 mmol of intermediate 3 and 320 mmol of hexamethylene diisocyanate were added to 150 mL of butyl acetate solvent. 1 mmol of catalyst DBTDL was added. The temperature was raised to 80 °C and the reaction was carried out for 3 h to obtain a modified polyisocyanate;

[0057] Step (5): Under a nitrogen atmosphere, 100 mmol of the modified polyisocyanate and 22 mmol of PEG400 were added to a three-necked flask, stirred and mixed evenly. The temperature was raised to 85 °C and the reaction was carried out for 3 h. Then the temperature was lowered to 40 °C. 10 mmol of DMPA and 15 mmol of BDO were added. The temperature was raised to 80 °C and the reaction was carried out for 60 min. Then the temperature was lowered to 40 °C. 0.8 mmol of catalyst DBTDL and 1.5 mmol of stannous octoate were added. Then the temperature was raised to 70 °C and the reaction was carried out for 4 h. After the reaction was completed, a modified polyurethane emulsion was obtained;

[0058] Step (6): 100 mmol of cyanuric chloride, 450 mmol of 3-hydroxybenzoyl chloride, 600 mol of sodium hydroxide, and 5.9 mol of deionized water were added to 150 mL of acetone solvent, and stirred and reacted for 2 - 3 h. After the reaction was completed, intermediate 4 was obtained;

[0059] Step (7): 100 g of fine tourmaline powder was added to 200 mL of DMF solvent. The temperature was raised to 40 °C. 3 mmol of intermediate 4 was added and the reaction was carried out for 2 h to obtain modified tourmaline;

[0060] Step (8): 200 g of ethyl cellulose and 100 g of modified tourmaline were added to 500 mL of dichloromethane solvent, stirred evenly. 15 g of emulsifier SDS was added, and stirred for 10 min. The temperature was raised to 35 °C and stirring reaction was continued for 3 h. After the reaction was completed, modified tourmaline microcapsules were obtained;

[0061] Step (9): 45 parts by weight of the modified polyurethane emulsion was added to a high-speed mixer. The temperature was raised to 95 °C and stirred at high speed for 20 min. 2.5 parts by weight of a film-forming aid, 0.8 part by weight of a leveling agent, and 0.4 part by weight of an antifoaming agent were added, and stirred for 8 min. Then 10 parts by weight of the modified tourmaline microcapsules, 3 parts by weight of nano-antimony tin oxide, and 6 parts by weight of titanium dioxide were added, and stirred at high speed for 25 min to mix evenly to obtain an antistatic negative oxygen ion coating;

[0062] Step (10): Polish the surface of the floor substrate to Ra≤1μm, brush on the antistatic negative oxygen ion coating, heat up to 80°C, and cure for 15 minutes to obtain the antistatic negative oxygen ion floor.

[0063] Example 3: A preparation method for long-term release of negative oxygen ions from antistatic floors

[0064] Step (1): Under a nitrogen atmosphere, add 320 mmol of 3-(chloromethyl)-2-(hydroxymethyl)phenol and 100 mmol of trimethylolphosphine to 150 mL of butyl acetate solution, heat up to 100°C, react for 10 h, after the reaction is completed, cool and precipitate, and perform vacuum distillation to obtain Intermediate 1;

[0065] Step (2): Add 700 mmol of paraformaldehyde to 150 mL of chloroform solvent, add 500 mmol of calcium hydride, heat up to 20°C, react for 40 min, then heat up to 70°C, add 350 mmol of 11-aminoundecyltrimethoxysilane, heat up to 70°C, add 100 mmol of Intermediate 1, and react for 90 min. After the reaction is completed, obtain Intermediate 2;

[0066] Step (3): Under a nitrogen atmosphere, add 100 mmol of Intermediate 2 and 1 mol of SPEPA to 150 mL of butyl acetate solvent, heat up to 90°C, perform fractional distillation reaction for 3 h, then heat up to 120°C, and perform fractional distillation reaction for 6 h. After the reaction is completed, obtain Intermediate 3;

[0067] Step (4): Add 100 mmol of Intermediate 3 and 350 mmol of hexamethylene diisocyanate to butyl acetate solvent, add 0.15 mmol of catalyst DBTDL, heat up to 70°C, and react for 2 h to obtain the modified polyisocyanate;

[0068] Step (5): Under a nitrogen atmosphere, add 100 mmol of the modified polyisocyanate and 25 mmol of PEG400 to a three-necked flask, stir and mix evenly, heat up to 80°C, react for 4 h, cool down to 35°C, add 14 mmol of DMPA and 18 mmol of BDO, heat up to 70°C, react for 90 min, cool down to 35°C, add 1 mmol of catalyst DBTDL and 1.8 mmol of stannous octoate, and then heat up to 60°C and react for 5 h. After the reaction is completed, obtain the modified polyurethane emulsion;

[0069] Step (6): Add 100 mmol of cyanuric chloride, 470 mmol of 3-hydroxybenzoyl chloride, 620 mmol of sodium hydroxide, and 6 mol of deionized water to 200 mL of acetone solvent, stir and react for 2 h. After the reaction is completed, obtain Intermediate 4;

[0070] Step (7): Add 100 g of fine tourmaline powder into 200 mL of DMF solvent, heat up to 30 °C, add 3.2 mmol of intermediate 4, and react for 3 h to obtain modified tourmaline;

[0071] Step (8): Add 220 g of ethyl cellulose and 100 g of modified tourmaline into 500 mL of dichloromethane solvent, stir evenly, add 16 g of emulsifier SDS, stir for 5 min, heat up to 40 °C, and continue to stir and react for 4 h. After the reaction is completed, obtain modified tourmaline microcapsules;

[0072] Step (9): Add 50 parts by weight of modified polyurethane emulsion into a high-speed mixer, heat up to 110 °C, stir at high speed for 15 min, add 3 parts by weight of film-forming aid, 1 part by weight of leveling agent, 0.5 part by weight of defoaming agent, stir for 5 min, then add 12 parts by weight of modified tourmaline microcapsules, 4 parts by weight of nano-antimony tin oxide, and 8 parts by weight of titanium dioxide, stir at high speed for 30 min, and mix evenly to obtain an antistatic negative oxygen ion coating;

[0073] Step (10): Polish the surface of the floor substrate so that Ra ≤ 1 μm, brush the antistatic negative oxygen ion coating, heat up to 70 °C, and cure for 10 min to obtain an antistatic negative oxygen ion floor.

[0074] Comparative Example 1:

[0075] Compared with Example 1, this comparative example did not add nano-antimony tin oxide during the preparation process of the antistatic negative oxygen ion coating. The remaining steps and parameters are the same, and this comparative example will not be repeated. Finally, an antistatic negative oxygen ion floor is obtained.

[0076] Comparative Example 2:

[0077] Compared with Example 1, this comparative example only replaced "modified tourmaline microcapsules" with "silane coupling agent modified tourmaline". The remaining steps and parameters are the same, and this comparative example will not be repeated. Finally, an antistatic negative oxygen ion floor is obtained.

[0078] Comparative Example 3:

[0079] Compared with Example 1, this comparative example only replaced "modified polyurethane emulsion" with "polyurethane emulsion". The remaining steps and parameters are the same, and this comparative example will not be repeated. Finally, an antistatic negative oxygen ion floor is obtained.

[0080] Performance test:

[0081] According to the provisions of the national standard GB1727-92, the paint film was prepared by brushing method. The substrate was tinplate, which was pre-polished with sandpaper to remove rust and oil. The coatings of Examples 1-3 and Comparative Examples 1-4 were taken, and the emulsion was brushed. The dry film thickness was 40μm. During brushing, it was quickly and evenly brushed in the horizontal and vertical directions to ensure that the emulsion did not overflow and the substrate was not left blank.

[0082] The painted films of Examples 1-3 and Comparative Examples 1-4 were placed in a constant temperature (30°C) and constant humidity (relative humidity 40%) chamber for 7 days before the performance test of the paint film could be carried out.

[0083] Antistatic detection:

[0084] The resistivity was tested in accordance with GB / T1410-89 "Test Methods for Volume Resistivity and Surface Resistivity of Solid Insulating Materials".

[0085] Impact resistance detection:

[0086] The impact resistance of the coating was tested in accordance with GB / T1732-1993 "Determination of Impact Resistance of Paint Films".

[0087] Adhesion detection:

[0088] The adhesion of the coating was tested in accordance with GB / T1720-1996 "Determination of Adhesion of Paint Films".

[0089] Flame retardancy detection

[0090] The paint films of Examples 1-3 and Comparative Examples 1-2 were prepared into a size of 100mm×6.5mm×3mm, and the LOI test was carried out using an oxygen index instrument according to the ASTM D2863 standard.

[0091] VOC detection:

[0092] According to the national standard GB18582-2001, the content of volatile organic compounds (VOC) is calculated as follows:

[0093] VOC = (V - V H2O ) × ρ × 10 3

[0094] In the formula:

[0095] VOC---The content of volatile organic compounds in the coating, g / L;

[0096] V----The mass fraction of total volatiles in the coating;

[0097] V H2O ---The mass fraction of water in the coating;

[0098] ρ---The density of the coating at (23±2)°C, g / mL.

[0099] Table 1 Detection data of each example and comparative example

[0100] Item Resistivity / (Ω / sq) Impact Strength / CM Adhesion / Grade VOC (g / L) LOI / % Example 1 <![CDATA[4.33×10 5 > 50 1 29.1 32.8 Example 2 <![CDATA[4.12×10 5 > 50 1 28.3 33.5 Example 3 <![CDATA[4.07×10 5 > 50 1 26.0 34.3 Comparative Example 1 <![CDATA[4.56×10 6 > 50 1 30.1 32.6 Comparative Example 2 <![CDATA[4.30×10 5 > 50 1 29.6 31.6 Comparative Example 3 <![CDATA[4.45×10 5 > 40 2 29.8 28.1

[0101] Determination of aging resistance:

[0102] Select a QUV ultraviolet accelerated aging tester to conduct the aging test on the floor paint films of Examples 1-3 and Comparative Examples 1-3. The aging resistance performance of the paint film is measured by the change in color difference. The smaller the change in color difference, the better the aging resistance performance of the paint film; one cycle is 12 h.

[0103] 1. UVA-340, light intensity 0.89 W / m 2 , irradiate for 8 h, temperature 60 °C;

[0104] 2. Condensation cycle for 4 h, temperature 50 °C;

[0105] 3. Use an ADCI-60-C full-automatic colorimeter to measure the chromaticity dL*, da*, db* of the paint film every 12 h; measure the original chromaticity coordinates dL0*, da0*, db0* before aging, and measure the chromaticity coordinates dL1*, da1*, db1* after aging for a certain period of time, calculate the change value of the chromaticity coordinates before and after to obtain ΔL*, Δa*, Δb*, and then according to the formula:

[0106] ΔE = [(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 1 / 2

[0107] Detection of negative ion release amount:

[0108] Place the negative ion detector IT-10 on the item to be tested to detect the negative oxygen ion concentration, and record the negative ion release amounts of the examples and comparative examples before and after the aging test.

[0109] Table 2 Detection data of aging resistance and negative oxygen ion concentration of each example and comparative example

[0110]

[0111]

[0112] (Note: The subscript number "1" of ΔE1 represents the first cycle of aging)

[0113] Data analysis:

[0114] It can be seen from Table 1 that the antistatic negative oxygen ion floor prepared by the present invention has better antistatic effect and impact resistance, and at the same time it also has good flame retardancy; ​

[0115] In Comparative Example 1, the absence of antimony tin oxide nanoparticles led to the lack of conductive pathways, and the resistivity increased by an order of magnitude compared to Example 1. The reason is that antimony tin oxide nanoparticles are transparent conductive fillers, and their flaky structure can form a conductive network, thereby reducing electrostatic accumulation to achieve the purpose of anti-static.

[0116] Compared with Example 1, the VOC of Comparative Example 2 increased. The reason may be that the microcapsules can reduce the side reaction between the surface hydroxyl groups of tourmaline and the resin, reducing solvent release. Since the ordinary tourmaline is not coated, more dispersants may be required or side reactions may occur, resulting in an increase in VOC. Its limiting oxygen index decreased. The reason is that the modified tourmaline contains triazine groups, and the triazine groups generate non-combustible gases such as nitrogen and ammonia at high temperatures. These non-combustible gases will block the entry of oxygen, thereby significantly increasing the limiting oxygen index of the composite material.

[0117] Compared with Example 1, the impact strength of Comparative Example 3 decreased. The reason may be that the modification with silane long chains can enhance the flexibility and crosslinking density of polyurethane. The molecular chains of unmodified polyurethane are highly rigid, resulting in reduced impact resistance. The reason for the poor adhesion may be that the modification with silane long chains improves the chemical bond binding between polyurethane and the floor, while unmodified polyurethane only relies on physical adsorption, so the adhesion decreases. The LOI decreased significantly. The reason is that Example 1 contains phosphorus, nitrogen, and silicon elements. The nitrogen element will decompose to produce a large amount of non-combustible gases during combustion. These non-combustible gases can dilute the concentration of oxygen around the coating. The silicon element can migrate to the outside of the material during combustion, and the Si-O bond in its molecule will be converted into Si-C bond. The generated white combustion residues and carbides form a covering layer on the surface of the coating, preventing the escape of combustion volatiles and blocking oxygen from contacting the matrix material, thereby improving the flame retardant performance of the coating. The phosphorus element will release a large amount of gases or high-density steam when heated or burned, which can dilute the oxygen and gaseous combustibles in the air and reduce the surface temperature of the combustible, resulting in the termination of combustion.

[0118] As can be seen from Table 2, the anti-static negative oxygen ion floor prepared by the present invention has the characteristics of long-term release of negative oxygen ions and aging resistance.

[0119] Compared with Example 1, the initial negative ion release amount of Comparative Example 1 was similar to that of Example 1, but the release amount decreased significantly after 10 aging cycles. The reason may be that the flaky structure of antimony tin oxide nanoparticles can form a conductive network, helping the charges in the floor to be evenly distributed, thereby reducing the passivation of tourmaline caused by charge accumulation. In Comparative Example 1, the absence of antimony tin oxide nanoparticles will cause local charge accumulation on the surface of tourmaline. After long-term aging, the polarization of tourmaline weakens, resulting in an exacerbation of the attenuation of negative ion release. At the same time, there is a synergistic effect between titanium dioxide and antimony tin oxide nanoparticles to enhance the production of reactive oxygen species by photocatalytic tourmaline. The lack of antimony tin oxide nanoparticles in Comparative Example 1 leads to a decrease in catalytic efficiency after aging.

[0120] Comparative Example 2 has the highest initial negative ion release amount compared to Example 1, but it drops sharply after 10 aging cycles. The reason may be that the high initial release in Comparative Example 2 is due to the uncoated common tourmaline, where the surface active sites on the tourmaline are directly exposed, making it easy to react with water molecules in the air, resulting in a fast negative ion release rate in the initial stage. However, as time goes by, the surface active sites on the tourmaline are completely covered, leading to a rapid decay in the ability to release negative ions in the later stage;

[0121] Comparative Example 3 has the lowest negative ion release amount both initially and after aging compared to Example 1. The reason may be that the antioxidant property of the modified polyurethane is improved. Unmodified polyurethane is prone to degradation in humid heat aging and releases acidic substances, which can damage the surface structure of the tourmaline. Or when the unmodified polyurethane degrades during aging, it causes an increase in microcracks in the coating, resulting in the shedding of tourmaline particles and further reducing the release amount.

[0122] Those of ordinary skill in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

[0123] The present invention aims to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing an antistatic floor for long-term release of negative oxygen ions, characterized in that: The preparation method is as follows: Step S1: adding the modified polyurethane emulsion into a high-speed mixer, heating to 90-110° C., stirring at high speed for 15-30 min, adding a film-forming aid (Texanol), a leveling agent (H-140), and a defoaming agent (W-0506), stirring for 5-10 min, then adding modified tourmaline microcapsules, nano-antimony tin oxide, and titanium dioxide, stirring at high speed for 20-30 min, and mixing evenly to obtain an antistatic negative oxygen ion coating; Step S2: Grind the surface of the floor substrate to Ra≤1μm, apply antistatic negative oxygen ion paint, heat to 70-90°C, and cure for 10-20min to obtain an antistatic negative oxygen ion floor.

2. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 1, characterized in that: The antistatic negative oxygen ion coating in step S1 comprises the following raw materials in parts by weight: 40-50 parts of modified polyurethane emulsion, 2-3 parts of film-forming aid, 0.5-1 parts of leveling agent, 0.3-0.5 parts of defoaming agent, 8-12 parts of modified tourmaline microcapsules, 2-4 parts of nano antimony tin oxide, and 5-8 parts of titanium dioxide.

3. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 1, characterized in that: The modified polyurethane emulsion preparation method is as follows: Step SS1: Under nitrogen environment, add 3-(chloromethyl)-2-(hydroxymethyl)phenol and trihydroxymethylphosphine to butyl acetate solution, raise the temperature to 100-120° C., react for 8-10 hours, and the reaction is completed to obtain intermediate 1; Step SS2: add paraformaldehyde to chloroform solvent, add calcium hydride, heat to 20-30°C, react for 20-40min, then heat to 50-70°C, add 11-aminoundecyltrimethoxysilane, heat to 70-90°C, add intermediate 1, react for 50-90min, and complete the reaction to obtain intermediate 2; Step SS3: Under a nitrogen atmosphere, add intermediate 2 and 1-sulfanylphospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane (SPEPA) to butyl acetate solvent, heat to 90-110° C., fractionate reaction for 1-3 h, then heat to 120-140° C., fractionate reaction for 4-6 h, and the reaction is completed to obtain intermediate 3; Step SS4: adding intermediate 3, hexamethylene diisocyanate into butyl acetate solvent, adding catalyst dibutyltin dilaurate (DBTDL), heating to 70-90° C., reacting for 2-4 hours, to obtain modified polyisocyanate; Step SS5: Under a nitrogen atmosphere, add the modified polyisocyanate and polyethylene glycol 400 (PEG400) into a three-necked flask, stir and mix evenly, heat to 80-90°C, react for 2-4h, cool to 35-55°C, add dimethylolpropionic acid (DMPA) and 1,4-butanediol (BDO), heat to 70-90°C, react for 30-90min, cool to 35-50°C, add catalyst dibutyltin dilaurate (DBTDL) and stannous octoate, heat to 60-80°C, react for 3-5h, and complete the reaction to obtain a modified polyurethane emulsion.

4. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 3, characterized in that: In step SS1, the molar ratio of 3-(chloromethyl)-2-(hydroxymethyl)phenol to trihydroxymethylphosphine is 2.8-3.2:

1.

5. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 3, characterized in that: In step SS2, the molar ratio of paraformaldehyde, calcium hydride, 11-aminoundecyltrimethoxysilane and intermediate 1 is 5.5-7:4-5:3-3.5:

1.

6. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 3, characterized in that: In step SS3, the molar ratio of intermediate 2 to SPEPA is 1:8-10.

7. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 3, characterized in that: The molar ratio of intermediate 3, DBDTDL and hexamethylene diisocyanate in step SS4 is 1:0.0005-0.0015:3-3.5; The molar ratio of the modified polyisocyanate, PEG400, DMPA, DBTDL, BDO and stannous octoate in step SS5 is 1:0.2-0.25:0.08-0.14:0.14-0.19:0.007-0.01:0.13-0.18:0.013-0.

018.

8. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 1, characterized in that: The modified tourmaline microcapsule preparation method is as follows: Step A: Add cyanuric chloride, 3-hydroxybenzoyl chloride, sodium hydroxide and deionized water into acetone solvent, stir and react for 2-3 hours. The reaction is completed to obtain intermediate 4; Step B: Add fine tourmaline powder to N,N-dimethylformamide (DMF) solvent, heat to 30-50° C., add intermediate 4, and react for 1-3 hours to obtain modified tourmaline; Step C: Add ethyl cellulose and modified tourmaline into dichloromethane solvent, stir evenly, add emulsifier sodium dodecyl sulfate (SDS), stir for 5-15 minutes, heat to 30-40° C., continue stirring and reacting for 2-4 hours, and the reaction is completed to obtain modified tourmaline microcapsules.

9. The method for preparing the antistatic floor for long-term release of negative oxygen ions according to claim 8, characterized in that: The molar ratio of cyanuric chloride, 3-hydroxybenzoyl chloride, sodium hydroxide and deionized water in step A is 1:4.3-4.7:5.8-6.2:58-60; The tourmaline and intermediate 4 in step B are used in a ratio of 1 g: 0.0028-0.0032 mol; The mass ratio of the modified tourmaline, ethyl cellulose and SDS in step C is 1:1.8-2.2:0.14-0.

16.

10. A process for long-term release of negative oxygen ions from antistatic flooring according to any one of claims 1 to 9, characterized in that: The negative oxygen ion activation process is as follows: Ultraviolet excitation: UV-C band (254nm) irradiation for 20-40min to activate the photocatalytic activity of TiO2; Wet heat treatment: raise the temperature to 50-70℃, humidity 80-90%, leave for 22-26 hours to promote tourmaline polarization.

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