Anti-static self-repairing polyurethane floor slurry and preparation method thereof

Abstract

The invention discloses anti-static self-repairing polyurethane floor slurry and a preparation method thereof, belongs to the technical field of floor slurry preparation, and aims to solve the technical problem that the anti-static performance and the self-repairing performance of the polyurethane floor slurry in the prior art need to be further improved. The material specifically comprises the following raw materials in parts by weight: 80-100 parts of cationic polyurethane and 64-80 parts of an auxiliary material, a cationic chain extender is prepared to hybridize a polyurethane chain segment, so that the wear resistance and hardness of the material are enhanced, the material is endowed with excellent antistatic performance, unsaturated double bonds are introduced, and the antistatic property of the material is improved. A large number of hydroxyl structures in a chain segment after chain extension promote dispersion of the self-repairing filler, unsaturated double bonds serve as active base points to improve the repairing efficiency, and modified siloxane in the self-repairing filler plays a role in repairing the damaged position of the floor and improving the durability of the antistatic performance.

Description

Technical Field

[0001] This invention relates to the field of floor slurry preparation technology, specifically to an antistatic self-healing polyurethane floor slurry and its preparation method. Background Technology

[0002] In modern industrial environments, the performance requirements for flooring materials are constantly upgrading, especially in the fields of electronics manufacturing and precision industry, where the requirements for antistatic and self-healing properties are extremely stringent. To address this need, the development of antistatic self-healing polyurethane flooring slurries has become a key solution. These flooring materials, by optimizing the formulation of self-healing polyurethane, introducing conductive additives, and adjusting the polymer matrix, have successfully achieved a combination of good physical strength and effective static dissipation capabilities. Further technological advancements include the use of nanotechnology to enhance self-healing performance and crosslinking density, enabling the flooring slurry not only to prevent safety issues caused by static electricity but also to withstand higher frequencies of mechanical wear, significantly extending its service life.

[0003] The prior art CN115558379B discloses a method for preparing carbon steel polyurethane flooring, including the following steps: (1) setting a sealing and curing primer layer on the surface of a concrete base layer; (2) setting a leveling layer on the surface of the sealing and curing primer layer; (3) setting a wear-resistant topcoat layer on the surface of the leveling layer. The sealing and curing agent of the sealing and curing primer layer of the present invention has a good sealing and curing effect, which can improve the strength and wear resistance of the concrete structure surface layer, and the addition of antifungal agent can prevent bacteria and mold. The addition of fiber to the leveling layer can improve the crack resistance of the leveling layer and enhance the toughness and structural strength of the flooring. The addition of graphene-modified carbon steel powder to the wear-resistant topcoat layer can greatly improve the hardness of the carbon steel powder after graphene modification, effectively improve the scratch resistance and wear resistance and hardness of the flooring surface, and the antistatic agent can prevent the flooring from easily generating static electricity after adding graphene-modified carbon steel powder.

[0004] However, the aforementioned patent introduces carbon steel into polyurethane flooring to improve its wear resistance and counteracts the negative impact of carbon steel powder on the antistatic properties of the flooring by adding antistatic agents. However, graphene-modified carbon steel has a high electrostatic effect, and it is difficult to bring a positive effect on the antistatic properties of the flooring by introducing polymeric antistatic agents. Furthermore, graphene-modified carbon steel has poor compatibility with polyurethane materials and is prone to agglomeration, thereby reducing the interfacial compatibility between materials. As a result, the wear resistance and antistatic properties of the material need to be further improved. Summary of the Invention

[0005] The purpose of this invention is to provide an antistatic self-healing polyurethane flooring slurry and its preparation method, which solves the technical problem that the antistatic and self-healing properties of polyurethane flooring in the prior art need to be further improved.

[0006] The objective of this invention can be achieved through the following technical solution: an antistatic self-healing polyurethane floor slurry, comprising the following raw material components by weight: 80-100 parts cationic polyurethane and 64-80 parts auxiliary materials;

[0007] The auxiliary materials consist of the following raw materials in parts by weight: 10-12 parts curing agent, 0.5-2 parts leveling agent, 0.5-1 part defoamer, 1-2 parts light stabilizer, 2-3 parts antistatic agent and 50-60 parts deionized water;

[0008] The preparation method of the cationic polyurethane includes the following steps:

[0009] A1. Polyethylene glycol, N,N-dimethylformamide and dibutyltin dilaurate were added to a reaction vessel and stirred to obtain a reaction precursor solution;

[0010] A2. Add the precursor solution to the reactor and stir. Raise the reactor temperature to 50-60℃. Add dimethyl biphenyl diisocyanate solution dropwise to the reactor and keep it at this temperature for 40-60 min. Add a cationic chain extender to the reactor and keep it at this temperature for 20-30 min. Add a self-healing filler to the reactor and keep it at this temperature for 90-120 min. Post-treatment yields cationic polyurethane.

[0011] The reaction equation for preparing cationic polyurethane is as follows:

[0012]

[0013] In the formula: "*" indicates a self-healing filler; "*" indicates an active linker site of the organic chain segment.

[0014] The reaction principle for preparing cationic polyurethane is as follows: During the reaction, dimethyl biphenyl diisocyanate is used as a crosslinking agent. Under the condition of a catalyst, the isocyanate groups on dimethyl biphenyl diisocyanate, as active groups, condense with the hydroxyl groups on polyethylene glycol to form a polyurethane prepolymer with polyethylene glycol segment intercalation. The multi-functional active epoxy groups on the cationic chain extender can react with the hydroxyl groups on the polyurethane prepolymer, promoting the reaction of the polyurethane prepolymer with the active epoxy groups on the self-healing filler after crosslinking, thus obtaining cationic polyurethane.

[0015] Further, in step A1, the ratio of polyethylene glycol, N,N-dimethylformamide, and dibutyltin dilaurate is 6-8g:35-40mL:0.5-0.8g; in step A2, the stirring speed of the reactor is 60-80rpm, and the ratio of the precursor solution, dimethylbiphenyl diisocyanate solution, cationic chain extender, and self-healing filler is 8-10mL:5-6mL:1-2g:2-3g. The dimethylbiphenyl diisocyanate solution is obtained by mixing dimethylbiphenyl diisocyanate and N,N-dimethylformamide at a ratio of 2-3g:5-6mL. The post-treatment includes: after the reaction is completed, the reactor is cooled to room temperature, and the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining cationic polyurethane.

[0016] Furthermore, the curing agent is one or more of isophorone diisocyanate, adipic acid diisocyanate, and diphenylmethane diisocyanate; the leveling agent is one or more of dimethylformamide, butanol, and methyl isobutyl ketone; the defoamer is one or more of dimethyl silicone oil, polydimethylsiloxane, and polyether-modified silicone oil; the light stabilizer is one or two of benzophenone and 3-hydroxybenzophenone; and the antistatic agent is one or more of octadecyltrimethylammonium bromide, sodium dodecyl sulfonate, and distearate dimethylammonium chloride.

[0017] Furthermore, the preparation method of the cationic chain extender is as follows: N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane and dimethylacetamide are added to a reaction vessel. After nitrogen protection, the temperature of the reaction vessel is raised to 50-70℃ and stirred for 20-25 min. Then, triethylamine is added to the reaction vessel and stirred for another 5-8 min. Next, 2-chloroethyl vinyl ether is added dropwise to the reaction vessel for 1-2 h. After stirring for 3-4 h, the cationic chain extender is obtained by post-treatment.

[0018] The reaction equation for preparing cationic chain extenders is as follows:

[0019]

[0020] The reaction principle for preparing cationic chain extenders is as follows: the tertiary amine group on N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane acts as a strong nucleophile, and the lone pair electrons on its nitrogen atom attack the carbon atom on 2-chloroethyl vinyl ether. The chlorine group on 2-chloroethyl vinyl ether acts as a leaving group and is released under nucleophilic attack to form a chloride ion. After the reaction, a positively charged tetrasubstituted nitrogen cation is finally formed, thus obtaining a cationic chain extender.

[0021] Furthermore, the stirring speed of the reactor is 60-80 rpm, and the ratio of N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, dimethylacetamide, triethylamine and 2-chloroethyl vinyl ether is 8.5-9.5 g: 70-80 mL: 1-1.2 g: 4-5 g. The post-treatment includes: after the reaction is completed, the reactor is cooled to room temperature, and the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining a cationic chain extender.

[0022] Furthermore, the preparation method of the self-healing filler includes the following steps:

[0023] B1. Add modified siloxane, tetramethyltetravinylcyclotetrasiloxane, diphenyl (2,4,6-trimethylbenzophenone) and methyl orthosilicate to a reaction vessel and stir for 5-10 minutes to obtain the hydrolysis precursor solution.

[0024] B2. Add the hydrolysis precursor liquid to a high-speed homogenizer, and pour the polyoxyethylene alkyl ether aqueous solution into the hydrolysis precursor liquid. Set the speed of the high-speed homogenizer to 8000-9000 rpm and stir at room temperature for 20-30 minutes to obtain a composite emulsion.

[0025] B3. Add the composite emulsion to the reactor and stir. Add 1-2 mol / L sodium hydroxide aqueous solution to the reactor to adjust the pH of the system to 8-10. Raise the temperature of the reactor to 40-50℃ and keep it at this temperature for 3-4 hours. Then add methyl orthosilicate to the reactor and keep it at this temperature for 2-3 hours. Add methyl orthosilicate to the reactor again and keep it at this temperature for 8-12 hours. The self-healing filler precursor is obtained after post-treatment.

[0026] B4. Add the self-healing filler precursor, ethanol, saturated sodium hydroxide solution and deionized water to the reactor and purge with nitrogen for protection. After the reactor temperature drops to 5-10℃, add 3-(2,3-epoxypropoxy)propyltrimethoxysilane to the reactor and keep it at the temperature for 20-30 min. The self-healing filler is then obtained after post-treatment.

[0027] The reaction principle for preparing self-healing fillers is as follows: after adding deionized water and surfactant to the hydrolysis precursor solution and stirring at high speed, an oil-in-water structure is generated. After adjusting the pH of the system, methyl orthosilicate in the oil phase solution hydrolyzes at the water-oil interface and finally hydrolyzes on the surface of the oil phase droplets to generate a stable cross-linked structure, thus preparing a self-healing filler precursor. Under the protection of an inert gas with low-temperature nitrogen protection, epoxy groups are modified on its surface to obtain the self-healing filler.

[0028] Further, in step B1, the stirring speed of the reactor is 60-80 rpm, and the ratio of modified siloxane, tetramethyltetravinylcyclotetrasiloxane, diphenyl (2,4,6-trimethylbenzophenone) and methyl orthosilicate is 3-4 g: 8-10 g: 0.3-0.5 g: 30-35 mL; in step B2, the ratio of hydrolysis precursor solution to polyoxyethylene alkyl ether aqueous solution is 2-3 g: 10-15 mL, and the polyoxyethylene alkyl ether aqueous solution is prepared by mixing polyoxyethylene alkyl ether and deionized water at a ratio of 1-2 g: 30-40 mL.

[0029] Furthermore, in step B3, the stirring speed of the reactor is 60-80 rpm, the ratio of composite emulsion to methyl orthosilicate is 40-50 mL: 4.4-6.6 mL, the ratio of methyl orthosilicate added twice is 1:1-1.2, and the post-treatment includes: after the reaction is completed, wait for the reactor temperature to drop to room temperature, filter the reaction solution to collect the filter cake, wash the filter cake 3-5 times with anhydrous ethanol and deionized water, transfer the filter cake to a drying oven at 60-80℃, and vacuum dry it to constant weight to obtain the self-healing filler precursor;

[0030] Furthermore, in step B4, the ratio of the self-healing packing precursor, ethanol, saturated sodium hydroxide solution, deionized water, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane is 8-10g:2-3g:2-3mL:40-60mL:3-5g. The post-treatment includes: after the reaction is completed, wait for the temperature of the reaction vessel to drop to room temperature, filter the reaction solution to collect the filter cake, wash the filter cake 3-5 times with anhydrous ethanol and deionized water, transfer the filter cake to a drying oven at a temperature of 60-80℃, and vacuum dry it to constant weight to obtain the self-healing packing.

[0031] Furthermore, the preparation method of modified siloxane includes the following steps:

[0032] C1. Vinylbenzylaminoethylaminopropyltrimethoxysilane, 4,4,4-trifluorobutanal, aluminum chloride and toluene are added to a reaction vessel. The temperature of the reaction vessel is raised to 40-50℃ and the reaction is maintained for 1-2 hours. The modified siloxane precursor is obtained after post-treatment.

[0033] The reaction equation for preparing the modified siloxane precursor is as follows:

[0034]

[0035] The reaction principle for preparing the modified siloxane precursor is as follows: The nitrogen atom in the secondary amino group of vinylbenzylaminoethylaminopropyltrimethoxysilane has a lone pair of electrons, exhibiting nucleophilicity. At the beginning of the reaction, the nitrogen atom of the secondary amino group nucleophilically attacks the carbon of the aldehyde group, forming a transition state, namely a hydroxylamine intermediate with a hydroxyl group and a new CN bond. Further dehydration reaction occurs, losing a water molecule, forming a double bond, and producing an enyl amino group, finally preparing the modified siloxane precursor. The mass spectrometry analysis data of the modified siloxane precursor are: m / z: 432.18 (100.0%), 433.22 (27.2%), 434.23 (4.1%), 434.21 (3.4%), 435.18 (1.1%).

[0036] C2. Add the modified siloxane precursor and dimethylacetamide to the reactor. After purging with nitrogen for protection, raise the reactor temperature to 50-70℃ and stir for 20-25 minutes. Then, add triethylamine to the reactor and continue stirring for 5-8 minutes. Next, add 2-chloroethyl vinyl ether dropwise to the reactor for 1-2 hours. Stir for 3-4 hours and then proceed with post-treatment to obtain the modified siloxane.

[0037] The reaction equation for preparing modified siloxanes is as follows:

[0038]

[0039] The reaction principle for preparing modified siloxanes is as follows: the tertiary amine group on the modified siloxane precursor acts as a strong nucleophile, and the lone pair electrons on its nitrogen atom attack the carbon atom on 2-chloroethyl vinyl ether. The chlorine group on 2-chloroethyl vinyl ether acts as a leaving group and is released under nucleophilic attack to form a chloride ion. After the reaction, a positively charged tetrasubstituted nitrogen cation is finally formed, and the modified siloxane is obtained.

[0040] Further, in step C1, the ratio of vinylbenzylaminoethylaminopropyltrimethoxysilane, 4,4,4-trifluorobutanal, aluminum chloride, and toluene is 9-10 g: 3-4 g: 0.3-0.5 g: 35-40 mL. The post-processing includes: after the reaction is completed, the reaction vessel is cooled to room temperature, and the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining the modified siloxane precursor.

[0041] Furthermore, in step C2, the stirring speed of the reactor is 60-80 rpm, and the ratio of the modified siloxane precursor, dimethylacetamide, triethylamine, and 2-chloroethyl vinyl ether is 9-10 g: 40-45 mL: 0.5-0.8 g: 2.5-3.5 g. The post-treatment includes: after the reaction is completed, the reactor is cooled to room temperature, and the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining the modified siloxane.

[0042] This invention also proposes a method for preparing an antistatic self-healing polyurethane floor slurry: after uniformly mixing cationic polyurethane and auxiliary materials, the mixture is passed through a 200-400 mesh sieve to obtain a polyurethane floor slurry.

[0043] The present invention has the following beneficial effects:

[0044] 1. This invention involves preparing cationic chain extenders to hybridize polyurethane segments, enhancing their wear resistance and hardness while imparting excellent antistatic properties and introducing unsaturated double bonds. The abundant hydroxyl structures within the extended polyurethane segments facilitate the uniform dispersion of self-healing fillers, and the unsaturated double bonds act as active sites to improve repair efficiency, significantly enhancing the material's self-healing efficiency. The modified siloxane structure not only performs repair functions when the material is damaged but also effectively enhances the antistatic durability of the flooring. This dual function ensures that the flooring maintains good performance and appearance even after long-term use. The cyclic tetramethyltetravinylcyclotetrasiloxane enriches the complexity of the self-polymerizing material segments, thereby further improving the material's wear resistance and hardness, making the repair process more efficient and stable, and endowing the flooring with excellent wear resistance and hardness while maintaining its integrity and functionality.

[0045] 2. In the preparation of cationic polyurethane, this invention uses a cationic chain extender to modify the polyurethane chain segments, promoting the formation of longer polymer chains. The longer chain structure exhibits stronger intermolecular interactions, enhancing the structural integrity of the material. These chains can intertwine over a larger area, increasing the stability of the entire network and thus enhancing the material's hardness and wear resistance. Furthermore, the introduction of the cationic structure reduces surface resistivity, allowing the polyurethane material to conduct and dissipate charge more effectively during charge accumulation. It also enables the formation of better ion channels on and within the polyurethane surface, promoting charge movement and allowing for faster dispersion of static charge during electrostatic accumulation, thereby reducing the risk of static buildup and electrostatic discharge. Additionally, the cationic polyurethane structure exhibits better wettability, attracting and retaining more water molecules, a good conductive medium, thus forming continuous conductive paths on and within the polyurethane surface, further reducing static electricity generation.

[0046] 3. In the process of introducing self-healing fillers into cationic polyurethane, the organic segments of the polyurethane, after modification by a cationic chain extender, exhibit a large number of hydroxyl groups. These hydroxyl groups react with the epoxy groups on the silicon shell of the self-healing filler, resulting in a more uniform dispersion of the self-healing filler within the polyurethane segments. This reduces the agglomeration of the self-healing filler. Furthermore, compared to the chain extender N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, the cationic chain extender contains unsaturated carbon-carbon double bonds on its segments. These serve as reaction sites, further enhancing the self-healing rate and thus improving the self-healing performance of the material. The cationized modified siloxane inside the self-healing filler not only repairs damaged areas of the flooring but also supplements the durability of the flooring's antistatic properties. Detailed Implementation

[0047] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0048] The polyvinyl alcohol used in this invention was purchased from Nanjing Reagent, with product code C0691870023;

[0049] The polyether-modified silicone oil used in this invention was purchased from Yisheng Mall, product number 41008ES10.

[0050] Example 1

[0051] This embodiment provides a method for preparing a cationic chain extender for an antistatic self-healing polyurethane floor slurry, comprising the following steps:

[0052] Weigh out 850.0g of N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane and 7.0L of dimethylacetamide and add them to a reaction vessel. The reaction vessel is stirred at 60rpm. After nitrogen protection, the temperature of the reaction vessel is raised to 50℃ and kept at this temperature for 20min. Then, 100.0g of triethylamine is added to the reaction vessel and kept at this temperature for 5min. Then, 400.0g of 2-chloroethyl vinyl ether is added dropwise to the reaction vessel and added dropwise for 1h. After stirring at this temperature for 3h, the reaction vessel is cooled to room temperature and the reaction solution is added to a rotary evaporator with a water bath temperature of 80℃. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining a cationic chain extender.

[0053] Example 2

[0054] This embodiment provides a method for preparing a cationic chain extender for an antistatic self-healing polyurethane floor slurry, comprising the following steps:

[0055] Weigh out 950.0 g of N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane and 8.0 L of dimethylacetamide and add them to a reaction vessel. The reaction vessel is stirred at 80 rpm. After nitrogen protection, the temperature of the reaction vessel is raised to 70 °C and kept at this temperature for 25 min. Then, 120.0 g of triethylamine is added to the reaction vessel and kept at this temperature for 8 min. Then, 500.0 g of 2-chloroethyl vinyl ether is added dropwise to the reaction vessel and added dropwise for 2 h. After stirring at this temperature for 4 h, the reaction vessel is cooled to room temperature and the reaction solution is added to a rotary evaporator with a water bath temperature of 100 °C. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining a cationic chain extender.

[0056] Example 3

[0057] This embodiment provides a method for preparing a cationic chain extender for an antistatic self-healing polyurethane floor slurry, comprising the following steps:

[0058] Weigh out 900.0 g of N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane and 7.5 L of dimethylacetamide and add them to a reaction vessel. The reaction vessel is stirred at 70 rpm. After nitrogen protection, the temperature of the reaction vessel is raised to 60 °C and stirred for 24 min. Then, 120.0 g of triethylamine is added to the reaction vessel and stirred for another 6 min. Then, 450.0 g of 2-chloroethyl vinyl ether is added dropwise to the reaction vessel and continued for 2 h. After stirring for 4 h, the reaction vessel is cooled to room temperature and the reaction solution is added to a rotary evaporator with a water bath temperature of 90 °C. The solution is then distilled under reduced pressure until no liquid is collected, yielding a cationic chain extender.

[0059] Example 4

[0060] This embodiment provides a method for preparing modified siloxane for antistatic self-healing polyurethane floor slurry, including the following steps:

[0061] Step ①: Modified siloxane precursor

[0062] Weigh out 900.0g of vinylbenzylaminoethylaminopropyltrimethoxysilane, 300.0g of 4,4,4-trifluorobutanal, 30.0g of aluminum chloride, and 3.5L of toluene and add them to a reaction vessel. Raise the temperature of the reaction vessel to 40℃ and keep it at that temperature for 1 hour. After the reaction is complete, cool the reaction vessel to room temperature and add the reaction solution to a rotary evaporator with a water bath temperature of 80℃. Distill under reduced pressure until no liquid is collected to obtain the modified siloxane precursor.

[0063] Step ②: Modified siloxane

[0064] Weigh 900.0 g of modified siloxane precursor and 4.0 L of dimethylacetamide and add them to a reaction vessel. The reaction vessel is stirred at 60 rpm. After nitrogen protection, the temperature of the reaction vessel is raised to 50 °C and stirred for 20 min. Then, 50.0 g of triethylamine is added to the reaction vessel and stirred for another 5 min. Then, 250.0 g of 2-chloroethyl vinyl ether is added dropwise to the reaction vessel and added dropwise for 1 h. After stirring for 3 h, the reaction vessel is cooled to room temperature and the reaction solution is added to a rotary evaporator with a water bath temperature of 80 °C. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining the modified siloxane.

[0065] Example 5

[0066] This embodiment provides a method for preparing modified siloxane for antistatic self-healing polyurethane floor slurry, including the following steps:

[0067] Step ①: Modified siloxane precursor

[0068] Weigh out 1000.0g of vinylbenzylaminoethylaminopropyltrimethoxysilane, 400.0g of 4,4,4-trifluorobutanal, 50.0g of aluminum chloride, and 4.0L of toluene and add them to a reaction vessel. Raise the temperature of the reaction vessel to 50℃ and keep it at that temperature for 2 hours. After the reaction is complete, cool the reaction vessel to room temperature and add the reaction solution to a rotary evaporator with a water bath temperature of 100℃. Distill under reduced pressure until no liquid is collected to obtain the modified siloxane precursor.

[0069] Step ②: Modified siloxane

[0070] Weigh 1000.0g of modified siloxane precursor and 4.5L of dimethylacetamide and add them to a reaction vessel. The reaction vessel is stirred at 80rpm. After nitrogen protection, the temperature of the reaction vessel is raised to 70℃ and stirred for 25min. Then, 80.0g of triethylamine is added to the reaction vessel and stirred for another 8min. Then, 350.0g of 2-chloroethyl vinyl ether is added dropwise to the reaction vessel and added dropwise for 2h. After stirring for 4h, the reaction vessel is cooled to room temperature and the reaction solution is added to a rotary evaporator with a water bath temperature of 100℃. The solution is distilled under reduced pressure until no liquid is collected, thus obtaining the modified siloxane.

[0071] Example 6

[0072] This embodiment provides a method for preparing modified siloxane for antistatic self-healing polyurethane floor slurry, including the following steps:

[0073] Step ①: Modified siloxane precursor

[0074] Weigh out 950.0g of vinylbenzylaminoethylaminopropyltrimethoxysilane, 350.0g of 4,4,4-trifluorobutanal, 40.0g of aluminum chloride, and 3.6L of toluene and add them to a reaction vessel. Raise the temperature of the reaction vessel to 45℃ and keep it at that temperature for 2 hours. After the reaction is complete, cool the reaction vessel to room temperature and add the reaction solution to a rotary evaporator with a water bath temperature of 90℃. Distill under reduced pressure until no liquid is collected to obtain the modified siloxane precursor.

[0075] Step ②: Modified siloxane

[0076] Weigh 950.0 g of modified siloxane precursor and 4.2 L of dimethylacetamide and add them to a reaction vessel. The reaction vessel is stirred at 70 rpm. After nitrogen protection, the temperature of the reaction vessel is raised to 60 °C and stirred for 24 min. Then, 72.0 g of triethylamine is added to the reaction vessel and stirred for another 6 min. Then, 300.0 g of 2-chloroethyl vinyl ether is added dropwise to the reaction vessel and added dropwise for 2 h. After stirring for 4 h, the reaction vessel is cooled to room temperature and the reaction solution is added to a rotary evaporator with a water bath temperature of 90 °C. The solution is then distilled under reduced pressure until no liquid is collected, thus obtaining the modified siloxane.

[0077] Example 7

[0078] This embodiment provides a method for preparing modified siloxane for antistatic self-healing polyurethane floor slurry, including the following steps:

[0079] Step (1) Preparation of hydrolysis precursor solution

[0080] Weigh out 300.0g of the modified siloxane prepared in Example 4, 800.0g of tetramethyltetravinylcyclotetrasiloxane, 30.0g of diphenyl (2,4,6-trimethylbenzophenone) and 3.0L of methyl orthosilicate and add them to the reaction vessel. Stir at 60 rpm for 5 min to obtain the hydrolysis precursor solution.

[0081] Step 2: Preparation of composite emulsion

[0082] Weigh 100.0g of polyoxyethylene alkyl ether and 3.0L of deionized water to prepare an aqueous solution of polyoxyethylene alkyl ether;

[0083] Weigh 200.0g of the hydrolysis precursor solution and add it to a high-speed homogenizer. Pour 1.0L of polyoxyethylene alkyl ether aqueous solution into the hydrolysis precursor solution. Set the speed of the high-speed homogenizer to 8000rpm and stir at room temperature for 20min to obtain a composite emulsion.

[0084] Step 3: Preparation of self-healing filler precursor

[0085] Weigh 4.0 L of the composite emulsion and add it to the reactor. Stir the mixture and add 1 mol / L sodium hydroxide aqueous solution to adjust the pH of the system to 8. Raise the temperature of the reactor to 40°C and keep it at this temperature for 3 hours. Then add 200.0 mL of methyl orthosilicate to the reactor and keep it at this temperature for another 2 hours. Add another 240.0 mL of methyl orthosilicate to the reactor and keep it at this temperature for another 8 hours. After the reaction is complete, wait for the temperature of the reactor to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake three times with anhydrous ethanol and deionized water. Transfer the filter cake to a drying oven at 60°C and vacuum dry it to constant weight to obtain the self-healing filler precursor.

[0086] Step 4: Preparation of self-healing filler

[0087] Weigh out 800.0g of self-healing filler precursor, 200.0g of ethanol, 200.0mL of saturated sodium hydroxide solution and 5.0L of deionized water and add them to the reactor. Purge with nitrogen for protection. After the reactor temperature drops to 10℃, add 300.0g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane to the reactor and keep it at the temperature for 20min. After the reaction is complete, wait for the reactor temperature to drop to room temperature, filter the reaction liquid and collect the filter cake. Wash the filter cake three times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 60℃ and vacuum dry it to constant weight to obtain the self-healing filler.

[0088] Example 8

[0089] This embodiment provides a method for preparing modified siloxane for antistatic self-healing polyurethane floor slurry, including the following steps:

[0090] Step (1) Preparation of hydrolysis precursor solution

[0091] Weigh out 400.0g of the modified siloxane prepared in Example 5, 1000.0g of tetramethyltetravinylcyclotetrasiloxane, 50.0g of diphenyl (2,4,6-trimethylbenzophenone) and 3.5L of methyl orthosilicate and add them to the reaction vessel. Stir at 80 rpm for 10 min to obtain the hydrolysis precursor solution.

[0092] Step 2: Preparation of composite emulsion

[0093] Weigh 200.0g of polyoxyethylene alkyl ether and 4.0L of deionized water to prepare an aqueous solution of polyoxyethylene alkyl ether;

[0094] Weigh 300.0g of the hydrolysis precursor solution and add it to a high-speed homogenizer. Pour 1.5L of polyoxyethylene alkyl ether aqueous solution into the hydrolysis precursor solution. Set the speed of the high-speed homogenizer to 9000rpm and stir at room temperature for 30min to obtain a composite emulsion.

[0095] Step 3: Preparation of self-healing filler precursor

[0096] Weigh 5.0 L of the composite emulsion and add it to the reaction vessel. Stir the mixture and add 2 mol / L sodium hydroxide aqueous solution to adjust the pH of the system to 10. Raise the temperature of the reaction vessel to 50℃ and keep it at this temperature for 4 h. Then add 300.0 mL of methyl orthosilicate to the reaction vessel and keep it at this temperature for another 3 h. Then add 360.0 mL of methyl orthosilicate to the reaction vessel and keep it at this temperature for another 12 h. After the reaction is complete, wait for the temperature of the reaction vessel to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with anhydrous ethanol and deionized water. Transfer the filter cake to a drying oven at 80℃ and vacuum dry it to constant weight to obtain the self-healing filler precursor.

[0097] Step 4: Preparation of self-healing filler

[0098] Weigh out 1000.0g of self-healing filler precursor, 300.0g of ethanol, 300.0mL of saturated sodium hydroxide solution and 6.0L of deionized water and add them to the reactor. Purge with nitrogen for protection. After the reactor temperature drops to 5℃, add 500.0g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane to the reactor and keep it at this temperature for 30min. After the reaction is complete, wait for the reactor temperature to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with anhydrous ethanol and deionized water, and then transfer the filter cake to a drying oven at 80℃ and vacuum dry it to constant weight to obtain the self-healing filler.

[0099] Example 9

[0100] This embodiment provides a method for preparing modified siloxane for antistatic self-healing polyurethane floor slurry, including the following steps:

[0101] Step (1) Preparation of hydrolysis precursor solution

[0102] Weigh out 350.0g of the modified siloxane prepared in Example 6, 900.0g of tetramethyltetravinylcyclotetrasiloxane, 40.0g of diphenyl (2,4,6-trimethylbenzophenone) and 3.2L of methyl orthosilicate and add them to the reaction vessel. Stir the reaction vessel at a stirring rate of 70 rpm for 8 min to obtain the hydrolysis precursor solution.

[0103] Step 2: Preparation of composite emulsion

[0104] Weigh 150.0 g of polyoxyethylene alkyl ether and 3.2 L of deionized water to prepare an aqueous solution of polyoxyethylene alkyl ether;

[0105] Weigh 250.0g of the hydrolysis precursor solution and add it to a high-speed homogenizer. Pour 1.2L of polyoxyethylene alkyl ether aqueous solution into the hydrolysis precursor solution. Set the speed of the high-speed homogenizer to 8500rpm and stir at room temperature for 24min to obtain a composite emulsion.

[0106] Step 3: Preparation of self-healing filler precursor

[0107] Weigh 4.2 L of composite emulsion and add it to the reaction vessel. Stir the mixture and add 1.5 mol / L sodium hydroxide aqueous solution to adjust the pH of the system to 9. Raise the temperature of the reaction vessel to 45℃ and keep it at this temperature for 4 hours. Then add 300.0 mL of methyl orthosilicate to the reaction vessel and keep it at this temperature for another 3 hours. Then add 360.0 mL of methyl orthosilicate to the reaction vessel and keep it at this temperature for another 10 hours. After the reaction is complete, wait for the temperature of the reaction vessel to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake four times with anhydrous ethanol and deionized water. Transfer the filter cake to a drying oven at 70℃ and vacuum dry it to constant weight to obtain the self-healing filler precursor.

[0108] Step 4: Preparation of self-healing filler

[0109] Weigh out 900.0g of self-healing filler precursor, 250.0g of ethanol, 250.0mL of saturated sodium hydroxide solution and 4.0L of deionized water and add them to the reactor. Purge with nitrogen for protection. After the reactor temperature drops to 8℃, add 400.0g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane to the reactor and keep it at this temperature for 25min. After the reaction is complete, wait for the reactor temperature to drop to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake four times with anhydrous ethanol and deionized water, then transfer the filter cake to a drying oven at 70℃ and vacuum dry to constant weight to obtain the self-healing filler.

[0110] Example 10

[0111] This embodiment provides a method for preparing an antistatic self-healing polyurethane floor slurry, including the following steps:

[0112] Step 1: Preparation of cationic polyurethane

[0113] Weigh out 600.0g of polyethylene glycol, 3.5L of N,N-dimethylformamide and 50.0g of dibutyltin dilaurate and add them to the reaction vessel and stir to obtain the reaction precursor solution;

[0114] Weigh out 200.0 g of dimethylbiphenyl diisocyanate and mix with 500.0 mL of N,N-dimethylformamide to obtain a dimethylbiphenyl diisocyanate solution;

[0115] Weigh 800.0 mL of the precursor solution and add it to the reaction vessel. Stir the reaction vessel and raise the temperature to 50°C. Add 500.0 mL of dimethyl biphenyl diisocyanate solution to the reaction vessel and keep it at the temperature for 40 min. Add 100.0 g of the cationic chain extender prepared in Example 1 to the reaction vessel and keep it at the temperature for 20 min. Add 200.0 g of the self-healing filler prepared in Example 7 to the reaction vessel and keep it at the temperature for 90 min to obtain cationic polyurethane.

[0116] Step 2: Preparation of polyurethane floor slurry

[0117] Weigh out 8000.0g cationic polyurethane, 1000.0g isophorone diisocyanate, 50.0g butanol, 50.0g polyether modified silicone oil, 100.0g 3-hydroxybenzophenone, 200.0g sodium dodecyl sulfonate and 5000.0g deionized water, mix them evenly, and pass them through a 200-mesh sieve to obtain polyurethane flooring slurry.

[0118] Example 11

[0119] This embodiment provides a method for preparing an antistatic self-healing polyurethane floor slurry, including the following steps:

[0120] Step 1: Preparation of cationic polyurethane

[0121] Weigh out 800.0g of polyethylene glycol, 4.0L of N,N-dimethylformamide and 80.0g of dibutyltin dilaurate and add them to the reaction vessel and stir to obtain the reaction precursor solution;

[0122] Weigh out 300.0 g of dimethylbiphenyl diisocyanate and 600.0 mL of N,N-dimethylformamide and mix them to obtain a dimethylbiphenyl diisocyanate solution;

[0123] Weigh 1000.0 mL of the reaction precursor solution and add it to the reaction vessel. Stir the reaction vessel and raise the temperature to 60°C. Add 600.0 mL of dimethyl biphenyl diisocyanate solution to the reaction vessel and keep it at the temperature for 60 min. Add 200.0 g of the cationic chain extender prepared in Example 2 to the reaction vessel and keep it at the temperature for 30 min. Add 300.0 g of the self-healing filler prepared in Example 8 to the reaction vessel and keep it at the temperature for 120 min to obtain cationic polyurethane.

[0124] Step 2: Preparation of polyurethane floor slurry

[0125] Weigh out 10000.0g cationic polyurethane, 1200.0g isophorone diisocyanate, 200.0g butanol, 100.0g polyether modified silicone oil, 200.0g 3-hydroxybenzophenone, 300.0g sodium dodecyl sulfonate and 6000.0g deionized water, mix them evenly, and pass them through a 400-mesh sieve to obtain polyurethane flooring slurry.

[0126] Example 12

[0127] This embodiment provides a method for preparing an antistatic self-healing polyurethane floor slurry, including the following steps:

[0128] Step 1: Preparation of cationic polyurethane

[0129] Weigh out 700.0g of polyethylene glycol, 3.6L of N,N-dimethylformamide and 72.0g of dibutyltin dilaurate and add them to the reaction vessel and stir to obtain the reaction precursor solution;

[0130] Weigh out 250.0 g of dimethylbiphenyl diisocyanate and 540.0 mL of N,N-dimethylformamide and mix them to obtain a dimethylbiphenyl diisocyanate solution;

[0131] Weigh 900.0 mL of the precursor solution and add it to the reaction vessel. Stir the reaction vessel and raise the temperature to 55°C. Add 550.0 mL of dimethyl biphenyl diisocyanate solution to the reaction vessel and keep it at the temperature for 50 min. Add 150.0 g of the cationic chain extender prepared in Example 3 to the reaction vessel and keep it at the temperature for 24 min. Add 250.0 g of the self-healing filler prepared in Example 9 to the reaction vessel and keep it at the temperature for 100 min to obtain cationic polyurethane.

[0132] Step 2: Preparation of polyurethane floor slurry

[0133] Weigh out 9000.0g cationic polyurethane, 1100.0g isophorone diisocyanate, 100.0g butanol, 80.0g polyether modified silicone oil, 120.0g 3-hydroxybenzophenone, 250.0g sodium dodecyl sulfonate and 5400.0g deionized water, mix them evenly, and pass them through a 300-mesh sieve to obtain polyurethane flooring slurry.

[0134] Comparative Example 1

[0135] The difference between this comparative example and Example 12 is that, in step one, the cationic chain extender is omitted.

[0136] Comparative Example 2

[0137] The difference between this comparative example and Example 12 is that, in step one, N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane is used in an equal amount to replace the cationic chain extender.

[0138] Comparative Example 3

[0139] The difference between this comparative example and Example 12 is that the modified siloxane was omitted during the preparation of the self-healing filler.

[0140] Performance testing:

[0141] The pencil hardness and abrasion resistance of the polyurethane flooring slurries prepared in Examples 10-12 and Comparative Examples 1-3 after curing were tested in accordance with the standard JC / T 2327-2015 "Waterborne Polyurethane Flooring".

[0142] The antistatic properties of the polyurethane flooring slurries prepared in Examples 10-12 and Comparative Examples 1-3 after curing were tested in accordance with the standard GB / T 15662-1995 "Test Method for Volume Resistivity of Conductive and Antistatic Plastics".

[0143] The self-healing time of the polyurethane floor slurries prepared in Examples 10-12 and Comparative Examples 1-3 after curing was tested in accordance with the standard HG / T 5675-2020 "Self-healing Hardening Film of Optical Functional Thin Film".

[0144] The antistatic properties of the self-healing areas of the polyurethane flooring slurries prepared in Examples 10-12 and Comparative Examples 1-3 were tested according to the standard GB / T 15662-1995 "Test Method for Volume Resistivity of Conductive and Antistatic Plastics". The specific data are shown in Table 1.

[0145] Table 1 - Performance test data of each sample

[0146]

[0147] Data Analysis:

[0148] Comparative analysis of the data in Table 1 above shows that the polyurethane flooring slurry prepared by this invention has a pencil hardness of 4H, an abrasion resistance (750g / 500r) of 0.015g, and a volume resistivity of 3.0×10⁻⁶. 5 The self-healing time is 7 min, and the volume resistivity of the self-healed region is 3.4 × 10⁻⁶ Ω·m. 5 Ω·m;

[0149] By comparing the pencil hardness and abrasion resistance data of polyurethane floor slurry after curing, it can be found that the pencil hardness of Comparative Example 1 decreased significantly. This indicates that the use of chain extenders promotes the formation of longer polymer chains. The long chain structure has stronger intermolecular interactions, enhances the structural integrity of the material, and can entangle with each other over a larger range, thereby increasing the stability of the entire network and thus enhancing the hardness and abrasion resistance of the material.

[0150] By comparing the volume resistivity data of the cured polyurethane flooring slurry, it can be found that the antistatic properties of Comparative Example 1 and Comparative Example 2 decreased significantly. This indicates that the introduction of the cationic structure reduces the surface resistance, enabling the polyurethane material to conduct and dissipate charges more effectively when they accumulate. It also allows for the formation of better ion channels on the surface and inside the polyurethane, thereby promoting charge movement and enabling the polyurethane to disperse these charges more quickly when static electricity accumulates, thus reducing the risk of static electricity accumulation and electrostatic discharge. Furthermore, the cationic polyurethane has better wettability, thereby attracting and retaining more water molecules, a good conductive medium, which forms a continuous conductive path on the surface and inside the polyurethane, further reducing the generation of static electricity.

[0151] By comparing the self-healing time data of polyurethane floor slurry after curing, it can be found that the self-healing performance of Comparative Example 1 decreased significantly. Compared with Comparative Example 1, the decrease in self-healing performance of Comparative Example 2 was smaller. This indicates that after chain extension by the epoxy-containing chain extender, a large number of hydroxyl groups appear in the organic segments of polyurethane. Through reaction with the epoxy groups on the silicon shell of the self-healing filler, the self-healing filler is more uniformly dispersed in the polyurethane segments, thereby reducing the aggregation of the self-healing filler. Moreover, compared with the chain extender N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, the cationic chain extender has unsaturated carbon-carbon double bonds on its segments. As a reaction site, it further enhances the self-healing rate, thereby further improving the self-healing performance of the material. This explains why the self-healing performance of Comparative Example 1 decreased significantly, while the performance of Comparative Example 2 decreased slightly.

[0152] By comparing the volume resistivity data of the self-healing area after the curing of polyurethane flooring slurry, it can be found that the resistance of the self-healing area in Examples 1-2 decreased significantly, while the resistance of the self-healing area in Comparative Example 3 increased significantly. This indicates that when the self-healing filler lacks modified siloxane with a cationic structure, although its self-healing performance will not decrease significantly, the monomers inside the self-healing filler will self-polymerize under the catalysis of the photoinitiator and cover the polyurethane structure, thereby reducing the antistatic performance of the material. This shows that the modified siloxane inside not only plays the role of repairing the damaged parts of the flooring, but also supplements the durability of the antistatic performance of the flooring.

[0153] This invention involves preparing cationic chain extenders to hybridize polyurethane segments, enhancing their wear resistance and hardness while imparting excellent antistatic properties and introducing unsaturated double bonds. The numerous hydroxyl structures within the extended chain segments promote the dispersion of the self-healing filler, and the unsaturated double bonds act as active sites to improve repair efficiency. The modified siloxane structure within the self-healing filler not only repairs damaged areas of the floor but also enhances the durability of the floor's antistatic properties.

[0154] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. An antistatic self-healing polyurethane floor slurry, characterized in that, It comprises the following raw material components by weight: 80-100 parts cationic polyurethane and 64-80 parts excipients; The auxiliary materials consist of the following raw materials in parts by weight: 10-12 parts curing agent, 0.5-2 parts leveling agent, 0.5-1 part defoamer, 1-2 parts light stabilizer, 2-3 parts antistatic agent and 50-60 parts deionized water; The preparation method of the cationic polyurethane includes the following steps: A1. Polyethylene glycol, N,N-dimethylformamide and dibutyltin dilaurate were added to a reaction vessel and stirred to obtain a reaction precursor solution; A2. Add the precursor solution to the reactor and stir. Raise the reactor temperature to 50-60℃. Add dimethyl biphenyl diisocyanate solution dropwise to the reactor and keep it at this temperature for 40-60 min. Add a cationic chain extender to the reactor and keep it at this temperature for 20-30 min. Add a self-healing filler to the reactor and keep it at this temperature for 90-120 min. Post-treatment yields cationic polyurethane.

2. The antistatic self-healing polyurethane floor slurry according to claim 1, characterized in that, In step A1, the ratio of polyethylene glycol, N,N-dimethylformamide, and dibutyltin dilaurate is 6-8g:35-40mL:0.5-0.8g; in step A2, the ratio of the reaction precursor solution, dimethylbiphenyl diisocyanate solution, cationic chain extender, and self-healing filler is 8-10mL:5-6mL:1-2g:2-3g. The dimethylbiphenyl diisocyanate solution is obtained by mixing dimethylbiphenyl diisocyanate and N,N-dimethylformamide in a ratio of 2-3g:5-6mL.

3. The antistatic self-healing polyurethane floor slurry according to claim 1, characterized in that, The cationic chain extender is prepared as follows: N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane and dimethylacetamide are added to a reaction vessel. After nitrogen protection, the temperature of the reaction vessel is raised to 50-70℃ and stirred for 20-25 minutes. Then, triethylamine is added to the reaction vessel and stirred for another 5-8 minutes. Next, 2-chloroethyl vinyl ether is added dropwise to the reaction vessel for 1-2 hours. The mixture is then stirred for 3-4 hours, and the cationic chain extender is obtained after post-treatment.

4. The antistatic self-healing polyurethane floor slurry according to claim 1, characterized in that, The ratio of N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, dimethylacetamide, triethylamine, and 2-chloroethyl vinyl ether is 8.5-9.5g:70-80mL:1-1.2g:4-5g.

5. The antistatic self-healing polyurethane floor slurry according to claim 1, characterized in that, The preparation method of the self-healing filler includes the following steps: B1. Add modified siloxane, tetramethyltetravinylcyclotetrasiloxane, diphenyl (2,4,6-trimethylbenzophenone) and methyl orthosilicate to a reaction vessel and stir for 5-10 minutes to obtain the hydrolysis precursor solution. B2. Add the hydrolysis precursor liquid to a high-speed homogenizer, and pour the polyoxyethylene alkyl ether aqueous solution into the hydrolysis precursor liquid. Set the speed of the high-speed homogenizer to 8000-9000 rpm and stir at room temperature for 20-30 minutes to obtain a composite emulsion. B3. Add the composite emulsion to the reactor and stir. Add 1-2 mol / L sodium hydroxide aqueous solution to the reactor to adjust the pH of the system to 8-10. Raise the temperature of the reactor to 40-50℃ and keep it at this temperature for 3-4 hours. Then add methyl orthosilicate to the reactor and keep it at this temperature for 2-3 hours. Add methyl orthosilicate to the reactor again and keep it at this temperature for 8-12 hours. The self-healing filler precursor is obtained after post-treatment. B4. Add the self-healing filler precursor, ethanol, saturated sodium hydroxide solution and deionized water to the reactor and purge with nitrogen for protection. After the reactor temperature drops to 5-10℃, add 3-(2,3-epoxypropoxy)propyltrimethoxysilane to the reactor and keep it at the temperature for 20-30 min. The self-healing filler is then obtained after post-treatment.

6. The antistatic self-healing polyurethane floor slurry according to claim 5, characterized in that, In step B1, the ratio of modified siloxane, tetramethyltetravinylcyclotetrasiloxane, diphenyl (2,4,6-trimethylbenzophenone), and methyl orthosilicate is 3-4 g: 8-10 g: 0.3-0.5 g: 30-35 mL; in step B2, the ratio of hydrolysis precursor solution to polyoxyethylene alkyl ether aqueous solution is 2-3 g: 10-15 mL, and the polyoxyethylene alkyl ether aqueous solution is composed of polyoxyethylene alkyl ether and deionized water in a ratio of 1-2 g: 30- 40 mL was prepared; in step B3, the ratio of composite emulsion to methyl orthosilicate was 40-50 mL: 4.4-6.6 mL, and the ratio of methyl orthosilicate added twice was 1:1-1.2; in step B4, the ratio of self-healing filler precursor, ethanol, saturated sodium hydroxide solution, deionized water and 3-(2,3-epoxypropoxy)propyltrimethoxysilane was 8-10 g: 2-3 g: 2-3 mL: 40-60 mL: 3-5 g.

7. The antistatic self-healing polyurethane floor slurry according to claim 5, characterized in that, The method for preparing the modified siloxane includes the following steps: C1. Vinylbenzylaminoethylaminopropyltrimethoxysilane, 4,4,4-trifluorobutanal, aluminum chloride and toluene are added to a reaction vessel. The temperature of the reaction vessel is raised to 40-50℃ and the reaction is maintained for 1-2 hours. The modified siloxane precursor is obtained after post-treatment. C2. Add the modified siloxane precursor and dimethylacetamide to the reactor. After purging with nitrogen for protection, raise the reactor temperature to 50-70℃ and stir for 20-25 minutes. Then, add triethylamine to the reactor and continue stirring for 5-8 minutes. Next, add 2-chloroethyl vinyl ether dropwise to the reactor for 1-2 hours. Stir for 3-4 hours and then proceed with post-treatment to obtain the modified siloxane.

8. The antistatic self-healing polyurethane floor slurry according to claim 7, characterized in that, In step C1, the ratio of vinylbenzylaminoethylaminopropyltrimethoxysilane, 4,4,4-trifluorobutanal, aluminum chloride, and toluene is 9-10 g: 3-4 g: 0.3-0.5 g: 35-40 mL; in step C2, the ratio of modified siloxane precursor, dimethylacetamide, triethylamine, and 2-chloroethyl vinyl ether is 9-10 g: 40-45 mL: 0.5-0.8 g: 2.5-3.5 g.

9. A method for preparing an antistatic self-healing polyurethane floor slurry, applied to the antistatic self-healing polyurethane floor slurry as described in any one of claims 1-8, characterized in that, After the cationic polyurethane and auxiliary materials are mixed evenly, the mixture is passed through a 200-400 mesh sieve to obtain polyurethane flooring slurry.

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