High-wear-resistance epoxy color sand self-leveling floor paint and preparation method thereof

Abstract

The application discloses a kind of high wear-resistant epoxy color sand self-leveling floor coatings and preparation method thereof, it is related to floor coating technical field.The high wear-resistant epoxy color sand self-leveling floor coatings includes the following weight fraction raw materials: epoxy resin 30-50 parts, active diluent 5-15 parts, antistatic agent 0.5-2 parts, modified flame-retardant reinforcing agent 3-6 parts, leveling agent 0.5-1.5 parts, film-forming aid 2-5 parts, wear-resistant functional filler 3-5 parts, fumed silica 0.5-2.5 parts, color sand 40-60 parts, curing agent 15-25 parts, defoaming agent 0.3-1.0 part;High wear-resistant epoxy color sand self-leveling floor coatings prepared by the application has excellent wear resistance, antistatic property, flame-retardant property and self-repairing property.

Description

Technical Field

[0001] This invention relates to the field of floor coating technology, specifically to a high wear-resistant epoxy colored sand self-leveling floor coating and its preparation method. Background Technology

[0002] Epoxy colored sand self-leveling flooring is widely used in industrial plants, commercial spaces, electronic cleanrooms, and public buildings due to its good integrity, excellent decorative effect, and high surface smoothness. However, existing epoxy colored sand self-leveling flooring coatings still have several performance shortcomings in actual use, making it difficult to meet the comprehensive requirements of high-standard operating environments. First, traditional epoxy colored sand flooring mostly uses insulating epoxy resin as the continuous phase, which has a high surface resistivity. It is prone to static electricity accumulation under the action of personnel walking, equipment operation, or friction. The static electricity release is unstable, which not only affects the safe operation of precision electronic equipment but may also cause safety hazards in flammable and explosive environments. Second, ordinary epoxy resin is a flammable polymer material that is prone to thermal decomposition and release of flammable gases under the action of a fire source, making it difficult to meet the fire safety requirements of public buildings and industrial sites, posing certain safety risks. In addition, existing epoxy colored sand self-leveling flooring is prone to cracking, sand shedding, or local damage under long-term high load or local impact. Once damaged, it is difficult to achieve effective integration of the old and new interfaces during the repair process. The repaired area differs significantly from the original flooring in terms of color, flatness, and mechanical properties, affecting the overall performance and aesthetics.

[0003] Chinese invention patent CN101818015A discloses a water-based antistatic epoxy floor coating, its preparation method, and its application. The epoxy floor coating comprises: 40-45 parts epoxy resin, 1-4 parts reactive diluent, 12-18 parts color paste, 0.05-0.2 parts dispersant, 0.05-0.2 parts wetting agent, 0.1-0.5 parts leveling agent, 0.1-0.5 parts defoamer, and 0... 0.01-0.1 parts defoamer, 0.5-2 parts organic wax powder, 2-6 parts quartz powder, 20-30 parts calcium carbonate and 5-10 parts conductive fiber are mixed to obtain component A: 50-80 parts water-based curing agent, 0.5-2 parts water-based film-forming aid, 20-50 parts water and 0.05-0.2 parts leveling agent are mixed. The epoxy floor coating prepared by this invention has low resistance and high hardness, but its flame retardant and self-healing properties need to be improved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a high-wear-resistant epoxy colored sand self-leveling floor coating and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A high-wear-resistant epoxy colored sand self-leveling floor coating comprises the following raw materials in parts by weight: 30-50 parts epoxy resin, 5-15 parts reactive diluent, 0.5-2 parts antistatic agent, 3-6 parts modified flame retardant reinforcing agent, 0.5-1.5 parts leveling agent, 2-5 parts film-forming aid, 3-5 parts wear-resistant functional filler, 0.5-2.5 parts fumed silica, 40-60 parts colored sand, 15-25 parts curing agent, and 0.3-1.0 parts defoamer; The antistatic agent is prepared by the following method: S1: 3-(3-(3-chloropropoxy)propoxy)propionic acid reacts with D-xylose to form a four-armed compound. S2: The four-armed compound reacts with dodecyl dimethyl tertiary amine to form a quaternary ammonium salt compound. S3: Quaternary ammonium salt compounds react with 1,3-bis((2,2-dimethyl-1,3-dioxapentane-4-yl)methoxy)prop-2-amine to generate heteropentane-modified quaternary ammonium salt compounds. S4: Heteropene-modified quaternary ammonium salt compounds hydrolyze to generate antistatic agents.

[0006] In step S1, the molar ratio of 3-(3-(3-chloropropoxy)propoxy)propionic acid to D-xylose is (4.05-4.1):1.

[0007] In step S2, the molar ratio of the four-armed compound to dodecyl dimethyl tertiary amine is 1:(4.02-4.05).

[0008] In step S3, the molar ratio of the quaternary ammonium salt compound to 1,3-bis((2,2-dimethyl-1,3-dioxapentane-4-yl)methoxy)prop-2-amine is 1:(1.05-1.1).

[0009] The modified flame retardant reinforcing agent is prepared by the following method: A1: 2,4,6,8-Tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane reacts with 4-mercaptophenylboronic acid to generate intermediate 1. A2: Intermediate 1 reacts with 3-amino-1,2-propanediol to generate intermediate 2. A3: Intermediate 2 reacts with lipoic acid to generate a modified flame retardant and reinforcing agent.

[0010] In step A1, the molar ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane to 4-mercaptophenylboronic acid is 1:4.02.

[0011] In step A2, the molar ratio of intermediate 1 to 3-amino-1,2-propanediol is 1:4.05; in step A3, the molar ratio of intermediate 2 to thioctic acid is 1:4.06.

[0012] The reactive diluent is benzyl glycidyl ether; the leveling agent is one of polyether-modified polysiloxane and polyester-modified polysiloxane; the film-forming aid is one of propylene glycol butyl ether and dipropylene glycol butyl ether; and the curing agent is an aqueous epoxy curing agent.

[0013] The defoamer is BYK-066N; the wear-resistant filler is one of corundum powder and silicon carbide powder.

[0014] A method for preparing a high-wear-resistant epoxy colored sand self-leveling floor coating includes the following steps: (1) Weigh out the following by weight: 30-50 parts epoxy resin, 5-15 parts reactive diluent, 0.5-2 parts antistatic agent, 3-6 parts modified flame retardant reinforcing agent, 0.5-1.5 parts leveling agent, 2-5 parts film-forming aid, 3-5 parts wear-resistant functional filler, 0.5-2.5 parts fumed silica, 40-60 parts colored sand, 15-25 parts curing agent, and 0.3-1.0 parts defoamer; (2) Add epoxy resin and reactive diluent to a dispersion tank and stir evenly; add antistatic agent, modified flame retardant reinforcing agent, leveling agent and film forming aid in sequence and disperse at high speed; slowly add wear-resistant functional filler and fumed silica and disperse at high speed; finally add colored sand and stir evenly to obtain component A; add curing agent to a mixing tank, then add defoamer and stir evenly to obtain component B; mix component A and component B, stir evenly and let stand to defoam, and then obtain high wear-resistant epoxy colored sand self-leveling floor coating.

[0015] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The self-leveling floor coating prepared by this invention has excellent wear resistance, antistatic properties, flame retardant properties and self-healing properties. Attached Figure Description

[0016] Figure 1 The 1H NMR spectrum of the antistatic agent prepared in step S4 of Example 1; Figure 2 This is a high-resolution mass spectrum of the antistatic agent prepared in step S4 of Example 1; Figure 3 The 1H NMR spectrum of the modified flame retardant enhancer prepared in step A3 of Example 4; Figure 4 This is a high-resolution mass spectrum of the modified flame retardant enhancer prepared in step A3 of Example 4. Detailed Implementation

[0017] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0018] Example 1: Preparation of Antistatic Agent S1: Under nitrogen protection, 400 ml of DMF (N,N-dimethylformamide), 0.405 mol of 3-(3-(3-chloropropoxy)propoxy)propionic acid, 0.41 mol of N,N'-dicyclohexylcarbodiimide, and 0.01 mol of 4-dimethylaminopyridine were added to the reactor. The mixture was stirred for 10 min, then 0.1 mol of D-xylose was added, and the reaction was carried out at room temperature for 10 h. The mixture was filtered, rotary evaporated at 65 °C for 1 h, and purified by silica gel column chromatography (using a petroleum ether / ethyl acetate mixture as eluent, with a gradient elution ratio of 10:1 to 5:1). The mixture was then distilled under reduced pressure at 50 °C for 1.5 h and dried under vacuum at 50 °C for 12 h to obtain the four-armed compound. The reaction equation is shown below:

[0019] Its 1H NMR spectrum data is as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 9.72 (dd, J =7.8, 1.9 Hz, 1H), 5.36 – 5.09 (m, 3H), 4.38 (m, 2H), 3.76 – 3.70 (m, 8H), 3.61 – 3.44 (m, 32H), 2.66 – 2.51 (m, 8H), 2.02 (tt, J = 5.0, 3.9 Hz, 8H), 1.83 (p, J = 6.7 Hz, 8H); HRMS (m / z): 977.3341[M+H] + .

[0020] S2: Under nitrogen protection, 600 ml of acetonitrile and 0.1 mol of the four-arm compound were added to the reactor. The mixture was stirred at room temperature for 5 min, and then 0.402 mol of dodecyl dimethyl tertiary amine was slowly added dropwise over 40 min. After the addition was complete, the temperature was raised to 60 °C and the reaction was carried out for 8 h. Then, the mixture was distilled under reduced pressure at 60 °C for 1 h. The solid was then slowly added to 600 ml of diethyl ether, stirred, and filtered. The solid was washed three times with diethyl ether (50 ml of diethyl ether each time) and dried under vacuum at 40 °C for 12 h to obtain the quaternary ammonium salt compound. The reaction equation is shown below:

[0021] Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 9.72 (dd, J =7.8, 1.9 Hz, 1H), 5.38 – 5.09 (m, 3H), 4.38 (m, 2H), 3.80 – 3.68 (m, 8H), 3.63 – 3.35 (m, 40H), 3.26 (s, 24H), HRMS (m / z): 422.1115[M-4Cl] 4+ .

[0022] S3: Under nitrogen protection, 700 ml of tetrahydrofuran, 0.1 mol of quaternary ammonium salt compound, and 40 g of 4A molecular sieve (sodium-A type molecular sieve) were added to the reactor and stirred until well mixed. Then, 200 ml of a tetrahydrofuran solution containing 0.105 mol of 1,3-bis((2,2-dimethyl-1,3-dioxapentyl-4-yl)methoxy)propyl-2-amine was slowly added dropwise over 1 hour. After the addition was complete, the mixture was heated to reflux for 6 hours, cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure at 40°C for 1 hour. Then, 600 ml of cold n-hexane was added, and the mixture was stirred to precipitate. The precipitate was filtered, washed three times with petroleum ether (50 ml each time), and dried under vacuum at 40°C for 12 hours to obtain the heteropentyl modified quaternary ammonium salt compound. The reaction equation is shown below.

[0023] Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.57 (dd, J =9.1, 1.8 Hz, 1H), 5.64 – 5.12 (m, 3H), 4.37 (m, 2H), 4.06 – 3.91 (m, 4H), 3.84 – 3.34 (m, 59H), 3.26 (s, 24H), 2.71 – 2.48 (m, 8H), 2.08 – 1.68 (m,24H), 1.46 – 1.18 (m, 84H), 0.96 – 0.82 (m, 12H); HRMS (m / z): 497.4088[M-4Cl] 4+ .

[0024] S4: Add 800 ml of anhydrous ethanol and 0.1 mol of heteropentane-modified quaternary ammonium salt compound to the reactor, then add 200 ml of 2 wt% dilute hydrochloric acid, stir to mix, react at 40 °C for 6 h, cool to room temperature, slowly add 5 wt% sodium hydroxide solution to adjust the pH to neutral, filter, wash three times with saturated sodium chloride solution (50 ml each time), and vacuum dry at 60 °C for 10 h to obtain the antistatic agent; the reaction equation is shown below:

[0025] Its 1H NMR spectrum is as follows Figure 1 As shown, its 1H NMR spectrum data are as follows: 1 H NMR (400 MHz, Chloroform- d δ 7.57 (dd, J = 9.1, 1.8 Hz, 1H), 5.64 – 5.13 (m, 3H), 4.37 (m, 2H), 3.88– 3.69 (m, 16H), 3.63 – 3.37 (m, 47H), 3.26 (s, 24H), 3.23 – 3.11 (m, 4H), 2.69 – 2.51 (m, 8H), 1.99 (tt, J = 9.1, 6.8 Hz, 8H), 1.87 – 1.68 (m, 16H), 1.42 – 1.21 (m, 72H), 0.94 – 0.84 (m, 12H); its high-resolution mass spectrum is as follows. Figure 2 As shown, HRMS (m / z): 477.3925 [M-4Cl] 4+ .

[0026] Example 2: Preparation of antistatic agent: S1: Under nitrogen protection, 400 ml DMF, 0.408 mol 3-(3-(3-chloropropoxy)propoxy)propionic acid, 0.41 mol N,N'-dicyclohexylcarbodiimide and 0.01 mol 4-dimethylaminopyridine were added to the reactor and stirred for 10 min. Then 0.1 mol D-xylose was added and the reaction was carried out at room temperature for 11 h. The mixture was filtered, rotary evaporated at 65 °C for 1 h, purified by silica gel column chromatography (using a petroleum ether / ethyl acetate mixture as eluent, with a gradient elution at a volume ratio of 10:1 to 5:1), distilled under reduced pressure at 50 °C for 1.5 h, and dried under vacuum at 50 °C for 12 h to obtain the four-armed compound. S2: Under nitrogen protection, 600 ml of acetonitrile and 0.1 mol of the four-arm compound were added to the reactor and stirred at room temperature for 5 min. Then, 0.403 mol of dodecyl dimethyl tertiary amine was slowly added dropwise over 40 min. After the addition was complete, the temperature was raised to 65 °C and reacted for 7.5 h. Then, the mixture was distilled under reduced pressure at 60 °C for 1 h. The solid was then slowly added to 600 ml of diethyl ether, stirred, and filtered. The solid was washed three times with diethyl ether (50 ml of diethyl ether each time) and dried under vacuum at 40 °C for 12 h to obtain the quaternary ammonium salt compound. S3: Under nitrogen protection, 700 ml of tetrahydrofuran, 0.1 mol of quaternary ammonium salt compound, and 40 g of 4A molecular sieve (sodium-A type molecular sieve) were added to the reactor and stirred until well mixed. 200 ml of tetrahydrofuran solution containing 0.108 mol of 1,3-bis((2,2-dimethyl-1,3-dioxapentyl-4-yl)methoxy)prop-2-amine was slowly added dropwise over 1 hour. After the addition was complete, the mixture was heated to reflux for 5.5 hours, cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure at 40°C for 1 hour. Then, 600 ml of cold n-hexane was added, and the precipitate was stirred to precipitate. The precipitate was filtered, washed three times with petroleum ether (50 ml each time), and dried under vacuum at 40°C for 12 hours to obtain the heptapentyl-modified quaternary ammonium salt compound. S4: Add 800 ml of anhydrous ethanol and 0.1 mol of heteropentane-modified quaternary ammonium salt compound to the reactor, then add 200 ml of 2 wt% dilute hydrochloric acid, stir and mix well, react at 50 °C for 5 h, cool to room temperature, slowly add 5 wt% sodium hydroxide solution to adjust the pH to neutral, filter, wash three times with saturated sodium chloride solution (50 ml each time), and vacuum dry at 60 °C for 10 h to obtain the antistatic agent.

[0027] Example 3: Preparation of antistatic agent: S1: Under nitrogen protection, 400 ml DMF, 0.41 mol 3-(3-(3-chloropropoxy)propoxy)propionic acid, 0.41 mol N,N'-dicyclohexylcarbodiimide and 0.01 mol 4-dimethylaminopyridine were added to the reactor and stirred for 10 min. Then 0.1 mol D-xylose was added and the reaction was carried out at room temperature for 12 h. The mixture was filtered, rotary evaporated at 65 °C for 1 h, purified by silica gel column chromatography (using a petroleum ether / ethyl acetate mixture as eluent, with a gradient elution at a volume ratio of 10:1 to 5:1), distilled under reduced pressure at 50 °C for 1.5 h, and dried under vacuum at 50 °C for 12 h to obtain the four-armed compound. S2: Under nitrogen protection, 600 ml of acetonitrile and 0.1 mol of the four-arm compound were added to the reactor and stirred at room temperature for 5 min. Then, 0.405 mol of dodecyl dimethyl tertiary amine was slowly added dropwise over 40 min. After the addition was complete, the temperature was raised to 70 °C and reacted for 7 h. Then, the mixture was distilled under reduced pressure at 60 °C for 1 h. The solid was then slowly added to 600 ml of diethyl ether, stirred, and filtered. The solid was washed three times with diethyl ether (50 ml of diethyl ether each time) and dried under vacuum at 40 °C for 12 h to obtain the quaternary ammonium salt compound. S3: Under nitrogen protection, 700 ml of tetrahydrofuran, 0.1 mol of quaternary ammonium salt compound, and 40 g of 4A molecular sieve (sodium-A type molecular sieve) were added to the reactor and stirred until well mixed. Then, 200 ml of tetrahydrofuran solution containing 0.11 mol of 1,3-bis((2,2-dimethyl-1,3-dioxapentyl-4-yl)methoxy)prop-2-amine was slowly added dropwise over 1 hour. After the addition was complete, the mixture was heated to reflux and reacted for 5 hours. Then, it was cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure at 40 °C for 1 hour. Then, 600 ml of cold n-hexane was added, and the precipitate was stirred to precipitate. The precipitate was filtered, washed three times with petroleum ether (50 ml each time), and dried under vacuum at 40 °C for 12 hours to obtain the heteropentyl modified quaternary ammonium salt compound. S4: Add 800 ml of anhydrous ethanol and 0.1 mol of heteropentane-modified quaternary ammonium salt compound to the reactor, then add 200 ml of 2 wt% dilute hydrochloric acid, stir and mix well, react at 60 °C for 4 h, cool to room temperature, slowly add 5 wt% sodium hydroxide solution to adjust the pH to neutral, filter, wash three times with saturated sodium chloride solution (50 ml each time), and vacuum dry at 60 °C for 10 h to obtain the antistatic agent.

[0028] Example 4: Preparation of modified flame retardant reinforcing agent: A1: Under nitrogen protection, add 500 ml of a mixed solution of tetrahydrofuran and methanol (V) to the reactor. 四氢呋喃 :V 甲醇 =3:1), 0.1 mol 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 0.402 mol 4-mercaptophenylboronic acid, and 1.0 g photoinitiator 184 were mixed and stirred until homogeneous. The mixture was then incubated at room temperature with an intensity of 8.4 mW / cm². 2 After irradiation under a 365nm UV LED lamp for 2 hours, the mixture was distilled under reduced pressure at 40℃ for 1 hour. The solution was then slowly poured into 500ml of cold diethyl ether, stirred, and a precipitate was formed. The precipitate was filtered, washed three times with 50ml of cold diethyl ether each time, and dried under vacuum at 40℃ for 12 hours to obtain intermediate 1. The reaction equation is shown below:

[0029] Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.26 (s, 8H), 7.69 –7.62 (m, 8H), 7.34 – 7.27 (m, 8H), 2.90 (s, 8H), 1.05 (t, J = 8.2 Hz, 8H), 0.06 (s, 12H); HRMS (m / z):961.1793[M+H] + .

[0030] A2: Under nitrogen protection, 800 ml of anhydrous toluene, 0.1 mol of intermediate 1, and 0.405 mol of 3-amino-1,2-propanediol were added to the reactor. The mixture was stirred and stirred until homogeneous. The mixture was then heated to reflux for 6 hours (using a Dean-Stark water separator for azeotropic dehydration). After cooling to room temperature, the mixture was rotary evaporated at 60°C for 1.5 hours. Then, 600 ml of n-hexane was added, and the mixture was stirred to precipitate the precipitate. The precipitate was filtered and dried under vacuum at 45°C for 12 hours to obtain intermediate 2. The reaction equation is shown below:

[0031] Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ 7.69 – 7.61 (m, 8H), 7.31 – 7.23 (m, 8H), 4.45 (dd, J = 10.9, 3.3 Hz, 4H), 4.40 (p, J = 3.4 Hz, 4H), 4.19 (dd, J = 10.9, 3.4 Hz, 4H), 3.02 (dtd, J = 12.0, 5.7, 3.4 Hz, 4H), 2.90 (d, J = 16.4 Hz, 8H), 2.82 – 2.71 (m, 4H), 1.74 (t, J = 5.7 Hz, 8H), 1.05 (t, J = 8.2 Hz, 8H), 0.06 (s, 12H); HRMS (m / z): 1181.3482 [M+H] + .

[0032] A3: Under nitrogen protection, 1000 ml of dichloromethane, 0.406 mol of lipoic acid, 0.41 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.41 mol of N-hydroxysuccinimide were added to the reactor and stirred until homogeneous. Then, 0.1 mol of intermediate 2 was added in four batches (5 min apart). The mixture was reacted at room temperature for 12 h, filtered, and distilled under reduced pressure at 30 °C for 1 h. The mixture was then purified by silica gel column chromatography (V...二氯甲烷 :V 甲醇 The modified flame retardant and reinforcing agent was obtained by distillation under reduced pressure at 40℃ for 1 hour and vacuum drying at 40℃ for 12 hours (ratio = 15:1). The reaction equation is shown below:

[0033] Its 1H NMR spectrum is as follows Figure 3 As shown, its 1H NMR spectrum data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ7.69 – 7.61 (m, 8H), 7.39 (t, J = 5.8 Hz, 4H), 7.30 – 7.24 (m, 8H), 4.60 (p,J = 3.7 Hz, 4H), 4.44 (dd, J = 11.3, 3.5 Hz, 4H), 4.19 (dd, J = 11.3, 3.5 Hz, 4H), 3.57 – 3.44 (m, 8H), 3.33 – 3.00 (m, 12H), 2.90 (t, J = 8.2 Hz, 8H), 2.35 – 1.99 (m, 16H), 1.80 – 1.27 (m, 24H), 1.05 (t, J = 8.2 Hz, 8H), 0.06(s, 12H); its high-resolution mass spectrum is as follows Figure 4 As shown, HRMS (m / z): 1933.4795 [M+H] + .

[0034] Example 5: Preparation of self-leveling floor coating: (1) Weigh out: 300g epoxy resin, 50g reactive diluent (benzyl glycidyl ether), 5g antistatic agent (prepared in Example 1), 30g modified flame retardant reinforcing agent (prepared in Example 4), 5g leveling agent (polyether modified polysiloxane), 20g film-forming aid (propylene glycol butyl ether), 30g wear-resistant functional filler (corundum powder), 5g fumed silica, 400g colored sand, 150g curing agent (waterborne epoxy curing agent), and 3g defoamer (BYK-066N); (2) Add epoxy resin and reactive diluent to a dispersion tank and stir at 350 rpm for 15 min to mix evenly; add antistatic agent, modified flame retardant reinforcing agent, leveling agent and film forming aid in sequence, and disperse at 1100 rpm for 6 min; slowly add wear-resistant functional filler and fumed silica, and disperse at 1200 rpm for 20 min; finally add colored sand, stir at 450 rpm for 20 min to mix evenly, and obtain component A; add curing agent to a mixing tank, then add defoamer, stir at 300 rpm for 10 min to mix evenly, and obtain component B; mix component A and component B, stir at 300 rpm for 20 min to mix evenly, and let stand to defoam for 10 min to obtain high wear-resistant epoxy colored sand self-leveling floor coating.

[0035] Example 6: Preparation of self-leveling floor coating: (1) Weigh out: 400g epoxy resin, 100g reactive diluent (benzyl glycidyl ether), 10g antistatic agent (prepared in Example 2), 40g modified flame retardant reinforcing agent (prepared in Example 4), 10g leveling agent (polyether modified polysiloxane), 30g film-forming aid (propylene glycol butyl ether), 40g wear-resistant functional filler (corundum powder), 15g fumed silica, 500g colored sand, 200g curing agent (waterborne epoxy curing agent), and 6g defoamer (BYK-066N); (2) Add epoxy resin and reactive diluent to a dispersion tank and stir at 350 rpm for 15 min to mix evenly; add antistatic agent, modified flame retardant reinforcing agent, leveling agent and film forming aid in sequence, and disperse at 1100 rpm for 6 min; slowly add wear-resistant functional filler and fumed silica, and disperse at 1200 rpm for 20 min; finally add colored sand, stir at 450 rpm for 20 min to mix evenly, and obtain component A; add curing agent to a mixing tank, then add defoamer, stir at 300 rpm for 10 min to mix evenly, and obtain component B; mix component A and component B, stir at 300 rpm for 20 min to mix evenly, and let stand to defoam for 10 min to obtain high wear-resistant epoxy colored sand self-leveling floor coating.

[0036] Example 7: Preparation of self-leveling floor coating: (1) Weigh out: 500g epoxy resin, 150g reactive diluent (benzyl glycidyl ether), 20g antistatic agent (prepared in Example 3), 60g modified flame retardant reinforcing agent (prepared in Example 4), 15g leveling agent (polyester modified polysiloxane), 50g film-forming aid (dipropylene glycol butyl ether), 50g wear-resistant functional filler (silicon carbide powder), 25g fumed silica, 600g colored sand, 250g curing agent (waterborne epoxy curing agent), and 10g defoamer (BYK-066N); (2) Add epoxy resin and reactive diluent to a dispersion tank and stir at 350 rpm for 15 min to mix evenly; add antistatic agent, modified flame retardant reinforcing agent, leveling agent and film forming aid in sequence, and disperse at 1100 rpm for 6 min; slowly add wear-resistant functional filler and fumed silica, and disperse at 1200 rpm for 20 min; finally add colored sand, stir at 450 rpm for 20 min to mix evenly, and obtain component A; add curing agent to a mixing tank, then add defoamer, stir at 300 rpm for 10 min to mix evenly, and obtain component B; mix component A and component B, stir at 300 rpm for 20 min to mix evenly, and let stand to defoam for 10 min to obtain high wear-resistant epoxy colored sand self-leveling floor coating.

[0037] Comparative Example 1, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the antistatic agent is replaced with an equal weight of an antistatic agent prepared by the following method: The preparation method of the antistatic agent is basically the same as that in Example 2, except that the D-xylose in step S1 is replaced with an equimolar amount of DL-glyceraldehyde; the amount of 3-(3-(3-chloropropoxy)propoxy)propionic acid in step S1 is replaced with 0.205 mol, and the amount of N,N'-dicyclohexylcarbodiimide is replaced with 0.21 mol; and the amount of dodecyl dimethyl tertiary amine in step S2 is replaced with 0.203 mol.

[0038] Comparative Example 2, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the antistatic agent is replaced with an equal weight of an antistatic agent prepared by the following method: The preparation method of the antistatic agent is basically the same as that in Example 2, except that 3-(3-(3-chloropropoxy)propoxy)propionic acid in step S1 is replaced with an equimolar amount of 8-chlorooctanoic acid.

[0039] Comparative Example 3, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the antistatic agent is replaced with an equal weight of an antistatic agent prepared by the following method: The preparation method of the antistatic agent is basically the same as that in Example 2, except that the dodecyl dimethyl tertiary amine in step S2 is replaced with an equimolar amount of N,N-dimethylhexylamine.

[0040] Comparative Example 4, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the antistatic agent is replaced with an equal weight of an antistatic agent prepared by the following method: The preparation method of the antistatic agent is basically the same as that in Example 2, except that 1,3-bis((2,2-dimethyl-1,3-dioxapentane-4-yl)methoxy)prop-2-amine in step S3 is replaced with an equimolar amount of 2,2-dimethyl-1,3-dioxapentane-4-methylamine.

[0041] Comparative Example 5, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the modified flame retardant reinforcing agent is replaced with an equal weight of the modified flame retardant reinforcing agent prepared by the following method: The preparation method of the modified flame retardant reinforcing agent is basically the same as that in Example 4, except that 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane in step A1 is replaced with an equimolar amount of 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane.

[0042] Comparative Example 6, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the modified flame retardant reinforcing agent is replaced with an equal weight of the modified flame retardant reinforcing agent prepared by the following method: The preparation method of the modified flame retardant reinforcing agent is basically the same as that in Example 4, except that the 4-mercaptophenylboronic acid in step A1 is replaced with an equimolar amount of 3-mercaptophenylboronic acid.

[0043] Comparative Example 7, the high-wear-resistant epoxy colored sand self-leveling floor coating is basically the same as that in Example 6, except that the modified flame retardant reinforcing agent is replaced with an equal weight of the modified flame retardant reinforcing agent prepared by the following method: The preparation method of the modified flame retardant reinforcing agent is basically the same as that in Example 4, except that the lipoic acid in step A3 is replaced with an equimolar amount of 4-(methyl disulfide)butyric acid.

[0044] The epoxy resin used in the embodiments and comparative examples of this application is model E-51; the polyether-modified polysiloxane is model BYK-333; the polyester-modified polysiloxane is model BYK-310; the waterborne epoxy curing agent is model TOCPOLY EH-3870; the corundum powder has a particle size of 45-75μm and is produced by Henan Sicheng Grinding Technology Co., Ltd.; the silicon carbide fine powder has a particle size of 40-70μm and is produced by Anyang Qiansheng Metallurgical Refractory Co., Ltd.; the fumed silica is model HDK®T40; and the colored sand is natural colored sand with a particle size of 0.45-0.85mm.

[0045] The performance of the floor coatings prepared in Examples 5-7 and Comparative Examples 1-7 was tested, and the test results are shown in Table 1.

[0046] Abrasion resistance test: The coating was uniformly applied to a circular aluminum plate (100 mm in diameter and 3 mm in thickness). The self-leveling floor coating was evenly rolled onto the surface of the circular aluminum plate using an SZQ-100 coating preparation device. The coating thickness was 30 μm. The coating was dried at room temperature for 7 days to obtain the coating. The mass M1 of the aluminum plate and the coating was weighed. Then, the abrasion resistance of the coating was tested on a Taber 5135 abrasion tester. The positive pressure load during the abrasion process was 750 g, the grinding wheel model was CS-10, the number of abrasion cycles was 500, and the rotation speed of the rotating friction disc was 60 r / min. After the coating abrasion test, the mass M2 of the aluminum plate and the coating was measured again. The amount of coating wear was calculated according to the following formula: P = M1 − M2.

[0047] Impact resistance test: Referring to GB / T 1732-2020 Test Method for Impact Resistance of Coating Film, a paint film impact tester was used to conduct a forward impact performance test on the high wear-resistant epoxy colored sand self-leveling floor coatings prepared in the examples and comparative examples. Tinplate (dimensions 120mm×50mm×0.2mm) was used as the substrate, and the tinplate met the technical requirements of GB / T 9271. The coating was evenly applied to the surface of the tinplate using an SZQ-100 coating preparation device, with a coating thickness of 100μm. The prepared sample was placed in a forced-air drying oven and dried at 130℃ for 24 hours to obtain the sample. The cured sample was placed flat on the base of the impact tester, and a 1kg weight was dropped freely from a height of 30cm to impact the coating. After the test, the sample was removed, and the impact point was observed with a magnifying glass for cracks, wrinkles, and peeling. If no cracks, wrinkles, or peeling are observed, repeat the test at higher positions (each time increasing the height by 5 cm or multiples of 5 cm) until cracks, wrinkles, or peeling are observed; if cracks, wrinkles, or peeling are observed, repeat the test at lower positions (each time decreasing by 1 cm) until no cracks, wrinkles, or peeling are observed. The result is expressed as the maximum height (cm) at which no cracks, wrinkles, or peeling are observed in three tests.

[0048] Sample preparation: The asbestos cement board (150mm×100mm×5mm) was sanded with 60-grit sandpaper to remove floating dust. After that, it was immersed in deionized water for ultrasonic cleaning. Then it was taken out and cured for 7 days under standard conditions of 23±2℃ and 50±5% relative humidity for later use. The asbestos cement board was fixed on a horizontal table. The self-leveling floor coating was evenly rolled onto the surface of the asbestos cement board using an SZQ-100 coating preparation tool. The coating thickness was 25μm. After the coating was completed, it was placed in an environment of room temperature and 50% relative humidity to dry for 48 hours to obtain the sample. The antistatic performance and self-healing performance of the sample were tested.

[0049] Antistatic performance test: According to GB / T 31838.3-2019, the surface resistivity of the sample was measured using electrode device A in a specific environment (temperature 23℃, relative humidity 50%), and the test voltage was set to 500V.

[0050] Self-healing performance test method: The sample is scratched with a scalpel with a scratch width of 20μm. Then the scratched coating is heated at 50℃ for 24h. The scratch width is tested and the repair rate is calculated as (scratch width before heating and repair - scratch width after heating and repair) / scratch width before heating and repair × 100%.

[0051] Flame retardancy test: The fiber cement board (2400mm×1200mm×8mm) was sanded with 60-grit sandpaper to remove dust. After cleaning, it was immersed in deionized water for ultrasonic cleaning. Then, it was taken out and cured for 7 days under standard conditions of 23±2℃ and 50±5% relative humidity. The fiber cement board was fixed on a horizontal table. The self-leveling floor coating was evenly rolled onto the surface of the fiber cement board using an SZQ-100 coating preparation tool. The coating thickness was 8mm. After the coating was rolled, it was placed in an environment of room temperature and 50% relative humidity to dry for 48 hours. The coating was then scraped off the fiber cement board to obtain the sample. The flame retardancy performance of the sample was tested according to GB 8624-2012 "Classification of Burning Performance of Building Materials and Products".

[0052] Table 1 Performance Test Data of High Abrasion-Resistant Epoxy Colored Sand Self-Leveling Floor Coating

[0053] As can be seen from Table 1, the self-leveling floor coatings prepared in Examples 5-7 of this application have good wear resistance, antistatic properties, flame retardant properties and self-healing properties.

[0054] The antistatic agent prepared in this application is centered on a D-xylose backbone, with four symmetrical flexible arms connected by ester groups. Each arm contains a polyether segment, and the chain ends are quaternized to form positively charged quaternary ammonium cation centers. As strongly hydrophilic ionic centers, the quaternary ammonium cations can migrate to the surface after the coating cures and form a continuous ionic conductive network, effectively dissipating static charge and providing a permanent antistatic effect. Multiple hydroxyl groups significantly enhance the compatibility and interfacial bonding between the compound and the epoxy resin matrix, and are uniformly dispersed in the continuous phase through hydrogen bonding, avoiding the aggregation or precipitation of traditional small-molecule antistatic agents. Simultaneously, the strong hydrophilicity of the hydroxyl groups allows them to adsorb trace amounts of moisture in low-humidity environments, forming auxiliary ion conduction channels and further reducing surface resistivity. The flexible polyether segments endow the molecules with good chain mobility, promoting the enrichment of quaternary ammonium ions to the coating surface, while improving overall flexibility and preventing coating embrittlement. The synergistic effect of multiple functional groups enables the antistatic agent to achieve low surface resistivity in epoxy colored sand self-leveling floor coatings.

[0055] In Comparative Example 2, replacing 3-(3-(3-chloropropoxy)propoxy)propionic acid with 8-chlorooctanoic acid led to a decrease in performance for the following reasons: the side chain structure changed from a flexible polyether chain to an alkane chain, which weakened the compatibility between the molecule and the resin matrix and the ability of chain segments to move. This resulted in a decrease in the migration ability of the molecule in the coating matrix and the surface enrichment efficiency, making it difficult for the quaternary ammonium salt cations and polyhydroxy functional groups to effectively diffuse to the coating surface to form a continuous conductive network. At the same time, the excessive hydrophobicity also damaged the compatibility between the molecule and the polar resin matrix, leading to agglomeration, which further hindered the construction of uniform conductive channels and resulted in a decrease in antistatic performance.

[0056] In Comparative Example 3, after replacing dodecyl dimethyl tertiary amine with N,N-dimethylhexylamine, the hydrophobic chain of the quaternary ammonium salt was shortened, resulting in poor compatibility with the resin matrix. This caused the antistatic agent to undergo phase separation and agglomeration in the coating, hindering its migration and enrichment on the coating surface. Consequently, the surface ionic conductive network density decreased, the antistatic performance was reduced, and the density and cohesion of the coating decreased, thus reducing the wear resistance.

[0057] The antistatic agent prepared in Comparative Example 4 has a reduced number of hydrolyzable hydroxyl groups, which weakens the hydrogen bonding between the molecule and the epoxy resin matrix, resulting in uneven dispersion and easy aggregation in the coating, hindering the continuity of the ionic conductive network. At the same time, the molecule's hydrophilicity decreases, and its ability to adsorb moisture and assist in conductivity in low humidity environments becomes worse, thus reducing its antistatic performance.

[0058] The modified flame retardant and reinforcing agent prepared in this application uses cyclotetrasiloxane as a backbone, with four p-boronic acid phenyl sulfide units linked by sulfur-carbon bonds, and then a propylene glycolamine structure linked by borate ester bonds, with thioctic acid grafted at the end. The siloxane cyclic core preferentially oxidizes during high-temperature combustion to form a dense silicon-carbon oxide ceramic layer, effectively blocking oxygen diffusion, heat transfer, and inhibiting the release of combustible gases. The benzene ring, as an aromatic carbon source, promotes rapid char formation on the material surface, forming an expanded carbon layer that further enhances heat insulation and smoke suppression. When the boron ester bonds decompose thermally, they release boron oxide (B2O3), which synergistically works with the carbon layer to promote the formation of a dense, crack-free glassy protective layer, achieving a multi-element synergistic flame-retardant mechanism of boron, silicon, and aromatics, thereby reducing the heat release rate. Simultaneously, the siloxane segments maintain the mechanical integrity of the coating, preventing embrittlement. Regarding self-healing properties, the boron ester bonds undergo reversible hydrolysis-esterification reactions upon mechanical damage, rapidly dissociating and reforming bonds, promoting crack closure and structural reconstruction. Disulfide bonds achieve dynamic bond recombination at room temperature or under mild external stimuli (such as heat or light), supporting segment migration and re-crosslinking of damaged areas. The cyclic POSS cage-like core provides a rigid multi-arm topology, ensuring the uniform distribution of the four functional arms and forming a high-density three-dimensional dynamic bond network, thereby enhancing repair efficiency. The synergistic effect of multiple functional groups significantly enhances the self-healing ability of the material, giving the coating excellent durability after repeated damage.

[0059] In Comparative Example 5, the significant decrease in the performance of the modified flame retardant enhancer after replacing 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane with an equimolar amount of 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane was mainly due to the transformation of the siloxane core from a highly symmetrical POSS structure to a flexible linear Si-O-Si structure. Although both provide four vinyl groups for mercapto-ene click reactions and ultimately graft the same number of functional arms, the linear disiloxane core has a lower thermal decomposition temperature and insufficient rigidity, resulting in a loose and brittle char layer at high temperatures and a weakened boron-silicon synergistic flame retardant effect, ultimately leading to a decline in coating performance.

[0060] In Comparative Example 6, when step 4-mercaptophenylboronic acid was replaced with 3-mercaptophenylboronic acid, the main reason for the performance decline was that the substitution position of the benzene ring changed from para to meta, which led to the destruction of molecular symmetry, increased steric hindrance, and uneven inter-arm arrangement. This caused the modified flame retardant reinforcing agent to easily aggregate in the coating matrix, resulting in poor compatibility, a loose high-temperature char layer, and a weakened silicon-boron-sulfur synergistic flame retardant effect, thus leading to a performance decline.

[0061] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A high-wear-resistant epoxy colored sand self-leveling floor coating, characterized in that, The raw materials include the following parts by weight: 30-50 parts epoxy resin, 5-15 parts reactive diluent, 0.5-2 parts antistatic agent, 3-6 parts modified flame retardant reinforcing agent, 0.5-1.5 parts leveling agent, 2-5 parts film-forming aid, 3-5 parts wear-resistant functional filler, 0.5-2.5 parts fumed silica, 40-60 parts colored sand, 15-25 parts curing agent, and 0.3-1.0 parts defoamer; The antistatic agent is prepared by the following method: S1: 3-(3-(3-chloropropoxy)propoxy)propionic acid reacts with D-xylose to form a four-armed compound. S2: The four-armed compound reacts with dodecyl dimethyl tertiary amine to form a quaternary ammonium salt compound. S3: Quaternary ammonium salt compounds react with 1,3-bis((2,2-dimethyl-1,3-dioxapentane-4-yl)methoxy)prop-2-amine to generate heteropentane-modified quaternary ammonium salt compounds. S4: Heteropene-modified quaternary ammonium salt compounds hydrolyze to generate antistatic agents.

2. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 1, characterized in that, In step S1, the molar ratio of 3-(3-(3-chloropropoxy)propoxy)propionic acid to D-xylose is (4.05-4.1):

1.

3. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 1, characterized in that, In step S2, the molar ratio of the four-armed compound to dodecyl dimethyl tertiary amine is 1:(4.02-4.05).

4. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 1, characterized in that, In step S3, the molar ratio of the quaternary ammonium salt compound to 1,3-bis((2,2-dimethyl-1,3-dioxapentane-4-yl)methoxy)prop-2-amine is 1:(1.05-1.1).

5. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 1, characterized in that, The modified flame retardant reinforcing agent is prepared by the following method: A1: 2,4,6,8-Tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane reacts with 4-mercaptophenylboronic acid to generate intermediate 1. A2: Intermediate 1 reacts with 3-amino-1,2-propanediol to generate intermediate 2. A3: Intermediate 2 reacts with lipoic acid to generate a modified flame retardant and reinforcing agent.

6. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 5, characterized in that, In step A1, the molar ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane to 4-mercaptophenylboronic acid is 1:4.

02.

7. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 5, characterized in that, In step A2, the molar ratio of intermediate 1 to 3-amino-1,2-propanediol is 1:4.05; in step A3, the molar ratio of intermediate 2 to thioctic acid is 1:4.

06.

8. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 1, characterized in that, The reactive diluent is benzyl glycidyl ether; the leveling agent is one of polyether-modified polysiloxane and polyester-modified polysiloxane; the film-forming aid is one of propylene glycol butyl ether and dipropylene glycol butyl ether; and the curing agent is an aqueous epoxy curing agent.

9. The high wear-resistant epoxy colored sand self-leveling floor coating according to claim 1, characterized in that, The defoamer is BYK-066N; the wear-resistant filler is one of corundum powder and silicon carbide powder.

10. A method for preparing a high-wear-resistant epoxy colored sand self-leveling floor coating according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 30-50 parts epoxy resin, 5-15 parts reactive diluent, 0.5-2 parts antistatic agent, 3-6 parts modified flame retardant reinforcing agent, 0.5-1.5 parts leveling agent, 2-5 parts film-forming aid, 3-5 parts wear-resistant functional filler, 0.5-2.5 parts fumed silica, 40-60 parts colored sand, 15-25 parts curing agent, and 0.3-1.0 parts defoamer; (2) Add epoxy resin and reactive diluent to a dispersion tank and stir evenly; add antistatic agent, modified flame retardant reinforcing agent, leveling agent and film-forming aid in sequence and disperse at high speed; add wear-resistant functional filler and fumed silica and disperse at high speed. Finally, add colored sand and stir evenly to obtain component A; add curing agent to the mixing tank, then add defoamer and stir evenly to obtain component B; mix component A and component B, stir evenly, and let stand to defoam, thus obtaining high wear-resistant epoxy colored sand self-leveling floor coating.

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