Floor paint resistant to temperature difference and preparation process thereof

Abstract

The present application relates to the technical field of paint, more particularly, it relates to a temperature difference resistant floor paint and a preparation process thereof.A temperature difference resistant floor paint and a preparation process thereof, comprising the following steps: resin blending modification, porous boron nitride microsphere preparation, composite temperature resistant filler preparation, composite temperature resistant filler coating treatment and floor paint preparation.In the present application, the weather resistance and aging resistance of the floor paint can be effectively improved by hybrid modification of the epoxy resin; the functionalized graphene oxide is intercalated into the porous boron nitride microspheres, the composite temperature resistant filler formed as a filling auxiliary is added to the floor paint, which can effectively improve the temperature difference resistance and aging resistance of the floor paint, and the coating treatment of the composite temperature resistant filler helps to increase the compatibility between the composite temperature resistant filler and the resin matrix, ensuring that the composite temperature resistant filler is uniformly dispersed in the floor paint.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and more specifically, to a temperature-resistant floor coating and its preparation process. Background Technology

[0002] Epoxy floor coatings are favored by many users in industrial flooring applications due to their strong film, good integrity, wear resistance, and corrosion resistance. They are widely used in the decoration of production workshops, underground parking lots, warehouses, and other places. However, epoxy floor coatings are quite sensitive to sudden temperature changes. Extreme temperature changes can exacerbate the thermal expansion and contraction effect of the coating film, leading to internal fatigue damage. Consequently, long-term or frequent temperature fluctuations can cause the coating film to crack or peel off, affecting the quality and performance of the floor coating. Therefore, the temperature resistance of epoxy floor coatings still needs improvement.

[0003] Chinese patent CN108707390A discloses an ultra-heat-resistant epoxy resin composite coating and its preparation method. This patent adds fillers such as boron nitride, carbon fiber, and nano-titanium nitride to epoxy resin. Although these heat-resistant fillers can endow the epoxy resin composite coating with heat resistance, making it suitable for use as an anti-rust primer, floor paint, industrial heavy-duty anti-corrosion paint, and oil tank paint, the patent does not disclose whether these heat-resistant fillers can improve the aging resistance and temperature difference resistance of the epoxy resin composite coating in environments with varying temperatures. In addition, the unmodified inorganic fillers such as boron nitride and nano-titanium nitride have poor compatibility with the epoxy resin matrix, and are prone to agglomeration and uneven dispersion. Among them, boron nitride has high hardness and brittleness, and its particles can easily cause stress concentration in the epoxy resin matrix, thereby damaging the epoxy resin matrix structure, affecting the performance and quality of the epoxy resin composite coating, and making it difficult to fully utilize the role of boron nitride. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a floor coating resistant to temperature differences and its preparation process.

[0005] A floor coating resistant to temperature differences, comprising the following components:

[0006] 50-120 parts by weight of waterborne alkyd hybrid epoxy resin, 5-30 parts by weight of coated composite heat-resistant filler, 2-5 parts by weight of reactive diluent, 20-80 parts by weight of curing agent, 0.05-0.5 parts by weight of dispersant, 0.1-0.5 parts by weight of leveling agent, 0.1-0.5 parts by weight of defoamer, and 0.5-1.5 parts by weight of thickener;

[0007] The raw materials for the waterborne alkyd hybrid epoxy resin include: 60-150 parts by weight of epoxy resin, 80-120 parts by weight of alkyd resin, 20-50 parts by weight of butanol, 0.3-1 parts by weight of benzoyl peroxide, 10-30 parts by weight of xylene, 10-25 parts by weight of triethanolamine and 100-200 parts by weight of water.

[0008] The raw materials for the coated composite heat-resistant filler include: 200-300 parts by weight of triaminomethane buffer solution, 6-20 parts by weight of dopamine hydrochloride, 9-15 parts by weight of sodium periodate, and 5-20 parts by weight of composite heat-resistant filler.

[0009] The raw materials for the composite heat-resistant filler include: 5-30 parts by weight of functionalized graphene oxide, 80-200 parts by weight of deionized water, 10-60 parts by weight of porous boron nitride microspheres, and 5-8 parts by weight of zirconia beads. The functionalized graphene oxide is obtained by mixing graphene oxide, deionized water, and p-aniline sulfonic acid through stirring, heating, filtering, washing, and drying. The porous boron nitride microspheres are obtained by ball milling hexagonal boron nitride, ammonium bicarbonate, and zirconia beads, mixing with water, high-speed exfoliation, standing, drying the supernatant, and calcining.

[0010] A process for preparing a temperature-difference resistant floor coating includes the following steps:

[0011] S1: Resin blending modification: Alkyd resin was prepared using soybean oil, pentaerythritol, glycerol, benzoic acid, lithium hydroxide, phthalic anhydride and xylene. After heating and stirring the alkyd resin, butanol, benzoyl peroxide and xylene, epoxy resin was added dropwise while stirring. After the epoxy resin was added, triethanolamine was added and the reaction was stirred continuously. After the reaction was completed, deionized water was added and ultrasonically dispersed to obtain waterborne alkyd hybrid epoxy resin.

[0012] S2: Preparation of porous boron nitride microspheres: Hexagonal boron nitride, ammonium bicarbonate and zirconium oxide beads are ball-milled to obtain a mixed powder. The mixed powder is added to deionized water and stirred to form a mixed solution. The mixed solution is peeled, allowed to stand, the supernatant is collected, dried and calcined to obtain porous boron nitride microspheres.

[0013] S3: Preparation of composite heat-resistant filler: Graphene oxide is dispersed and mixed in deionized water, p-aniline sulfonic acid is added, and after stirring, mixing, heating and reacting, filtering, washing and drying, functionalized graphene oxide is obtained. Functionalized graphene oxide, porous boron nitride microspheres and zirconium oxide beads are dispersed in deionized water to obtain a mixture. The mixture is ball-milled, filtered, washed and dried to obtain composite heat-resistant filler.

[0014] S4: Composite heat-resistant filler coating treatment: Dissolve triaminomethane buffer in deionized water to obtain triaminomethane buffer aqueous solution. Add dopamine hydrochloride, sodium periodate and composite heat-resistant filler to triaminomethane buffer aqueous solution and stir to mix. After filtration and drying, the coated composite heat-resistant filler is obtained.

[0015] S5: Preparation of floor coating: Dispersant, leveling agent, defoamer, thickener, reactive diluent, coated composite heat-resistant filler, water-based alkyd hybrid epoxy resin and curing agent are stirred and mixed to obtain floor coating.

[0016] Furthermore, the resin blending modification in step S1 specifically includes the following steps:

[0017] S1.1: Add 90-130 parts by weight of soybean oil, 15-30 parts by weight of pentaerythritol, 5-25 parts by weight of glycerol, 5-10 parts by weight of benzoic acid and 0.5-2 parts by weight of lithium hydroxide into the reactor, and heat while stirring to 240-248°C, and keep warm for 1-2 hours for alcoholysis.

[0018] S1.2: After alcoholysis, the mixture is allowed to cool naturally to 170-190°C. Then, 50-70 parts by weight of phthalic anhydride and 8-15 parts by weight of xylene are added to the reactor. The mixture is stirred and mixed, heated to 210-220°C and refluxed for 1-3 hours. After cooling to room temperature, the filtrate is filtered to obtain alkyd resin.

[0019] S1.3: Add 80-120 parts by weight of alkyd resin, 20-50 parts by weight of butanol, 0.3-1 parts by weight of benzoyl peroxide and 10-30 parts by weight of xylene to the reactor in sequence, heat to 110-120°C, stir for 10-15 min, maintain the temperature at 110-120°C, add 60-150 parts by weight of epoxy resin dropwise to the reactor while stirring, control the dropwise addition time to 2-3 h, after the epoxy resin dropwise addition is complete, add 10-25 parts by weight of triethanolamine, and continue stirring to react for 2-4 h;

[0020] S1.4: After the reaction is complete, add 100-200 parts by weight of deionized water to the reactor and ultrasonically disperse for 20-40 minutes to obtain waterborne alkyd hybrid epoxy resin.

[0021] Furthermore, both the reactor and the reaction vessel are equipped with a stirrer, a thermometer, and a reflux condenser.

[0022] Furthermore, step S2, the preparation of porous boron nitride microspheres, specifically includes the following steps:

[0023] S2.1: Place 30-60 parts by weight of hexagonal boron nitride, 50-100 parts by weight of ammonium bicarbonate and 5-8 parts by weight of zirconium oxide beads into a ball mill jar and ball mill for 10-12 hours at a speed of 320-360 r / min to obtain a mixed powder. Wash and dry the mixed powder for later use.

[0024] S2.2: Add the mixed powder to deionized water, with a solid-liquid mixing weight ratio of (1-10):100. After stirring and mixing, a mixed solution is obtained. The mixed solution is poured into a high-speed homogenizer for exfoliation for 3-4 hours at a speed of 5000-6000 r / min. Then, it is allowed to stand for 24-48 hours. The supernatant after standing is taken and dried to obtain functionalized boron nitride.

[0025] S2.3: Functionalized boron nitride is placed in a tube furnace and calcined at a temperature of 450–500℃ for 24–32 h to obtain porous boron nitride microspheres.

[0026] Furthermore, step S3, the preparation of the composite heat-resistant filler, specifically includes the following steps:

[0027] S3.1: Add 1-30 parts by weight of graphene oxide to 100-200 parts by weight of deionized water, and ultrasonically disperse for 10-30 min to obtain a graphene oxide dispersion. Then, add 1-15 parts by weight of p-aniline sulfonic acid to the graphene oxide dispersion, stir and mix, heat to 70-80℃ and react for 8-12 h. After filtration, washing and drying, functionalized graphene oxide is obtained.

[0028] S3.2: Take 5-30 parts by weight of functionalized graphene oxide and add it to 80-200 parts by weight of deionized water. After ultrasonic dispersion for 10-30 minutes, add 10-60 parts by weight of porous boron nitride microspheres and 5-8 parts by weight of zirconium oxide beads. Mix evenly to obtain a mixture.

[0029] S3.3: Add the mixture to a ball mill and ball mill for 1 to 3 hours at a speed of 280 to 400 r / min. After ball milling, filter, wash and dry to obtain the composite heat-resistant filler.

[0030] Furthermore, the diameter of the zirconia beads is 10–50 mm.

[0031] Furthermore, step S4, the composite heat-resistant filler coating treatment, specifically includes the following steps:

[0032] S4.1: Dissolve 0.1 to 2 parts by weight of triaminomethane buffer solution in 200 to 300 parts by weight of deionized water, stir well, and adjust the pH to 8.0 to 8.5 to obtain a triaminomethane buffer solution.

[0033] S4.2: Take 100-150 parts by weight of triaminomethane buffer solution and put it into container A. Add 6-20 parts by weight of dopamine hydrochloride to container A and stir well to obtain solution A. Then take 100-150 parts by weight of triaminomethane buffer solution and put it into container B. Add 9-15 parts by weight of sodium periodate to container B and stir well to obtain solution B.

[0034] S4.3: Take 5-20 parts by weight of composite heat-resistant filler and add it to solution B. After stirring evenly, ultrasonically disperse for 1-2 hours. Then pour solution A into container B and stir to mix. Ultrasonically disperse for 1-2 hours. Next, filter the suspension obtained in container B. Put the filter cake into a dryer and dry it at 100-120℃ for 40-80 minutes to obtain the coated composite heat-resistant filler.

[0035] Furthermore, step S5, the preparation of the floor coating, specifically includes the following steps:

[0036] S5.1: Mix 0.05-0.5 parts by weight of dispersant, 0.1-0.5 parts by weight of leveling agent, 0.1-0.5 parts by weight of defoamer, and 0.5-1.5 parts by weight of thickener to obtain mixture A;

[0037] S5.2: Add 2-5 parts by weight of reactive diluent and 5-30 parts by weight of coated composite heat-resistant filler to 50-120 parts by weight of waterborne alkyd hybrid epoxy resin in sequence. After stirring evenly, add 20-80 parts by weight of curing agent to obtain mixture B.

[0038] S5.3: Mix mixture A and mixture B to obtain floor paint.

[0039] Furthermore, the dispersant is triethylhexylphosphate, sodium dodecyl sulfate, or methylpentanol; the leveling agent is polydimethylsiloxane or melamine-formaldehyde resin; the thickener is methylcellulose or hydroxypropyl methylcellulose; the reactive diluent is butyl glycidyl ether, allyl glycidyl ether, or C10-C12 alkyl glycidyl ether; the curing agent is a fatty amine curing agent or a polyamide curing agent; and the defoamer is a silicone oil-type silicone defoamer, an emulsion-type silicone defoamer, or a silicone oil solution-type silicone defoamer.

[0040] The present invention has the following advantages:

[0041] 1. In this invention, by hybridizing the epoxy resin to graft copolymerize the epoxy resin and alkyd resin, the prepared waterborne alkyd hybrid epoxy resin has good aging resistance, which is beneficial to improving the weather resistance of the floor paint against natural factors such as ultraviolet radiation, wind and rain, and can also improve the temperature difference resistance of the floor paint. After the floor paint is applied to the substrate to form a paint film, the paint film can adapt to the expansion and contraction of the substrate under different temperature differences, reducing the cracking or peeling of the paint film caused by stress concentration.

[0042] 2. In this invention, functionalized graphene oxide is intercalated into porous boron nitride microspheres to form a composite heat-resistant filler. The composite heat-resistant filler is added to the floor paint as a filler, so that the functionalized graphene oxide and porous boron nitride microspheres synergistically enhance the thermal stability of the floor paint, thereby effectively improving the temperature difference resistance and aging resistance of the floor paint. This allows the formed paint film to maintain a good working condition in environments with fluctuating temperature changes, and it is not easy to deform, crack or degrade in performance.

[0043] 3. In this invention, by coating the surface of the composite heat-resistant filler with dopamine, the compatibility between the composite heat-resistant filler and the resin matrix is ​​increased, ensuring that the composite heat-resistant filler is uniformly dispersed in the floor paint, and ensuring that the paint film has stable temperature difference resistance and aging resistance after formation, thus avoiding the impact on the quality and performance of the floor paint due to uneven dispersion of the composite heat-resistant filler. Detailed Implementation

[0044] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.

[0045] Example 1

[0046] A process for preparing a temperature-difference resistant floor coating includes the following steps:

[0047] S1: Resin blending modification

[0048] S1.1: Add 130 parts by weight of soybean oil, 30 parts by weight of pentaerythritol, 25 parts by weight of glycerol, 10 parts by weight of benzoic acid and 2 parts by weight of lithium hydroxide into the reactor, and heat while stirring to 248°C, and keep warm for 2 hours for alcoholysis.

[0049] S1.2: After the alcoholysis is completed, the temperature is naturally cooled to 190°C. Then, 70 parts by weight of phthalic anhydride and 15 parts by weight of xylene are added to the reactor. The mixture is stirred and mixed. The temperature is heated to 220°C and refluxed for 3 hours. After cooling to room temperature, the filtrate is filtered to obtain alkyd resin.

[0050] S1.3: 120 parts by weight of alkyd resin, 50 parts by weight of butanol, 1 part by weight of benzoyl peroxide and 30 parts by weight of xylene were added sequentially to the reaction vessel, heated to 120°C, stirred for 15 min, and the temperature was maintained at 120°C. 150 parts by weight of epoxy resin were added dropwise to the reaction vessel while stirring, and the addition time was controlled at 3 h. After the epoxy resin was added, 25 parts by weight of triethanolamine were added, and the reaction was stirred continuously for 4 h.

[0051] S1.4: After the reaction is complete, add 200 parts by weight of water to the reactor and ultrasonically disperse for 40 min to obtain waterborne alkyd hybrid epoxy resin;

[0052] S2: Preparation of porous boron nitride microspheres

[0053] S2.1: Place 60 parts by weight of hexagonal boron nitride, 100 parts by weight of ammonium bicarbonate and 8 parts by weight of zirconia beads with a diameter of 30 mm into a ball mill jar and ball mill for 12 hours at a speed of 360 r / min to obtain a mixed powder. Wash and dry the mixed powder for later use.

[0054] S2.2: Add the mixed powder to deionized water, with a solid-liquid mixing weight ratio of 1:10. After stirring and mixing, a mixed solution is obtained. The mixed solution is poured into a high-speed homogenizer and peeled for 4 hours at a speed of 6000 r / min. Then, it is allowed to stand for 48 hours. The supernatant after standing is taken and dried to obtain functionalized boron nitride.

[0055] S2.3: Functionalized boron nitride was placed in a tube furnace and calcined at 500℃ for 32 hours to obtain porous boron nitride microspheres.

[0056] S3: Preparation of composite heat-resistant filler

[0057] S3.1: 30 parts by weight of graphene oxide were added to 200 parts by weight of deionized water and ultrasonically dispersed for 30 min to obtain a graphene oxide dispersion. Then, 15 parts by weight of p-aniline sulfonic acid were added to the graphene oxide dispersion, stirred and mixed, and heated to 80°C for 12 h. After filtration, washing and drying, functionalized graphene oxide was obtained.

[0058] S3.2: Take 30 parts by weight of functionalized graphene oxide and add it to 200 parts by weight of deionized water. After ultrasonic dispersion for 30 min, add 60 parts by weight of porous boron nitride microspheres and 8 parts by weight of zirconia beads with a diameter of 30 mm. After mixing evenly, a mixture is obtained.

[0059] S3.3: Add the mixture to a ball mill and ball mill for 3 hours at a speed of 400 r / min. After ball milling, filter, wash and dry to obtain composite heat-resistant filler.

[0060] S4: Composite heat-resistant filler coating treatment

[0061] S4.1: Dissolve 2 parts by weight of triaminomethane buffer solution in 300 parts by weight of deionized water, stir well, and adjust the pH to 8.5 using a pH meter and dilute hydrochloric acid to obtain a triaminomethane buffer solution.

[0062] S4.2: Take 150 parts by weight of triaminomethane buffer solution and put it into container A. Add 20 parts by weight of dopamine hydrochloride to container A and stir well to obtain solution A. Then take 150 parts by weight of triaminomethane buffer solution and put it into container B. Add 15 parts by weight of sodium periodate to container B and stir well to obtain solution B.

[0063] S4.3: Take 20 parts by weight of composite heat-resistant filler and add it to solution B. After stirring evenly, it is ultrasonically dispersed for 2 hours. Then, pour solution A into container B and stir to mix. It is ultrasonically dispersed for 2 hours. Next, filter the suspension obtained in container B. Put the filter cake into a dryer and dry it at 120℃ for 80 minutes to obtain the coated composite heat-resistant filler.

[0064] S5: Preparation of floor coating

[0065] S5.1: Mix 0.5 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of polydimethylsiloxane, 0.5 parts by weight of silicone oil-type organosilicon defoamer, and 1.5 parts by weight of methylcellulose to obtain mixture A;

[0066] S5.2: Add 5 parts by weight of butyl glycidyl ether and 30 parts by weight of the coated composite heat-resistant filler to 100 parts by weight of waterborne alkyd hybrid epoxy resin in sequence. After stirring evenly, add 60 parts by weight of fatty amine curing agent to obtain mixture B.

[0067] S5.3: Mix mixture A and mixture B to obtain floor paint.

[0068] Example 2

[0069] A process for preparing a temperature-difference resistant floor coating includes the following steps:

[0070] S1: Resin blending modification

[0071] S1.1: Add 130 parts by weight of soybean oil, 30 parts by weight of pentaerythritol, 25 parts by weight of glycerol, 10 parts by weight of benzoic acid and 2 parts by weight of lithium hydroxide into the reactor, and heat while stirring to 240°C, and keep warm for 1 hour for alcoholysis.

[0072] S1.2: After the alcoholysis is completed, the temperature is naturally cooled to 170°C. Then, 70 parts by weight of phthalic anhydride and 15 parts by weight of xylene are added to the reactor. The mixture is stirred and mixed. The temperature is heated to 210°C and refluxed for 1 hour. After cooling to room temperature, the filtrate is filtered to obtain alkyd resin.

[0073] S1.3: 120 parts by weight of alkyd resin, 50 parts by weight of butanol, 1 part by weight of benzoyl peroxide and 30 parts by weight of xylene were added sequentially to the reaction vessel, heated to 110°C, stirred for 10 min, and the temperature was maintained at 110°C. 150 parts by weight of epoxy resin were added dropwise to the reaction vessel while stirring, and the addition time was controlled at 2 h. After the epoxy resin was added, 25 parts by weight of triethanolamine were added, and the reaction was stirred continuously for 2 h.

[0074] S1.4: After the reaction is complete, add 200 parts by weight of water to the reactor and ultrasonically disperse for 20 minutes to obtain waterborne alkyd hybrid epoxy resin;

[0075] S2: Preparation of porous boron nitride microspheres

[0076] S2.1: Place 60 parts by weight of hexagonal boron nitride, 100 parts by weight of ammonium bicarbonate and 8 parts by weight of zirconia beads with a diameter of 30 mm into a ball mill jar and ball mill for 10 hours at a speed of 320 r / min to obtain a mixed powder. Wash and dry the mixed powder for later use.

[0077] S2.2: Add the mixed powder to deionized water, with a solid-liquid mixing weight ratio of 1:10. After stirring and mixing, a mixed solution is obtained. The mixed solution is poured into a high-speed homogenizer for exfoliation for 3 hours at a speed of 5000 r / min. Then, it is allowed to stand for 24 hours. The supernatant after standing is taken and dried to obtain functionalized boron nitride.

[0078] S2.3: Functionalized boron nitride is placed in a tube furnace and calcined at 450℃ for 24 hours to obtain porous boron nitride microspheres.

[0079] S3: Preparation of composite heat-resistant filler

[0080] S3.1: 30 parts by weight of graphene oxide were added to 200 parts by weight of deionized water and ultrasonically dispersed for 10 min to obtain a graphene oxide dispersion. Then, 15 parts by weight of p-aniline sulfonic acid were added to the graphene oxide dispersion, stirred and mixed, and heated to 70°C for 8 h. After filtration, washing and drying, functionalized graphene oxide was obtained.

[0081] S3.2: Take 30 parts by weight of functionalized graphene oxide and add it to 200 parts by weight of deionized water. After ultrasonic dispersion for 10 min, add 60 parts by weight of porous boron nitride microspheres and 8 parts by weight of zirconia beads with a diameter of 30 mm. After mixing evenly, a mixture is obtained.

[0082] S3.3: Add the mixture to a ball mill and ball mill for 1 hour at a speed of 280 r / min. After ball milling, filter, wash and dry to obtain composite heat-resistant filler.

[0083] S4: Composite heat-resistant filler coating treatment

[0084] S4.1: Dissolve 2 parts by weight of triaminomethane buffer in 300 parts by weight of deionized water, stir well, and adjust the pH to 8.0 using a pH meter and dilute hydrochloric acid to obtain a triaminomethane buffer aqueous solution.

[0085] S4.2: Take 150 parts by weight of triaminomethane buffer solution and put it into container A. Add 20 parts by weight of dopamine hydrochloride to container A and stir well to obtain solution A. Then take 150 parts by weight of triaminomethane buffer solution and put it into container B. Add 15 parts by weight of sodium periodate to container B and stir well to obtain solution B.

[0086] S4.3: Take 20 parts by weight of composite heat-resistant filler and add it to solution B. After stirring evenly, it is ultrasonically dispersed for 1 hour. Then, pour solution A into container B and stir to mix. It is ultrasonically dispersed for 1 hour. Next, filter the suspension obtained in container B. Put the filter cake into a dryer and dry it at 100℃ for 50 minutes to obtain the coated composite heat-resistant filler.

[0087] S5: Preparation of floor coating

[0088] S5.1: Mix 0.5 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of polydimethylsiloxane, 0.5 parts by weight of silicone oil-type organosilicon defoamer, and 1.5 parts by weight of methylcellulose to obtain mixture A;

[0089] S5.2: Add 5 parts by weight of butyl glycidyl ether and 30 parts by weight of the coated composite heat-resistant filler to 100 parts by weight of waterborne alkyd hybrid epoxy resin in sequence. After stirring evenly, add 60 parts by weight of fatty amine curing agent to obtain mixture B.

[0090] S5.3: Mix mixture A and mixture B to obtain floor paint.

[0091] Example 3

[0092] A process for preparing a temperature-difference resistant floor coating includes the following steps:

[0093] S1: Resin blending modification

[0094] S1.1: Add 90 parts by weight of soybean oil, 15 parts by weight of pentaerythritol, 5 parts by weight of glycerol, 5 parts by weight of benzoic acid and 0.5 parts by weight of lithium hydroxide into the reactor, and heat while stirring to 248°C, and keep warm for 2 hours for alcoholysis.

[0095] S1.2: After the alcoholysis is completed, the temperature is naturally cooled to 190°C. Then, 50 parts by weight of phthalic anhydride and 8 parts by weight of xylene are added to the reactor. The mixture is stirred and mixed, heated to 220°C and refluxed for 3 hours. After cooling to room temperature, the filtrate is filtered to obtain alkyd resin.

[0096] S1.3: 80 parts by weight of alkyd resin, 20 parts by weight of butanol, 0.3 parts by weight of benzoyl peroxide and 10 parts by weight of xylene were added sequentially to the reaction vessel, heated to 120°C, stirred for 15 min, and the temperature was maintained at 120°C. 80 parts by weight of epoxy resin were added dropwise to the reaction vessel while stirring, and the addition time was controlled at 3 h. After the epoxy resin was added, 10 parts by weight of triethanolamine were added, and the reaction was stirred continuously for 4 h.

[0097] S1.4: After the reaction is complete, add 100 parts by weight of water to the reactor and ultrasonically disperse for 40 min to obtain waterborne alkyd hybrid epoxy resin;

[0098] S2: Preparation of porous boron nitride microspheres

[0099] S2.1: Place 30 parts by weight of hexagonal boron nitride, 50 parts by weight of ammonium bicarbonate and 5 parts by weight of zirconia beads with a diameter of 30 mm into a ball mill jar and ball mill for 12 hours at a speed of 360 r / min to obtain a mixed powder. Wash and dry the mixed powder for later use.

[0100] S2.2: Add the mixed powder to deionized water, with a solid-liquid mixing weight ratio of 1:20. After stirring and mixing, a mixed solution is obtained. The mixed solution is poured into a high-speed homogenizer and peeled for 4 hours at a speed of 6000 r / min. Then, it is allowed to stand for 48 hours. The supernatant after standing is taken and dried to obtain functionalized boron nitride.

[0101] S2.3: Functionalized boron nitride was placed in a tube furnace and calcined at 500℃ for 32 hours to obtain porous boron nitride microspheres.

[0102] S3: Preparation of composite heat-resistant filler

[0103] S3.1: 10 parts by weight of graphene oxide were added to 100 parts by weight of deionized water and ultrasonically dispersed for 30 min to obtain a graphene oxide dispersion. Then, 10 parts by weight of p-aniline sulfonic acid were added to the graphene oxide dispersion, stirred and mixed, and heated to 80°C for 12 h. After filtration, washing and drying, functionalized graphene oxide was obtained.

[0104] S3.2: Take 10 parts by weight of functionalized graphene oxide and add it to 80 parts by weight of deionized water. After ultrasonic dispersion for 30 min, add 10 parts by weight of porous boron nitride microspheres and 5 parts by weight of zirconia beads with a diameter of 30 mm. After mixing evenly, a mixture is obtained.

[0105] S3.3: Add the mixture to a ball mill and ball mill for 3 hours at a speed of 400 r / min. After ball milling, filter, wash and dry to obtain composite heat-resistant filler.

[0106] S4: Composite heat-resistant filler coating treatment

[0107] S4.1: Dissolve 0.1 parts by weight of triaminomethane buffer in 200 parts by weight of deionized water, stir well, and adjust the pH to 8.5 using a pH meter and dilute hydrochloric acid to obtain a triaminomethane buffer aqueous solution.

[0108] S4.2: Take 100 parts by weight of triaminomethane buffer solution and put it into container A. Add 6 parts by weight of dopamine hydrochloride to container A and stir well to obtain solution A. Then take 100 parts by weight of triaminomethane buffer solution and put it into container B. Add 9 parts by weight of sodium periodate to container B and stir well to obtain solution B.

[0109] S4.3: Take 5 parts by weight of composite heat-resistant filler and add it to solution B. After stirring evenly, it is ultrasonically dispersed for 2 hours. Then, pour solution A into container B and stir to mix. It is ultrasonically dispersed for 2 hours. Next, filter the suspension obtained in container B. Put the filter cake into a dryer and dry it at 120°C for 80 minutes to obtain the coated composite heat-resistant filler.

[0110] S5: Preparation of floor coating

[0111] S5.1: Mix 0.05 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of polydimethylsiloxane, 0.1 parts by weight of silicone oil-based organosilicon defoamer, and 0.5 parts by weight of methylcellulose to obtain mixture A;

[0112] S5.2: Add 2 parts by weight of butyl glycidyl ether and 5 parts by weight of the coated composite heat-resistant filler to 50 parts by weight of waterborne alkyd hybrid epoxy resin in sequence. After stirring evenly, add 20 parts by weight of fatty amine curing agent to obtain mixture B.

[0113] S5.3: Mix mixture A and mixture B to obtain floor paint.

[0114] Comparative Example 1

[0115] Compared with Example 1, the difference of Comparative Example 1 is that step S1 is removed, and the waterborne alkyd hybrid epoxy resin used in step S5.2 is replaced with an equal part by weight of the epoxy resin used in the original step S1.3. The other steps remain unchanged, and the floor paint is prepared. This is called Comparative Example 1.

[0116] Comparative Example 2

[0117] Compared with Example 1, the difference of Comparative Example 2 is that step S2 is removed, and the porous boron nitride microspheres used in step S3.2 are replaced with an equal part by weight of functionalized graphene oxide (so that step S3.2 becomes: 90 parts by weight of functionalized graphene oxide and 8 parts by weight of zirconia beads with a diameter of 30 mm are added to 200 parts by weight of deionized water and mixed evenly to obtain a mixture). The other steps remain unchanged, and the floor paint is prepared. This is called Comparative Example 2.

[0118] Comparative Example 3

[0119] Compared with Example 1, the difference in Comparative Example 3 is that the functionalized graphene oxide used in step S3.2 is replaced with an equal part by weight of porous boron nitride microspheres (making step S3.2 become: 90 parts by weight of porous boron nitride microspheres and 8 parts by weight of zirconia beads with a diameter of 30 mm are added to 200 parts by weight of deionized water and mixed evenly to obtain a mixture). The other steps remain unchanged, and the floor paint is prepared. This is called Comparative Example 3.

[0120] Comparative Example 4

[0121] Compared with Example 1, the difference of Comparative Example 4 is that step S4 is removed, and the composite heat-resistant filler with coating treatment used in step S5.2 is replaced with an equal part by weight of composite heat-resistant filler. The other steps remain unchanged, and the floor paint is prepared. This is called Comparative Example 4.

[0122] Performance testing

[0123] Thermal cycling resistance test: The floor coatings of Examples 1-3 and Comparative Examples 1-4 were respectively rolled onto glass surfaces of the same size (10cm x 10cm) to form a coating with a thickness of 0.1cm. After the coatings dried, test samples were obtained. Each test sample was placed in a constant temperature testing chamber. The temperature was first lowered from room temperature to -20℃ and maintained for 2 hours, then raised to 60℃ and maintained for 2 hours, then lowered to room temperature and maintained for 2 hours. The temperature change time did not exceed 1 hour. This thermal cycling was repeated 30 times. The paint film was then checked for cracking, discoloration, loss of gloss, or peeling. If the paint film showed no change, the performance met the requirements. The results are shown in Table 1.

[0124] Resistance to thermal cycling Example 1 No change in paint film Example 2 No change in paint film Example 3 No change in paint film Comparative Example 1 Extensive cracking and partial peeling of the paint film Comparative Example 2 Slight cracking of paint film Comparative Example 3 Slight cracking of paint film Comparative Example 4 Minor cracks in the paint film

[0125] Table 1

[0126] As shown in Table 1, after 30 cycles of hot and cold treatment, the paint films formed by roller coating of the floor paints in Examples 1-3 did not exhibit cracking, discoloration, or peeling, indicating that the temperature difference resistance of the floor paints in Examples 1-3 met the requirements. In contrast, the paint film of Comparative Example 1 showed large-area cracking and local peeling, indicating that directly using epoxy resin as the resin matrix material of the floor paint resulted in poor temperature difference resistance, while the water-based alkyd hybrid epoxy resin used in Examples 1-3 helped to give the floor paint good temperature difference resistance. Furthermore, after 30 cycles of hot and cold cycling, the paint films in Comparative Examples 2-4 all exhibited varying degrees of cracking. This indicates that simply adding porous boron nitride microspheres and functionalized graphene to the floor paint alone does not provide adequate temperature difference resistance. However, intercalating functionalized graphene into porous boron nitride microspheres to create a composite heat-resistant filler, and then adding this composite heat-resistant filler to the floor paint, significantly improves its temperature difference resistance. In other words, the porous boron nitride microspheres and functionalized graphene in the composite heat-resistant filler synergistically enhance the temperature difference resistance of the floor paint. Moreover, coating the composite heat-resistant filler before use helps ensure better dispersion of it within the floor paint, resulting in stable temperature difference resistance and preventing localized cracking or peeling of the paint film caused by uneven distribution of the composite heat-resistant filler.

[0127] Artificial weathering resistance test: The floor coatings of Examples 1-3 and Comparative Examples 1-4 were tested for artificial weathering resistance in accordance with GB / T1865-2009 Paints and Varnishes - Artificial weathering and artificial radiation exposure filtered xenon arc radiation standard and GB / T1766-2008 Paints and Varnishes - Rating method for coating aging. The results are shown in Table 2.

[0128] Degree of damage and change Example 1 Level 0 Example 2 Level 0 Example 3 Level 0 Comparative Example 1 Level 2 Comparative Example 2 Level 2 Comparative Example 3 Level 2 Comparative Example 4 Level 1

[0129] Table 2

[0130] As shown in Table 2, the floor coatings of Examples 1-3 all showed a damage change level of 0 after testing, indicating that the coating films formed by the floor coatings of Examples 1-3 did not exhibit blistering, peeling, cracking, or chalking after artificial weathering aging tests. In contrast, the floor coatings of Comparative Examples 1-4 showed a damage change level ≥1 after testing, indicating blistering and chalking, with Comparative Examples 1-3 showing the most significant damage changes. This demonstrates that the use of waterborne alkyd hybrid epoxy resin as the resin matrix material for floor coatings, along with the use of composite heat-resistant fillers, effectively improves the aging resistance of floor coatings, enhancing their ability to resist weathering. Furthermore, coating the composite heat-resistant fillers during the preparation of the floor coating further improves its aging resistance, ensuring the quality and effectiveness of the floor coating.

[0131] It should be understood that those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims. Parts not described in detail in this specification are prior art known to those skilled in the art.

Claims

1. A floor coating resistant to temperature differences, characterized in that, Includes the following ingredients: 50-120 parts by weight of waterborne alkyd hybrid epoxy resin, 5-30 parts by weight of coated composite heat-resistant filler, 2-5 parts by weight of reactive diluent, 20-80 parts by weight of curing agent, 0.05-0.5 parts by weight of dispersant, 0.1-0.5 parts by weight of leveling agent, 0.1-0.5 parts by weight of defoamer, and 0.5-1.5 parts by weight of thickener; The raw materials for the waterborne alkyd hybrid epoxy resin include: 60-150 parts by weight of epoxy resin, 80-120 parts by weight of alkyd resin, 20-50 parts by weight of butanol, 0.3-1 parts by weight of benzoyl peroxide, 10-30 parts by weight of xylene, 10-25 parts by weight of triethanolamine and 100-200 parts by weight of water. The raw materials for the coated composite heat-resistant filler include: 200-300 parts by weight of triaminomethane buffer solution, 6-20 parts by weight of dopamine hydrochloride, 9-15 parts by weight of sodium periodate, and 5-20 parts by weight of composite heat-resistant filler. The raw materials for the composite heat-resistant filler include: 5-30 parts by weight of functionalized graphene oxide, 80-200 parts by weight of deionized water, 10-60 parts by weight of porous boron nitride microspheres, and 5-8 parts by weight of zirconium oxide beads. The functionalized graphene oxide is obtained by mixing graphene oxide, deionized water, and p-aniline sulfonic acid through stirring, heating reaction, filtration, washing, and drying. The porous boron nitride microspheres are obtained by ball milling hexagonal boron nitride, ammonium bicarbonate, and zirconium oxide beads, mixing with water, high-speed exfoliation, standing, drying the supernatant, and calcining. Includes the following steps: S1: Resin blending modification: Alkyd resin was prepared using soybean oil, pentaerythritol, glycerol, benzoic acid, lithium hydroxide, phthalic anhydride and xylene. After heating and stirring the alkyd resin, butanol, benzoyl peroxide and xylene, epoxy resin was added dropwise while stirring. After the epoxy resin was added, triethanolamine was added and the reaction was stirred continuously. After the reaction was completed, deionized water was added and ultrasonically dispersed to obtain waterborne alkyd hybrid epoxy resin. S2: Preparation of porous boron nitride microspheres, specifically including the following steps: S2.1: Place 30-60 parts by weight of hexagonal boron nitride, 50-100 parts by weight of ammonium bicarbonate and 5-8 parts by weight of zirconium oxide beads into a ball mill jar and ball mill for 10-12 hours at a speed of 320-360 r / min to obtain a mixed powder. Wash and dry the mixed powder for later use. S2.2: Add the mixed powder to deionized water, with a solid-liquid mixing weight ratio of (1-10):

100. After stirring and mixing, a mixed solution is obtained. The mixed solution is poured into a high-speed homogenizer for exfoliation for 3-4 hours at a speed of 5000-6000 r / min. Then, it is allowed to stand for 24-48 hours. The supernatant after standing is taken and dried to obtain functionalized boron nitride. S2.3: Functionalized boron nitride is placed in a tube furnace and calcined at a temperature of 450-500℃ for 24-32 hours to obtain porous boron nitride microspheres. S3: Preparation of composite heat-resistant filler, specifically including the following steps: S3.1: Add 1-30 parts by weight of graphene oxide to 100-200 parts by weight of deionized water, and ultrasonically disperse for 10-30 min to obtain a graphene oxide dispersion. Then, add 1-15 parts by weight of p-aniline sulfonic acid to the graphene oxide dispersion, stir and mix, heat to 70-80℃ and react for 8-12 h. After filtration, washing and drying, functionalized graphene oxide is obtained. S3.2: Take 5-30 parts by weight of functionalized graphene oxide and add it to 80-200 parts by weight of deionized water. After ultrasonic dispersion for 10-30 minutes, add 10-60 parts by weight of porous boron nitride microspheres and 5-8 parts by weight of zirconium oxide beads. Mix evenly to obtain a mixture. S3.3: Add the mixture to a ball mill and ball mill for 1 to 3 hours at a speed of 280 to 400 r / min. After ball milling, filter, wash and dry to obtain the composite heat-resistant filler. S4: Composite heat-resistant filler coating treatment: Dissolve triaminomethane buffer in deionized water to obtain triaminomethane buffer aqueous solution. Add dopamine hydrochloride, sodium periodate and composite heat-resistant filler to triaminomethane buffer aqueous solution and stir to mix. After filtration and drying, the coated composite heat-resistant filler is obtained. S5: Preparation of floor coating: Dispersant, leveling agent, defoamer, thickener, reactive diluent, coated composite heat-resistant filler, water-based alkyd hybrid epoxy resin and curing agent are stirred and mixed to obtain floor coating.

2. The temperature-difference resistant floor coating according to claim 1, characterized in that, Step S1, resin blending modification, specifically includes the following steps: S1.1: Add 90-130 parts by weight of soybean oil, 15-30 parts by weight of pentaerythritol, 5-25 parts by weight of glycerol, 5-10 parts by weight of benzoic acid and 0.5-2 parts by weight of lithium hydroxide into the reactor, and heat while stirring to 240-248°C, and keep warm for 1-2 hours for alcoholysis. S1.2: After alcoholysis, the mixture is allowed to cool naturally to 170-190°C. Then, 50-70 parts by weight of phthalic anhydride and 8-15 parts by weight of xylene are added to the reactor. The mixture is stirred and mixed, heated to 210-220°C and refluxed for 1-3 hours. After cooling to room temperature, the filtrate is filtered to obtain alkyd resin. S1.3: Add 80-120 parts by weight of alkyd resin, 20-50 parts by weight of butanol, 0.3-1 parts by weight of benzoyl peroxide and 10-30 parts by weight of xylene to the reactor in sequence, heat to 110-120°C, stir for 10-15 min, maintain the temperature at 110-120°C, add 60-150 parts by weight of epoxy resin dropwise to the reactor while stirring, control the dropwise addition time to 2-3 h, after the epoxy resin dropwise addition is complete, add 10-25 parts by weight of triethanolamine, and continue stirring to react for 2-4 h; S1.4: After the reaction is complete, add 100-200 parts by weight of deionized water to the reactor and ultrasonically disperse for 20-40 minutes to obtain waterborne alkyd hybrid epoxy resin.

3. The temperature-difference resistant floor coating according to claim 2, characterized in that, Both the reactor and the reaction vessel are equipped with a stirrer, a thermometer, and a reflux condenser.

4. The temperature-difference resistant floor coating according to claim 3, characterized in that, The diameter of the zirconia beads is 10-50 mm.

5. The temperature-difference resistant floor coating according to claim 1, characterized in that, Step S4, the composite heat-resistant filler coating treatment, specifically includes the following steps: S4.1: Dissolve 0.1 to 2 parts by weight of triaminomethane buffer solution in 200 to 300 parts by weight of deionized water, stir well, and adjust the pH to 8.0 to 8.5 to obtain a triaminomethane buffer solution. S4.2: Take 100-150 parts by weight of triaminomethane buffer solution and put it into container A. Add 6-20 parts by weight of dopamine hydrochloride to container A and stir well to obtain solution A. Then take 100-150 parts by weight of triaminomethane buffer solution and put it into container B. Add 9-15 parts by weight of sodium periodate to container B and stir well to obtain solution B. S4.3: Take 5-20 parts by weight of composite heat-resistant filler and add it to solution B. After stirring evenly, ultrasonically disperse for 1-2 hours. Then pour solution A into container B and stir to mix. Ultrasonically disperse for 1-2 hours. Next, filter the suspension obtained in container B. Put the filter cake into a dryer and dry it at 100-120℃ for 40-80 minutes to obtain the coated composite heat-resistant filler.

6. The temperature-difference resistant floor coating according to claim 1, characterized in that, Step S5, the preparation of the floor coating, specifically includes the following steps: S5.1: Mix 0.05-0.5 parts by weight of dispersant, 0.1-0.5 parts by weight of leveling agent, 0.1-0.5 parts by weight of defoamer, and 0.5-1.5 parts by weight of thickener to obtain mixture A; S5.2: Add 2-5 parts by weight of reactive diluent and 5-30 parts by weight of coated composite heat-resistant filler to 50-120 parts by weight of waterborne alkyd hybrid epoxy resin in sequence. After stirring evenly, add 20-80 parts by weight of curing agent to obtain mixture B. S5.3: Mix mixture A and mixture B to obtain floor paint.

7. The temperature-difference resistant floor coating according to claim 6, characterized in that, The dispersant is triethylhexylphosphate, sodium dodecyl sulfate, or methylpentanol; the leveling agent is polydimethylsiloxane or melamine-formaldehyde resin; the thickener is methylcellulose or hydroxypropyl methylcellulose; the reactive diluent is butyl glycidyl ether, allyl glycidyl ether, or C10-C12 alkyl glycidyl ether; the curing agent is a fatty amine curing agent or a polyamide curing agent; and the defoamer is a silicone oil-type silicone defoamer, an emulsion-type silicone defoamer, or a silicone oil solution-type silicone defoamer.