A solvent-free polysiloxane colored sand self-leveling floor paint composition and a preparation method thereof

Abstract

The application provides a solvent-free polysiloxane colored sand self-leveling floor paint composition and a preparation method thereof, and raw materials for preparing the solvent-free polysiloxane colored sand self-leveling floor paint composition by weight parts include: 10-40 parts of hydrogenated epoxy resin, 15-50 parts of amine-based silicon resin, 1-15 parts of epoxy-based cage type oligomeric silsesquioxane, 100-500 parts of colored aggregate, and 0.1-10 parts of auxiliary agent; the amine-based silicon resin is a polysiloxane polyamine polymer, the Si-O bond content of the polysiloxane polyamine polymer is greater than or equal to 35%, the amine value is 50-350 mgKOH / g, and the viscosity at 25 DEG C is 500-10000 mPa s; the epoxy-based cage type oligomeric silsesquioxane contains at least two epoxy groups. The composition of the application is solvent-free, zero VOC, has excellent construction performance, and can be widely applied to outdoor heavy-load floors, parking lots, industrial workshops, landscape floors and other places with high requirements for wear resistance, weather resistance and decoration.

Description

Technical Field

[0001] This invention relates to the field of floor coating technology, specifically to a solvent-free polysiloxane colored sand self-leveling floor coating composition and its preparation method. Background Technology

[0002] Epoxy floor coatings are widely used in industrial plants, parking lots, commercial spaces, and outdoor landscaping. With increasingly stringent environmental regulations and rising user demands for both aesthetics and durability, solvent-free, high-solids-content, and high-performance polysiloxane-modified epoxy floor coatings have become the technological trend in this field. Polysiloxane-modified epoxy resins combine the high adhesion and chemical resistance of epoxy resins with the weather resistance and yellowing resistance of polysiloxanes, demonstrating broad application prospects in the field of heavy-duty outdoor flooring.

[0003] Chinese invention patent application CN117925050A discloses a crack-resistant and impact-resistant polysiloxane coating and its preparation method, which combines hydrogenated epoxy resin, organosilicon intermediate, dendritic crosslinking modified resin, and aminosilane coupling agent to improve surface cracking during thick coating application and enhance impact resistance. However, this technical solution has the following inherent defects:

[0004] 1. The organosilicon component lacks reactive epoxy groups: The organosilicon intermediates used are methyl silicone resin or methyl phenyl silicone resin, which only contain a Si-O-Si framework structure and cannot participate in the epoxy-amine crosslinking reaction. The addition of this component will dilute the effective concentration of epoxy groups in the system, resulting in a decrease in the crosslinking density of the coating, and the Shore D hardness cannot meet the high wear resistance requirements of heavy-duty flooring.

[0005] 2. The aminosilane coupling agent has a low Si-O bond content: aminosilane coupling agents are small molecule compounds, and their Si-O bond content is usually only 20~30%. After curing, it is difficult to form a continuous and dense Si-O-Si inorganic network structure, which has a limited effect on improving the weather resistance of the coating. It is prone to chalking and loss of gloss under long-term outdoor exposure.

[0006] 3. Dendritic crosslinking resin is a pure organic structure: Although dendritic polymers can increase the crosslinking density of the system to a certain extent, they cannot introduce inorganic hybrid properties, and their effect on improving the scratch resistance and wear resistance of the coating is limited; especially in the high-filling colored sand system, the interfacial bonding force between the resin and inorganic aggregate is easily weakened due to the lack of inorganic hybrid structure, which leads to problems such as colored sand falling off and coating whitening.

[0007] 4. No technical solutions adapted to colored sand systems have been disclosed: Existing technologies mainly focus on varnish or colored paint systems and do not address key technical issues such as the compatibility of inorganic aggregates and resins in colored sand self-leveling flooring and aggregate settling control. It is difficult to achieve uniform distribution of colored sand in the coating to form a stable three-dimensional texture and decorative effect, which cannot meet the application requirements of high-end decorative flooring.

[0008] Therefore, how to significantly increase the Si-O bond content of the system without sacrificing the effective concentration of epoxy groups, thereby achieving a synergistic improvement in high hardness, high wear resistance, and high weather resistance, and adapting it to solvent-free colored sand self-leveling construction systems, has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides a solvent-free polysiloxane colored sand self-leveling floor coating composition and its preparation method.

[0010] To achieve the above objectives, the present invention provides the following technical solution:

[0011] This invention provides a solvent-free polysiloxane colored sand self-leveling floor coating composition, which, by weight, comprises the following raw materials: 10-40 parts hydrogenated epoxy resin, 15-50 parts amino silicone resin, 1-15 parts epoxy-based cage-type oligomeric silsesquioxane, 100-500 parts colored aggregate, and 0.1-10 parts additives; wherein the amino silicone resin is a polysiloxane polyamine polymer with a Si-O bond content ≥35%, an amine value of 50-350 mgKOH / g, and a viscosity of 500-10000 mPa·s at 25°C; wherein the epoxy-based cage-type oligomeric silsesquioxane contains at least two epoxy groups.

[0012] Using the above technical solution, hydrogenated epoxy resin provides epoxy groups for the coating system, serving as the basic framework for the film-forming resin to form the coating; amine silicone resin, as a polysiloxane polyamine polymer, has a high Si-O bond content that can improve the weather resistance of the coating, and the amine groups can undergo cross-linking reactions with the epoxy groups to increase the cross-linking density of the coating; suitable viscosity ensures the construction performance of the system; epoxy cage-type oligomeric silsesquioxane contains at least two epoxy groups that can participate in the cross-linking reaction, further increasing the cross-linking density of the coating, while its cage-type structure can enhance the physical properties of the coating; colored aggregate, as a filler component, improves the wear resistance, impact resistance, and other mechanical properties of the coating, and provides the required color for the floor coating; additives can improve the dispersion, leveling, defoaming, and other processing properties of the coating system, ensuring the coating forming quality. The synergistic effect of each component allows the solvent-free polysiloxane colored sand self-leveling floor coating to form a coating with excellent comprehensive performance after curing.

[0013] Preferably, the amino-based silicone resin is a hydrogenated epoxy resin ring-opening modified amino polysiloxane, which is prepared by reacting amino polysiloxane with hydrogenated epoxy resin, and its number average molecular weight is 2000~10000.

[0014] Using the above technical solution, the amino-based silicone resin is prepared by reacting amino-based polysiloxanes with hydrogenated epoxy resins. The amino-based polysiloxane structure, modified by ring-opening of hydrogenated epoxy resin, can improve the compatibility of the amino-based silicone resin with hydrogenated epoxy resins and epoxy-based cage-type oligomeric silsesquioxanes. By controlling the number-average molecular weight within the range of 2000 to 10000, the amino-based silicone resin can maintain a suitable molecular chain length and intermolecular forces, ensuring its good dispersibility and reactivity in the system. The amino-based silicone resin with this structure and molecular weight can participate in the cross-linking reaction of the system, improving the degree of cross-linking bonding of the coating system.

[0015] Preferably, the epoxy-based cage-type oligomeric silsesquioxane is at least one of epoxy cyclohexylethyl cage-type oligomeric silsesquioxane and glycidyl cage-type oligomeric silsesquioxane, and the epoxy equivalent is 150~400g / eq.

[0016] Using the above technical solution, both epoxy cyclohexylethyl cage-type oligomeric silsesquioxane and glycidyl cage-type oligomeric silsesquioxane are epoxy-based cage-type oligomeric silsesquioxanes containing cage structures, and their cage structures can improve the physical properties of the coating. The epoxy groups contained in the molecules of the two types of substances can participate in the cross-linking reaction of the system, increasing the cross-linking density of the coating. By controlling the epoxy equivalent in the range of 150~400g / eq, the epoxy-based cage-type oligomeric silsesquioxane can maintain an appropriate epoxy group content, ensuring that it has good reactivity in the system and can fully undergo cross-linking reactions with other components containing amine and epoxy groups in the system, thereby improving the degree of cross-linking and structural density of the coating.

[0017] Preferably, the hydrogenated epoxy resin is hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F epoxy resin, and the epoxy equivalent is 180~250 g / eq.

[0018] Using the above technical solution, both hydrogenated bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin are hydrogenated epoxy resins with a saturated cyclic hydrocarbon structure. This structure can improve the weather resistance and yellowing resistance of the coating. The epoxy equivalent of the hydrogenated epoxy resin is controlled within the range of 180~250g / eq, which can maintain a suitable epoxy group concentration in the system and ensure the efficiency of crosslinking reaction with amino silicone resin and epoxy cage-type oligomeric silsesquioxane. The suitable epoxy equivalent can also maintain a suitable molecular chain length of hydrogenated epoxy resin in the system, taking into account both the application viscosity of the coating system and the crosslinking density of the cured coating.

[0019] Preferably, the colored aggregate is at least one of colored quartz sand, ceramic particles, and glass sand, with a particle size of 0.1~2.0 mm, and the colored aggregate is colored aggregate that has been pre-treated with a silane coupling agent.

[0020] Using the above technical solution, colored quartz sand, ceramic particles, and glass sand are inorganic aggregates, which can improve the mechanical properties of the coating, such as wear resistance and impact resistance. The particle size is controlled within the range of 0.1~2.0mm, which can make the colored aggregate form a reasonable particle size distribution in the coating system and increase the packing density between the aggregates. The surface treatment of the colored aggregate with silane coupling agent can improve the interfacial bonding force between the colored aggregate and organic phases such as hydrogenated epoxy resin and amino silicone resin, and reduce interfacial defects. The modification treatment of silane coupling agent can also improve the dispersibility of colored aggregate in the coating system, so that the colored aggregate is more evenly distributed in the coating.

[0021] Preferably, the additives include at least one of wetting and dispersing agents, defoamers, leveling agents, ultraviolet absorbers, and hindered amine light stabilizers.

[0022] Using the above technical solutions, wetting and dispersing agents can improve the dispersion uniformity of each component in the system and reduce particle agglomeration; defoamers can eliminate bubbles generated during the preparation and application of the coating system, reducing the probability of defects such as pinholes and craters in the coating; leveling agents can adjust the leveling properties of the coating, resulting in a smooth and even coating surface after application; UV absorbers can absorb UV energy, reducing the degradation of organic segments by UV rays; hindered amine light stabilizers can capture photo-oxidative free radicals and inhibit chain reactions; simultaneously, amine silicone resin and epoxy POSS form a high-content Si-O-Si inorganic framework, blocking UV penetration. The synergistic effect of these three agents significantly improves the weather resistance of the coating. Each additive plays its role, synergistically ensuring the preparation, application performance, and appearance and weather resistance quality of the coating after curing.

[0023] This invention also provides a method for preparing a solvent-free polysiloxane colored sand self-leveling floor coating composition, comprising the following steps:

[0024] S1. Preparation of the main agent: Hydrogenated epoxy resin, epoxy cage-type oligomeric silsesquioxane and the first part of the additives are mixed evenly to obtain the main agent; the first part of the additives is at least one of wetting and dispersing agent and defoamer.

[0025] S2. Preparation of curing agent: Mix the amine silicone resin and the second part of the additives evenly to obtain the curing agent; the second part of the additives is at least one of leveling agent, ultraviolet absorber, and hindered amine light stabilizer.

[0026] S3. Construction: Before construction, mix the main agent and curing agent in proportion, add colored aggregate and stir evenly to obtain a solvent-free polysiloxane colored sand self-leveling floor coating composition.

[0027] By adopting the above technical solution, the main agent and curing agent are mixed in proportion before the colored aggregate is added and stirred. This can reduce the sedimentation of the colored aggregate in the system, improve the uniformity of the distribution of the colored aggregate in the coating composition, and avoid the curing reaction caused by pre-mixing from affecting the construction performance. The component matching and mixing sequence of each step are adapted to the solvent-free characteristics of the coating composition, ensuring that each component plays its full role and improving the construction performance of the coating composition and the overall performance of the cured coating.

[0028] Preferably, the coating thickness of the prepared floor coating composition is 1-2 mm, the Shore D hardness is ≥90, the Taber abrasion resistance value measured according to GB / T1768-2006 is ≤50 mg / 1000r, and the QUV 1000h gloss retention rate measured according to GB / T 1865-2009 is ≥90%.

[0029] By adopting the above technical solution, the coating thickness is controlled within 1~2mm, which allows the coating formed after the floor coating composition is cured to maintain suitable physical and performance properties, taking into account both the structural strength and construction efficiency of the coating. The performance index of Shore D hardness ≥90 indicates that the coating has high surface hardness and can resist external indentation and scratching. Taber abrasion resistance value ≤50mg / 1000r indicates that the coating has excellent abrasion resistance and can reduce surface wear during long-term use. QUV 1000h gloss retention rate ≥90% reflects the excellent weather resistance and light aging resistance of the coating, which can maintain surface gloss under long-term ultraviolet irradiation and reduce the degree of surface chalking and loss of gloss.

[0030] Preferably, the raw materials for preparation further include, by weight, 0.1 to 5 parts of epoxy-modified graphene nanosheets; the epoxy-modified graphene nanosheets are obtained by dispersing graphene oxide in an ethanol-water mixed solvent, adding an epoxy-silane coupling agent, stirring and reacting at 60 to 80°C for 4 to 8 hours, and then washing and drying to obtain epoxy-modified graphene nanosheets with ≤10 layers and a sheet diameter of 1 to 10 μm; the epoxy-silane coupling agent is γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane.

[0031] Using the above technical solution, γ-glycidyl etheroxypropyltrimethoxysilane and γ-glycidyl etheroxypropyltriethoxysilane can introduce epoxy groups on the surface of graphene oxide, improving the compatibility and bonding force between epoxy-modified graphene nanosheets and epoxy- and amine-containing components in the system; stirring the reaction at 60~80℃ for 4~8h can ensure that the modification reaction between the epoxy-modified silane coupling agent and graphene oxide is fully carried out, so that the modified product has a stable structure and properties; the structural characteristics of epoxy-modified graphene nanosheets with ≤10 layers and a sheet diameter of 1~10μm can exert the physical reinforcement effect of the two-dimensional sheets, improving the density and mechanical properties of the coating; the addition of epoxy-modified graphene nanosheets can participate in the cross-linking reaction of the system, further increasing the cross-linking density of the coating, thereby improving the wear resistance, weather resistance and other properties of the coating.

[0032] Preferably, the raw materials for preparation further include, by weight, 3-20 parts of terminal amino hyperbranched polysiloxane; the terminal amino hyperbranched polysiloxane is prepared by mixing (3-aminopropyl)methyldiethoxysilane with deionized water at a molar ratio of 1:1.5-2.0, hydrolyzing and polycondensing at 40-60°C for 2-4 hours under nitrogen protection and in the presence of a catalyst, then heating to 80-100°C and continuing the reaction for 2-3 hours, followed by vacuum distillation to remove low-boiling substances, to obtain terminal amino hyperbranched polysiloxane with a number average molecular weight of 1000-8000, an amine value of 200-600 mgKOH / g, and a molar degree of branching of 0.4-0.6.

[0033] Using the above technical solution, the specific molar ratio of (3-aminopropyl)methyldiethoxysilane to deionized water ensures the full progress of the hydrolysis-condensation reaction. Nitrogen protection and the presence of a catalyst provide a stable reaction environment and improve reaction efficiency. Temperature and reaction time control at different stages allow for the regulation of the structure and properties of the terminal amino hyperbranched polysiloxane. Vacuum distillation to remove low-boiling-point substances improves the purity of the terminal amino hyperbranched polysiloxane. Controlling the number-average molecular weight of the terminal amino hyperbranched polysiloxane within the range of 1000-8000 allows for the efficient processing of this component in bulk. The system maintains suitable dispersibility and reactivity; the amine value of 200~600mgKOH / g provides sufficient reactive amino groups to crosslink with the epoxy groups in the system, thereby increasing the crosslinking density of the coating; the molar branching degree of 0.4~0.6 endows the terminal amino hyperbranched polysiloxane with a hyperbranched molecular structure, which can reduce the application viscosity of the coating system and introduce flexible segments to the coating to improve its flexibility. This component works synergistically with other components in the system to simultaneously improve the application performance of the coating and the comprehensive mechanical properties of the cured coating.

[0034] The beneficial effects of this invention are as follows:

[0035] This invention departs from the traditional "dilution-type" reinforcement technology of organosilicon-modified epoxy, employing a compound system of epoxy-based cage-type oligomeric silsesquioxanes (epoxy-based POSS) and amino-based silicone resins with high Si-O bond content. The epoxy-based POSS not only constructs a high-content Si-O-Si inorganic framework but also possesses reactive epoxy groups, which, upon addition, can increase the functionality of the epoxy system rather than reduce its viscosity. The amino-based silicone resin has a Si-O bond content ≥35%, significantly higher than that of aminosilane coupling agents, and after curing, it can form a continuous and dense organic-inorganic interpenetrating network structure.

[0036] The floor coating composition provided by this invention, after curing, forms a coating with a Shore D hardness of 92-94, a Taber abrasion resistance value ≤50mg, a gloss retention rate ≥90% after 1000h QUV aging, adhesion ≥7.5MPa, and excellent scratch resistance. Compared with existing technologies, the coating hardness is increased by ≥15%, and the abrasion resistance and weather resistance are significantly improved, achieving a significant upgrade from basic performance to high-performance applications.

[0037] This invention utilizes the excellent dispersing effect of amino silicone resin on epoxy-based POSS and the good chemical compatibility of both with hydrogenated epoxy resin, enabling the floor coating composition to possess excellent wetting and coating capabilities and anti-settling properties for colored aggregates. After curing, the colored sand is evenly distributed, and the coating exhibits no whitening or mottling, forming a decorative surface layer with a natural stone texture. All components are solvent-free, achieving zero VOC emissions and meeting green environmental protection requirements; the system has moderate viscosity and good self-leveling properties, allowing for a single coat thickness of 2-5 mm without sagging or cracking. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] The specific information on the raw materials used in the embodiments of the present invention is shown in the table below.

[0040] Components Specifications / Model source Hydrogenated epoxy resin Hydrogenated bisphenol A epoxy resin, epoxy equivalent of 180~250 g / eq Shanghai Kaiyin Chemical Co., Ltd. Hydrogenated bisphenol F epoxy resin, epoxy equivalent of 180~250 g / eq Shanghai Kaiyin Chemical Co., Ltd. Amino polysiloxane resin Number average molecular weight approximately 2000, amine value approximately 280 mgKOH / g Wacker Chemie Boron trifluoride diethyl ether complex 98% purity, Brand: McLean Aladdin TCI Shanghai Hans Chemical Co., Ltd. γ-(2,3-epoxypropoxy)propyltrimethoxysilane 99% purity Hubei Kewode Chemical Co., Ltd. Tetrabutylammonium fluoride 99% purity Wuhan Kanos Technology Co., Ltd. 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 99% purity Nanjing Quanxi New Materials Co., Ltd. Colored Quartz Sand 0.1~2.0mm Qingdao Wanhong Mining Co., Ltd. ceramic particles 0.1~2.0mm Jiangsu Gumai New Material Technology Co., Ltd. Glass sand 0.1~2.0mm Hebei Huayuan Mining Co., Ltd. wetting and dispersing agents BYK-163 BYK Chemical Defoamer BYK-066N BYK Chemical Leveling agent BYK-358N BYK Chemical UV absorber Tinuvin 1130 BASF (China) Co., Ltd. Hindered amine light stabilizers Tinuvin 292 BASF (China) Co., Ltd. Epoxysilane coupling agents γ-glycidoxypropyltrimethoxysilane Nanjing Shuguang Chemical Group Co., Ltd. Graphene oxide 99.9% purity Anhui Kerun Nanotechnology Co., Ltd. (3-Aminopropyl)methyldiethoxysilane 97% purity Shanghai Jizhi Biochemical Technology Co., Ltd.

[0041] Amino silicone resins, epoxy-based cage-type oligomeric silsesquioxanes, epoxy-modified graphene nanosheets, and amino-terminated hyperbranched polysiloxanes can be prepared in-house according to the following synthesis examples.

[0042] Synthesis Example 1: Preparation of Amino Silicone Resin (B-1)

[0043] In a reactor equipped with a stirrer, thermometer, and reflux condenser, 100 parts by weight of amino-based polysiloxane resin (number average molecular weight approximately 2000, amine value approximately 50 mgKOH / g), 30 parts by weight of hydrogenated bisphenol A epoxy resin (epoxy equivalent approximately 210 g / eq), and a suitable catalyst (boron trifluoride diethyl ether complex) were added. The mixture was heated to 80–100 °C under nitrogen protection and reacted for 3–5 hours. The reaction was stopped when the amine value dropped to 150–200 mgKOH / g. The product was cooled and discharged to obtain amino-based silicone resin (B-1). Infrared spectroscopy confirmed that the amine value was 1100 cm⁻¹. -1 The characteristic absorption peak of Si-O-Si appears at the point, the measured amine value is 180 mgKOH / g, the viscosity at 25℃ is 3500 mPa·s, and the Si-O bond content is about 38%.

[0044] Synthesis Example 2: Preparation of Amino Silicone Resin (B-2)

[0045] Referring to Synthesis Example 1, the molecular weight of the amino-based polysiloxane was adjusted to 5000, the amine value to approximately 20 mgKOH / g, and the amount used was 100 parts by weight; the amount of hydrogenated bisphenol A epoxy resin was 50 parts by weight; the reaction temperature was 80~100℃, and the reaction time was 4~6h, yielding amino-based silicone resin (B-2). The measured amine value was 95 mgKOH / g, the viscosity at 25℃ was 8200 mPa·s, and the Si-O bond content was approximately 42%.

[0046] Synthetic Example 3: Preparation of Epoxy POSS (C-1)

[0047] In a reaction flask equipped with a stirrer and a reflux condenser, 100 parts by weight of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 15 parts by weight of deionized water, and an appropriate amount of hydrolysis catalyst (tetrabutylammonium fluoride) were added. The mixture was stirred at room temperature for 24 h, then extracted with toluene. The organic phase was washed with water until neutral, and the solvent was evaporated to obtain a white solid product. 29Si NMR and FT-IR confirmed that it was a cage-like silsesquioxane structure, with a measured epoxy equivalent of 220 g / eq.

[0048] Synthetic Example 4: Preparation of Epoxy POSS (C-2)

[0049] Referring to Synthesis Example 3, γ-(2,3-epoxypropoxy)propyltrimethoxysilane was replaced with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane to obtain epoxycyclohexylethyl POSS (C-2), with an actual epoxy equivalent of 180 g / eq.

[0050] Synthesis Example 5: Preparation of Epoxy-Modified Graphene Nanosheets

[0051] Five parts by weight of graphene oxide (monolayer ratio >90%, sheet diameter 1~5 μm, thickness 0.8~1.2 nm) were dispersed in 500 parts by weight of an ethanol-water mixed solvent (volume ratio 9:1) and dispersed for 45 min under ultrasonic power of 300 W and frequency of 40 kHz to form a uniform dispersion. Five parts by weight of γ-glycidyl etheroxypropyltrimethoxysilane were added, and the pH was adjusted to 4.0~5.0 with hydrochloric acid (concentration 37%, purchased from Sinopharm Chemical Reagent Co., Ltd.). The mixture was stirred at 70 °C for 6 h, cooled to room temperature, centrifuged at 8000~9000 r / min for 10~15 min, washed (3 times with ethanol and 2 times with deionized water) until neutral, and then dried at -0.095 MPa and 70 °C for 18 h. The nanosheets were then ground through a 400 mesh sieve to obtain epoxy-modified graphene nanosheets (EGN-1). XPS analysis showed that the surface epoxy group content was 2.8 at%, and TEM analysis showed that the number of layers was ≤5.

[0052] Synthesis Example 6: Preparation of amino-terminated hyperbranched polysiloxanes

[0053] In a reactor equipped with a stirrer, thermometer, and reflux condenser, under nitrogen protection, 221 parts by weight of (3-aminopropyl)methyldiethoxysilane was mixed with 18 parts by weight of deionized water, and 1.1 parts by weight of acetic acid (catalyst, 99% concentration, purchased from Sinopharm Chemical Reagent Co., Ltd.) was added. The mixture was hydrolyzed and polycondensed at 50°C for 3 hours, then the temperature was raised to 90°C and the reaction continued for 2.5 hours. The low-boiling components (ethanol and water) were removed by distillation under reduced pressure to -0.09 MPa to obtain an amino-terminated hyperbranched polysiloxane (AHBP-1). GPC analysis showed a number-average molecular weight of approximately 4500, an amine value of 380 mgKOH / g, and a branching degree of 0.52 (as determined by GPC). 29 (Si-NMR measurement).

[0054] Performance testing methods:

[0055] Shore D hardness: According to GB / T 2411-2008, the sample thickness is ≥6 mm.

[0056] Taber wear resistance: According to GB / T 1768-2006, CS-17 grinding wheel, load 1000g, 1000 rpm, weighing loss.

[0057] Scratch resistance: According to GB / T 9279-2015, apply 5N with a pencil hardness tester and observe the scratches.

[0058] Adhesion: According to GB / T 5210-2006, pull-off test.

[0059] Weather resistance: According to GB / T 1865-2009, fluorescent ultraviolet lamp (UVA-340), irradiance 0.68 W / m 2Cycle: Irradiate at 60℃ for 4 hours, condense at 50℃ for 4 hours, and measure gloss retention and color difference after 1000 hours.

[0060] Uniformity of colored sand distribution: Visually inspect the coating surface for any blooming, floating color, or sedimentation.

[0061] Example 1:

[0062] Components weight Hydrogenated bisphenol A epoxy resin (epoxy equivalent 210 g / eq) 20 Amino silicone resin (B-1) 30 Epoxy-based POSS (C-1) 5 Colored quartz sand (40~80 mesh) (KH-550 surface treated) 300 BYK-163 Wetting and Dispersing Agent 0.5 BYK-066N Defoamer 0.3 BYK-358N Leveling Agent 0.2 Tinuvin 292 light stabilizer 0.5 Tinuvin 1130 UV absorber 0.5

[0063] Preparation method: According to the above formula, hydrogenated epoxy resin, epoxy-based POSS, wetting and dispersing agent, defoamer, leveling agent, light stabilizer, and UV absorber are mixed and dispersed evenly at high speed to form the main agent; amino silicone resin is used alone as the curing agent. Before construction, the main agent and curing agent are mixed, colored quartz sand is added and stirred for 3-5 minutes, and then scraped onto a cement board with a primer coating to a thickness of about 2 mm. It is cured at room temperature for 24 hours and then cured at 50℃ for 24 hours to obtain the coating.

[0064] Performance testing:

[0065] Shore D hardness: 93

[0066] Taber abrasion resistance value: 42 mg

[0067] Scratch resistance: No visible scratches

[0068] Adhesion: 8.5 MPa

[0069] Weather resistance: 93% gloss retention, color difference ΔE 1.2

[0070] Uniformity of colored sand distribution: Visually, there are no mottled spots or whitening.

[0071] Example 2:

[0072] Components weight Hydrogenated bisphenol F epoxy resin (epoxy equivalent 190 g / eq) 15 Amino silicone resin (B-2) 40 Epoxy-based POSS (C-2) 8 Ceramic particles (20~60 mesh) 400 The additives are the same as in Example 1. 1.8

[0073] The preparation method is the same as in Example 1.

[0074] Performance testing:

[0075] Shore D hardness: 94

[0076] Taber abrasion resistance value: 38 mg

[0077] Scratch resistance: No visible scratches

[0078] Adhesion: 9.2 MPa

[0079] Weather resistance: 95% gloss retention, color difference ΔE 0.9

[0080] Uniformity of colored sand distribution: Excellent.

[0081] Example 3:

[0082] Components weight Hydrogenated bisphenol A epoxy resin 30 Amino silicone resin (B-1) 20 Epoxy-based POSS (C-1) 10 Glass frit (60~100 mesh) 250 The additives are the same as in Example 1. 2.0

[0083] The preparation method is the same as in Example 1.

[0084] Performance testing:

[0085] Shore D hardness: 92

[0086] Taber abrasion resistance value: 47 mg

[0087] Scratch resistance: No visible scratches

[0088] Adhesion: 7.8 MPa

[0089] Weather resistance: 91% gloss retention, color difference ΔE 1.5

[0090] Uniformity of colored sand distribution: Good.

[0091] Example 4:

[0092] Components weight Hydrogenated bisphenol A epoxy resin 20 Amino silicone resin (B-1) 30 Epoxy-based POSS (C-1) 6 Epoxy-modified graphene nanosheets (EGN-1, prepared according to synthesis example 5) 2 Amino-terminated hyperbranched polysiloxane (AHBP-1, prepared according to synthesis example 3) 8 Colored quartz sand (40~80 mesh) (KH-550 surface treated) 350 BYK-163 wetting and dispersing agent 0.6 BYK-066N Defoamer 0.4 BYK-358N Leveling Agent 0.3 Tinuvin 292 light stabilizer 0.6 Tinuvin 1130 UV absorber 0.6

[0093] Preparation method:

[0094] (1) Preparation of the main agent: 2 parts by weight of epoxy-modified graphene nanosheets (EGN-1) were added to 20 parts by weight of hydrogenated bisphenol A epoxy resin and ultrasonically dispersed (power 300W, frequency 40kHz, temperature 30℃) for 45min. Then, 6 parts by weight of epoxy POSS, 8 parts by weight of amino-terminated hyperbranched polysiloxane (AHBP-1), 0.6 parts by weight of BYK-163 wetting and dispersing agent, and 0.4 parts by weight of BYK-066N defoamer were added and stirred for 45min under vacuum of -0.095MPa, temperature of 35℃ and speed of 800r / min to obtain the main agent.

[0095] (2) Preparation of curing agent: 30 parts by weight of amino silicone resin (B-1), 0.3 parts by weight of BYK-358N leveling agent, 0.6 parts by weight of Tinuvin 292 light stabilizer, and 0.6 parts by weight of Tinuvin 1130 UV absorber are mixed and stirred at 600 r / min for 20 min to obtain curing agent;

[0096] (3) Construction: Before construction, mix the main agent and the curing agent at a weight ratio of 100:30, add 350 parts by weight of colored quartz sand, stir at 600r / min for 4min, and immediately scrape it onto the cement substrate that has been treated with primer (epoxy primer). Control the wet film thickness to about 2.5mm, cure at room temperature (25℃) for 24h, and then cure in an oven at 50℃ for 24h to obtain solvent-free polysiloxane colored sand self-leveling floor coating.

[0097] Comparative Example 1: Control Group

[0098] The floor coating composition was prepared according to the method disclosed in CN117925050A, and the formulation is as follows:

[0099] Components weight Hydrogenated bisphenol A epoxy resin 20 Organosilicon intermediate (commercially available methylphenyl silicone resin, solid content 60%) 30 Dendritic crosslinked modified resin (Boltorn H2004) 6 Aminosilane coupling agent (KH-550) 94 BYK-066N Defoamer 0.6 BYK-358N Leveling Agent 0.6 BYK-163 wetting and dispersing agent 0.9 Tinuvin 292 light stabilizer 0.5 Tinuvin 1130 UV absorber 0.5

[0100] The preparation method is as described in this patent.

[0101] Actual performance:

[0102] Shore D hardness: 78

[0103] Taber abrasion resistance value: 105 mg

[0104] Scratch resistance: Obvious scratches under 3N load

[0105] Adhesion: 5.6 MPa

[0106] Weather resistance: 62% gloss retention after 1000h QUV testing, color difference ΔE 4.8

[0107] Colored sand system compatibility: Colored sand settles significantly and turns white on the surface.

[0108] Comparative Example 2: Comparison of Curing Agents (Commercially Available Aminosilane Coupling Agents)

[0109] Fixed formulation: 20 parts hydrogenated bisphenol A epoxy resin, 5 parts epoxy-based POSS (C-1), 300 parts colored quartz sand, additives as in Example 1, and curing agents as follows:

[0110] (a) 30 parts of self-developed amino-based silicone resin (B-1) (Example 1)

[0111] (b) 30 commercially available KH-550 products

[0112] (c) 30 parts of commercially available polyamide curing agent (amine value 200 mgKOH / g)

[0113] Performance comparison:

[0114] Curing agent type Shore D hardness Taber abrasion resistance (mg) Weather resistance and gloss retention (%) (a) Amino silicone resin 93 42 93 (b) KH-550 76 112 58 (c) Polyamide 81 95 41

[0115] Comparative Example 3: Comparison of Crosslinking Reinforcing Components

[0116] Fixed formulation: 20 parts hydrogenated bisphenol A epoxy resin, 30 parts amino silicone resin (B-1), 300 parts colored quartz sand, and additives as in Example 1. The crosslinking reinforcement components are as follows:

[0117] (a) 5 parts of epoxy-based POSS (C-1) (Example 1)

[0118] (b) 5 parts of dendritic crosslinking resin (Boltorn H2004)

[0119] (c) 10 parts of methyl silicone resin (commercially available, 50% solids content) (5 parts on a solids basis).

[0120] (d) Nano-sized silica (vapor phase method, specific surface area 200 m²) 2 5 parts ( / g) (direct blending)

[0121] Performance comparison:

[0122] Crosslinking reinforced components Shore D hardness Scratch resistance (5N) Adhesion (MPa) Storage stability (50℃, 7 days) (a) Epoxy-based POSS 93 No scratches 8.5 Viscosity stability (b) Dendritic resin 86 Obvious scratches 6.8 Stablize (c) Methyl silicone resin 74 Severe scratches 5.2 Stablize <![CDATA[(d) Nano - SiO2]]> 82 Minor scratches 4.5 Thickening, Aggregation

[0123] Comparative Example 4: Epoxy-free POSS (hydrogenated bisphenol A epoxy resin + amino silicone resin only)

[0124] 20 parts of hydrogenated bisphenol A epoxy resin, 30 parts of amino silicone resin (B-1), 300 parts of colored quartz sand, and the same additives as in Example 1, but without the addition of epoxy group POSS.

[0125] Performance: Shore D hardness 75, Taber abrasion resistance 138 mg, weather resistance and gloss retention 72%, adhesion 6.1 MPa.

[0126] Comparative Example 5: Amine-free silicone resin (hydrogenated bisphenol A epoxy resin + epoxy POSS + commercially available amine curing agent)

[0127] 20 parts of hydrogenated bisphenol A epoxy resin, 5 parts of epoxy-based POSS (C-1), 30 parts of commercially available polyamide curing agent, 300 parts of colored quartz sand, and the same additives as in Example 1.

[0128] Performance: Shore D hardness 82, coating film is brittle, micro-cracks appear during scraping, adhesion 4.8MPa, weather resistance and gloss retention 65%.

[0129] Comparative Example 6: Ordinary silicone resin replaces epoxy-based POSS (hydrogenated bisphenol A epoxy resin + amino silicone resin + methyl silicone resin)

[0130] 20 parts of hydrogenated bisphenol A epoxy resin, 30 parts of amino silicone resin (B-1), 10 parts of methyl silicone resin (50% solid content), 300 parts of colored quartz sand, and the same additives as in Example 1.

[0131] Performance: Shore D hardness 71, Taber abrasion resistance 146 mg, weather resistance and gloss retention 58%, severe scratches.

[0132] Comparative Example 7: Comparison of Epoxy POSSPOSS Dosage

[0133] Fixed formulation: 20 parts hydrogenated bisphenol A epoxy resin, 30 parts amino silicone resin (B-1), 300 parts colored quartz sand, and additives as in Example 1. The amount of epoxy group POSS (C-1) varied: 0.5 parts, 2 parts, 5 parts, 8 parts, 12 parts, and 15 parts.

[0134] Dosage of epoxy-based POSS (parts) Shore D hardness Coating status 0.5 78 good 2 85 good 5 93 good 8 94 good 12 91 Slightly brittle 15 87 Explicitly brittle, with microcracks

[0135] It can be seen that a balance between high hardness and toughness can be obtained by using 2 to 10 parts of epoxy-based POSS. The present invention preferably uses 2 to 10 parts, and more preferably 5 to 8 parts.

[0136] Compared with Comparative Example 1 (existing patented technology), the Shore D hardness of the present invention is increased from 78 to over 92, the abrasion resistance value is reduced by over 60%, the weather resistance and gloss retention rate is increased from 62% to over 90%, while maintaining good adhesion, workability and colored sand dispersibility.

[0137] Comparative Examples 1-5 fully demonstrate that replacing the curing agent or the crosslinking reinforcement component alone, or using other types of organosilicon / nanofillers, cannot achieve the comprehensive performance leap of this invention. The composition of this invention achieves a significant increase in Si-O bond content without sacrificing the epoxy group concentration, forming an organic-inorganic interpenetrating network structure, which has excellent synergistic effects.

[0138] The coating composition of the present invention is solvent-free and environmentally friendly, and is suitable for outdoor colored sand self-leveling flooring, industrial flooring, parking lots, outdoor landscapes and other places with high requirements for wear resistance, weather resistance and decoration.

[0139] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A solvent-free polysiloxane colored sand self-leveling floor coating composition, characterized in that, The raw materials for its preparation, by weight, include: 10-40 parts of hydrogenated epoxy resin, 15-50 parts of amino silicone resin, 1-15 parts of epoxy-based cage-type oligomeric silsesquioxane, 100-500 parts of colored aggregate, and 0.1-10 parts of additives; wherein the amino silicone resin is a polysiloxane polyamine polymer with a Si-O bond content ≥35%, an amine value of 50-350 mgKOH / g, and a viscosity of 500-10000 mPa·s at 25℃; wherein the epoxy-based cage-type oligomeric silsesquioxane contains at least two epoxy groups.

2. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The amino-based silicone resin is a hydrogenated epoxy resin ring-opening modified amino polysiloxane, which is prepared by reacting amino polysiloxane with hydrogenated epoxy resin, and its number average molecular weight is 2000~10000.

3. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The epoxy-based cage-type oligomeric silsesquioxane is at least one of epoxy cyclohexylethyl cage-type oligomeric silsesquioxane and glycidyl cage-type oligomeric silsesquioxane, with an epoxy equivalent of 150~400 g / eq.

4. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The hydrogenated epoxy resin is hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F epoxy resin, with an epoxy equivalent of 180~250 g / eq.

5. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The colored aggregate is at least one of colored quartz sand, ceramic particles, and glass sand, with a particle size of 0.1~2.0mm. The colored aggregate is a colored aggregate that has been pre-treated with a silane coupling agent.

6. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The additives include at least one of wetting and dispersing agents, defoamers, leveling agents, ultraviolet absorbers, and hindered amine light stabilizers.

7. A method for preparing the solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 6, characterized in that, Includes the following steps: S1. The hydrogenated epoxy resin, the epoxy-based cage-type oligomeric silsesquioxane, and the first part of the additives are mixed evenly to obtain the main agent; the first part of the additives is at least one of the wetting and dispersing agents and defoamers. S2. Mix the amine silicone resin and the second part of the additives evenly to obtain a curing agent; the second part of the additives is at least one of leveling agent, ultraviolet absorber, and hindered amine light stabilizer. S3. Before construction, mix the main agent and curing agent in proportion, add colored aggregate and stir evenly to obtain a solvent-free polysiloxane colored sand self-leveling floor coating composition.

8. The method for preparing the solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 7, characterized in that, The prepared floor coating composition has a coating thickness of 1-2 mm, a Shore D hardness of ≥90, a Taber abrasion resistance of ≤50 mg / 1000r, and a QUV 1000h gloss retention rate of ≥90%.

9. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The raw materials for its preparation, by weight, also include: 0.1-5 parts of epoxy-modified graphene nanosheets; the epoxy-modified graphene nanosheets are obtained by dispersing graphene oxide in an ethanol-water mixed solvent, adding an epoxy-silane coupling agent, stirring and reacting at 60-80℃ for 4-8 hours, and then washing and drying to obtain epoxy-modified graphene nanosheets with ≤10 layers and a sheet diameter of 1-10 μm; the epoxy-silane coupling agent is γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane.

10. The solvent-free polysiloxane colored sand self-leveling floor coating composition according to claim 1, characterized in that, The raw materials for its preparation, by weight, also include: 3-20 parts of terminal amino hyperbranched polysiloxane; the terminal amino hyperbranched polysiloxane is prepared by mixing (3-aminopropyl)methyldiethoxysilane with deionized water at a molar ratio of 1:1.5-2.0, hydrolyzing and polycondensing at 40-60°C for 2-4 hours under nitrogen protection and in the presence of a catalyst, then heating to 80-100°C and continuing the reaction for 2-3 hours, followed by vacuum distillation to remove low-boiling substances, to obtain terminal amino hyperbranched polysiloxane with a number average molecular weight of 1000-8000, an amine value of 200-600 mgKOH / g, and a molar degree of branching of 0.4-0.6.