An environment-friendly liquid ceramic with high hardness and flexibility

Abstract

The application discloses an environment-friendly liquid ceramic with high hardness and flexibility, which comprises components A and B, wherein the component A comprises the following components in parts by weight: epoxy oligomeric siloxane resin 30-40 parts, polysiloxane copolymer 10-20 parts, potassium aluminosilicate 4-8 parts, ceramic microspheres 5-10 parts, nano silicon dioxide 2-5 parts, and auxiliary agent 1-3 parts; and the component B comprises the following components in parts by weight: amino-terminated polyurea 20-30 parts and amine curing agent 5-10 parts. The combination of the epoxy oligomeric siloxane resin and the polysiloxane copolymer in the component A can provide high hardness of the liquid ceramic while maintaining certain flexibility. Meanwhile, the epoxy oligomeric siloxane resin and the polysiloxane copolymer have excellent high-temperature resistance and chemical corrosion resistance, and especially the stability of the siloxane bond enables the material to maintain its performance in high temperature and harsh chemical environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coatings, in particular to an environmentally friendly liquid ceramic with high hardness and flexibility. BACKGROUND

[0002] Liquid ceramic, as a new type of material with both inorganic and organic components, has been widely used in modern industrial fields, especially in coatings, protective layers and high-performance films. Liquid ceramic materials, with their excellent wear resistance, high temperature resistance, corrosion resistance and other properties, are widely used in aerospace, automobile manufacturing, electronic equipment and building decoration fields. However, traditional ceramic coating materials often have high hardness but high brittleness and insufficient toughness, which limits their widespread application in practice, especially in situations that require both impact resistance and flexibility.

[0003] In order to overcome these problems, in recent years there has been a trend of research on organically modified inorganic ceramic materials. These materials introduce organic polymers into ceramic coatings in order to improve the toughness and flexibility of the coating, so that the material has both high hardness and toughness. In particular, the emergence of organosilicon ceramic coatings has further improved the performance of traditional ceramic coatings. Silicone resins have become an ideal coating substrate due to their excellent weather resistance, chemical corrosion resistance and thermal stability. At present, coatings based on alkoxy silane, silica sol and acrylic emulsion composite material systems have shown excellent mechanical properties and environmental friendliness. However, how to further improve the flexibility and comprehensive performance of the coating through the synergistic effect of organosilicon and polymers is still a technical problem. In addition, there is an increasing demand for room temperature curing coatings to meet the needs of applications that do not require high temperature baking, therefore, the development of an environmentally friendly, easy-to-apply liquid ceramic coating with high hardness and flexibility has become a technical problem to be solved. SUMMARY

[0004] Based on the problems in the background art, the present application provides an environmentally friendly liquid ceramic with high hardness and flexibility.

[0005] The present application is implemented by the following technical solutions:

[0006] An environmentally friendly liquid ceramic with high hardness and flexibility, comprising A component and B component, the A component comprises the following components by weight: epoxy oligomeric siloxane resin 30-40 parts, polysiloxane copolymer 10-20 parts, potassium aluminosilicate 4-8 parts, ceramic microspheres 5-10 parts, nano-silicon dioxide 2-5 parts, and auxiliary agent 1-3 parts.

[0007] The B component comprises the following components by weight: amino-terminated polyurea 20-30 parts, amine curing agent 5-10 parts.

[0008] Further, the preparation method of the epoxy oligomeric siloxane resin is specifically as follows: phenyl triethoxysilane, tetraethyl silicate and gamma-glycidyl ether oxypropyl trimethoxysilane are added into a mixed solution of ethanol and deionized water, stirred at 60 DEG C for 30 min, then hydrochloric acid is added, heated and condensed to reflux at 60 DEG C for 12 h, after the reaction is completed, low-boiling substances are removed by distillation under reduced pressure to obtain the epoxy oligomeric siloxane resin.

[0009] Further, the molar ratio of phenyl triethoxysilane, tetraethyl silicate and gamma-glycidyl ether oxypropyl trimethoxysilane is (1.2-1.6):(0.4-0.8):1.

[0010] Further, the weight ratio of ethanol and deionized water is (30-40):10.

[0011] The weight of ethanol is 2-3 times the weight of gamma-glycidyl ether oxypropyl trimethoxysilane.

[0012] The weight of hydrochloric acid is 10-20% of the weight of gamma-glycidyl ether oxypropyl trimethoxysilane.

[0013] Further, the preparation method of the polysiloxane copolymer is specifically as follows: phenyl triethoxysilane is added into a reaction kettle, a 0.1-2% mass concentration hydrochloric acid aqueous solution is added dropwise at 5-10 DEG C, after the dropwise addition is completed, the temperature is raised to 65 DEG C, and reaction is carried out for 2-3 h, then hydroxyl-terminated polysiloxane is continuously added, the temperature is raised to 110 DEG C, and reaction is carried out for 2-3 h, after the reaction is completed, low-boiling substances are removed by distillation under reduced pressure to obtain the polysiloxane copolymer.

[0014] Further, the mass ratio of phenyl triethoxysilane, the hydrochloric acid aqueous solution and the hydroxyl-terminated polysiloxane is (2-10):(0.3-1.6):1.

[0015] Further, the auxiliary agent includes a leveling agent, a defoaming agent and a dispersing agent, and the mass ratio is (1-2):(1-2):(1-2).

[0016] The leveling agent is a polyether modified polymethylalkylsiloxane, the defoaming agent is a polysiloxane defoaming agent, and the dispersing agent is BYK-2055.

[0017] Further, the amino-terminated polyurea is prepared from polyether amine D400 and isophorone diisocyanate.

[0018] Further, a solvent is further included, and the solvent is propylene glycol methyl ether acetate.

[0019] The application further discloses a preparation method of the environment-friendly liquid ceramic with high hardness and flexibility.

[0020] (1) corresponding raw materials are prepared according to a formula;

[0021] (2) Add epoxy oligomeric silicone resin, polysiloxane copolymer, ceramic microspheres, defoamer and dispersant into a container, disperse at high speed for 20 min, then grind and disperse to fineness of 1-10 microns using a sand mill, continue to add potassium aluminosilicate, nano-silica and leveling agent and disperse at high speed for 30 min, finally add solvent to adjust viscosity and solid content to obtain component A;

[0022] (3) Mix amino-terminated polyurea and amine curing agent to obtain component B.

[0023] Advantages of the present application:

[0024] 1. The combination of epoxy oligomeric silicone resin and polysiloxane copolymer in component A in the present application can provide high hardness of the liquid ceramic while maintaining certain flexibility. The crosslinking reaction between epoxy groups and siloxane can provide higher structural strength, while the flexible segment (polysiloxane) in the polysiloxane copolymer can endow the material with excellent flexibility. At the same time, the epoxy oligomeric silicone resin and the polysiloxane copolymer have excellent high-temperature resistance and chemical corrosion resistance, especially the stability of the siloxane bond enables the material to maintain its performance in high temperature and harsh chemical environment. Both the epoxy group and the siloxane bond in the material have good resistance to acid and alkali environment, ensuring that the material can remain stable in acid and alkali environment. Ceramic microspheres, nano-silica and potassium aluminosilicate as fillers can further improve the hardness of the material, especially in the microstructure by forming a dense particle reinforced network to further improve the surface hardness (more than 9H) without significantly reducing the flexibility.

[0025] 2. The combination of amino-terminated polyurea and amine curing agent in component B in the present application enables the component B to be quickly cured with component A under low temperature conditions. The polyurea curing agent has high reactivity and can quickly crosslink and form a strong network structure at a lower temperature. Therefore, the liquid ceramic in this formulation can also be cured in a low temperature environment, suitable for different use scenarios, especially in low temperature construction conditions. Propylene glycol methyl ether acetate as a solvent has low volatility and can maintain good solubility and flowability in a low temperature environment, helping the material to cure smoothly at low temperature.

[0026] 3. Propylene glycol methyl ether acetate is an environmentally friendly solvent with low volatility and low toxicity, which meets the modern environmental regulations on volatile organic compounds (VOC). It can help reduce the VOC emissions of the material, meet the environmental requirements, especially in fields with strict environmental standards (such as architectural coatings, automotive coatings, etc.). This formulation does not use traditional high-toxicity and high-pollution solvents or additives, and the entire material system is relatively environmentally friendly, which helps to reduce the negative impact on the environment and also reduces the health hazards to the construction personnel. DETAILED DESCRIPTION

[0027] The technical solutions of the present application are further described in detail below in combination with specific examples, but the protection scope of the present application is not limited to the following examples.

[0028] Example 1

[0029] Preparation method of epoxy oligomeric siloxane resin

[0030] Phenyl triethoxysilane, tetraethyl silicate and gamma-glycidoxypropyl trimethoxysilane are added to a mixed solution of ethanol and deionized water in a molar ratio of 1.4:0.6:1, the weight ratio of ethanol and deionized water is 30:10, the weight of ethanol is 2.5 times the weight of gamma-glycidoxypropyl trimethoxysilane, 60℃ stirring for 30min, then add hydrochloric acid, the weight of hydrochloric acid is 15% of the weight of gamma-glycidoxypropyl trimethoxysilane, 60℃ heating and condensing reflux for 12h, after the reaction is completed, remove the low boiling point material by distillation under reduced pressure, to obtain epoxy oligomeric siloxane resin.

[0031] The preparation method of the polysiloxane copolymer is as follows: phenyl triethoxysilane is added to a reaction kettle, 1% mass concentration hydrochloric acid aqueous solution is added dropwise at 5℃, after dropwise addition is completed, the temperature is raised to 65℃, and reaction is carried out for 2h, then hydroxyl-terminated polysiloxane is continuously added, the temperature is raised to 110℃, and reaction is carried out for 2h, after the reaction is completed, low boiling point material is removed by distillation under reduced pressure, to obtain polysiloxane copolymer. The mass ratio of phenyl triethoxysilane, hydrochloric acid aqueous solution and hydroxyl-terminated polysiloxane is 6:1:1 during the whole reaction process.

[0032] An environmentally friendly liquid ceramic with high hardness and flexibility comprises A component and B component, the A component comprises the following components by weight parts: epoxy oligomeric siloxane resin 35 parts, polysiloxane copolymer 15 parts, potassium aluminosilicate 6 parts, ceramic microspheres 8 parts, nano silicon dioxide 3 parts, leveling agent polyether modified polymethylalkylsiloxane 1 part, polysiloxane defoaming agent 1 part and dispersant BYK-2055 1 part.

[0033] The B component comprises the following components by weight parts: amino-terminated polyurea 25 parts, amine curing agent 8 parts.

[0034] The preparation method of the environmentally friendly liquid ceramic with high hardness and flexibility comprises the following steps:

[0035] (1) Prepare the corresponding raw materials according to the formula by weight parts;

[0036] (2) Add epoxy oligomeric silicone resin, polysiloxane copolymer, ceramic microspheres, defoaming agent and dispersing agent into a container, disperse at high speed for 20 min, then grind and disperse to fineness of 1-10 microns using a sander, continue to add potassium aluminosilicate, nano silicon dioxide and leveling agent and disperse at high speed for 30 min, finally add solvent propylene glycol methyl ether acetate to adjust the viscosity and solid content, to obtain component A;

[0037] (3) Mix the amino-terminated polyurea and amine curing agent uniformly to obtain component B.

[0038] In this embodiment, the process of grinding and dispersing to a fineness of 1-10 microns using a sander also includes:

[0039] Obtain the grinding power of the sander respectively ground to 1-10 microns, and determine the grinding frequency of the sander respectively ground to 1-10 microns according to the respective grinding power;

[0040] Determine the oscillation attribute of the sander respectively ground to 1-10 microns according to the grinding frequency, and the oscillation attribute includes: basic oscillation and basic oscillation plus load oscillation;

[0041] Determine the monitoring torque parameter of the sander respectively ground to 1-10 microns according to the oscillation attribute, and determine the grinding rate of the sander respectively ground to 1-10 microns according to the monitoring torque parameter;

[0042] Determine the state monitoring frame distance based on the grinding rate of the sander respectively ground to 1-10 microns and the grinding morphology of the sander respectively ground to 1-10 microns;

[0043] Set the monitoring index and index threshold in each grinding image according to the state monitoring frame distance, and construct the process state time sequence feature of the sander respectively ground to 1-10 microns based on the monitoring index and index threshold;

[0044] Determine the rotational speed time sequence feature of the sander respectively ground to 1-10 microns according to the process state time sequence feature and the grinding frequency of the sander respectively ground to 1-10 microns;

[0045] Establish the correlation feature between the process state time sequence feature and the rotational speed time sequence feature using a Bayesian model, and determine the rotational speed adjustment parameter of the sander respectively ground to 1-10 microns according to the correlation feature;

[0046] Adaptively adjust the grinding rotational speed of the sander respectively ground to 1-10 microns through the rotational speed adjustment parameter, and simultaneously perform state monitoring, and issue an abnormality reminder when the monitoring state is abnormal.

[0047] The beneficial effects of the above technical scheme are: by determining the respective speed adjustment parameters of the sanding machine for grinding to 1-10 microns, the best grinding quality of the grinding machine can be achieved on the basis of ensuring the grinding effect, the grinding reliability and stability are improved, further, by determining the monitoring index and then performing state monitoring, it can be ensured that the ground product meets the actual demand, the cost is reduced, and the practicality and reliability are improved.

[0048] Example 2

[0049] The difference between this embodiment and example 1 is that the A component includes the following components by weight parts: epoxy oligomeric siloxane resin 35 parts, polysiloxane copolymer 10 parts, potassium aluminosilicate 6 parts, ceramic microspheres 8 parts, nano silicon dioxide 3 parts, leveling agent polyether modified polymethylalkylsiloxane 1 part, polysiloxane defoaming agent 1 part and dispersant BYK-2055 1 part.

[0050] The rest is the same as example 1.

[0051] Example 3

[0052] The difference between this embodiment and example 1 is that the A component includes the following components by weight parts: epoxy oligomeric siloxane resin 35 parts, polysiloxane copolymer 20 parts, potassium aluminosilicate 6 parts, ceramic microspheres 8 parts, nano silicon dioxide 3 parts, leveling agent polyether modified polymethylalkylsiloxane 1 part, polysiloxane defoaming agent 1 part and dispersant BYK-2055 1 part.

[0053] The rest is the same as example 1.

[0054] Comparative example 1

[0055] The difference between this comparative example and example 1 is that the A component includes the following components by weight parts: polysiloxane resin (phenyl triethoxysilane) 35 parts, polysiloxane copolymer 15 parts, potassium aluminosilicate 6 parts, ceramic microspheres 8 parts, nano silicon dioxide 3 parts, leveling agent polyether modified polymethylalkylsiloxane 1 part, polysiloxane defoaming agent 1 part and dispersant BYK-2055 1 part.

[0056] Comparative example 2

[0057] The difference between this comparative example and example 1 is that the A component includes the following components by weight parts: epoxy oligomeric siloxane resin 35 parts, potassium aluminosilicate 6 parts, ceramic microspheres 8 parts, nano silicon dioxide 3 parts, leveling agent polyether modified polymethylalkylsiloxane 1 part, polysiloxane defoaming agent 1 part and dispersant BYK-2055 1 part.

[0058] Comparative example 3

[0059] The difference between the present comparative example and example 1 is that the component A comprises the following components by weight parts: epoxy oligomeric silicone resin 35 parts, polysiloxane copolymer 30 parts, potassium aluminosilicate 6 parts, ceramic microspheres 8 parts, nano-silica 3 parts, leveling agent polyether modified polymethylalkylsiloxane 1 part, polysiloxane defoaming agent 1 part and dispersant BYK-2055 1 part.

[0060] Comparative example 4

[0061] The difference between the present comparative example and example 1 is that the preparation method of the polysiloxane copolymer is as follows: phenyl triethoxysilane is added into a reaction kettle, 1% mass concentration hydrochloric acid aqueous solution is added dropwise at 5℃, after the dropwise addition is completed, the temperature is raised to 65℃, and reacted for 2h, then hydroxyl-terminated polysiloxane is continuously added, the temperature is raised to 110℃, and reacted for 2h, after the reaction is completed, low boiling point substances are removed by distillation under reduced pressure to obtain the polysiloxane copolymer. The mass ratio of phenyl triethoxysilane, hydrochloric acid aqueous solution and hydroxyl-terminated polysiloxane in the whole reaction process is 15:1.5:1.

[0062] Comparative example 5

[0063] The difference between the present comparative example and example 1 is that the component B comprises the following components by weight parts: amino-terminated polyurea 33 parts.

[0064] Performance test

[0065] The components A and B of examples 1-2 and comparative examples 1-6 are poured into a container according to a mass ratio of 1:1, stirred at a uniform speed of 300r / min for 2-3 minutes by using a blender, and directly sprayed or brushed on a sample plate, and sample preparation detection is carried out according to the standard, and the detection standard and detection results are shown in Table 1 and Table 2.

[0066] Table 1

[0067]

[0068]

[0069] Table 2

[0070]

[0071] Finally, it should be noted that the above examples only express several embodiments of the present application, and are not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art without departing from the concept of the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

Claims

1. An environmentally friendly liquid ceramic having high hardness and flexibility, comprising a component A and a component B, characterized in that, The A component comprises the following components by weight parts: epoxy oligomeric siloxane resin 30-40 parts, polysiloxane copolymer 10-20 parts, potassium aluminosilicate 4-8 parts, ceramic microspheres 5-10 parts, nano-silicon dioxide 2-5 parts, and auxiliary agent 1-3 parts; The B component is obtained by uniformly mixing amino-terminated polyurea 20-30 parts and amine curing agent 5-10 parts by weight parts; The preparation method of the epoxy oligomeric siloxane resin is specifically as follows: phenyl triethoxysilane, tetraethyl silicate and γ-glycidyl ether oxypropyl trimethoxysilane are added into a mixed solution of ethanol and deionized water, stirred at 60°C for 30 min, then hydrochloric acid is added, heated and condensed to reflux at 60°C for 12 h, after the reaction is completed, low-boiling substances are removed by distillation under reduced pressure to obtain the epoxy oligomeric siloxane resin; wherein the molar ratio of phenyl triethoxysilane, tetraethyl silicate and γ-glycidyl ether oxypropyl trimethoxysilane is (1.2-1.6):(0.4-0.8):

1. The preparation method of the polysiloxane copolymer is specifically as follows: phenyl triethoxysilane is added into a reaction kettle, a 0.1-2% mass concentration hydrochloric acid aqueous solution is added dropwise at 5-10°C, after the dropwise addition is completed, the temperature is raised to 65°C, and the reaction is carried out for 2-3 h, then hydroxyl-terminated polysiloxane is continuously added, the temperature is raised to 110°C, and the reaction is carried out for 2-3 h, after the reaction is completed, low-boiling substances are removed by distillation under reduced pressure to obtain the polysiloxane copolymer; wherein the mass ratio of phenyl triethoxysilane, hydrochloric acid aqueous solution and hydroxyl-terminated polysiloxane is (2-10):(0.3-1.6):

1.

2. The environmentally friendly liquid ceramic having both high hardness and flexibility according to claim 1, characterized in that, The weight ratio of ethanol and deionized water is (30-40):10; The weight of ethanol is 2-3 times the weight of γ-glycidyl ether oxypropyl trimethoxysilane; The weight of hydrochloric acid is 10-20% of the weight of γ-glycidyl ether oxypropyl trimethoxysilane.

3. The environmentally friendly liquid ceramic having both high hardness and flexibility according to claim 1, characterized in that, The auxiliary agent comprises leveling agent, defoaming agent and dispersant, and the mass ratio is (1-2):(1-2):(1-2); The leveling agent is polyether modified polymethylalkylsiloxane, the defoaming agent is polysiloxane defoaming agent, and the dispersant is BYK-2055.

4. The environmentally friendly liquid ceramic having both high hardness and flexibility according to claim 1, characterized in that, The amino-terminated polyurea is prepared from polyether amine D400 and isophorone diisocyanate.

5. The environmentally friendly liquid ceramic having both high hardness and flexibility according to claim 1, characterized in that, A solvent is further included, and the solvent is propylene glycol methyl ether acetate.

6. The method for preparing the liquid ceramic with high hardness and flexibility according to any one of claims 1-5, characterized in that, The following steps are included: (1) preparing corresponding raw materials according to the formula; (2) adding epoxy oligomeric siloxane resin, polysiloxane copolymer, ceramic microspheres, defoaming agent and dispersant into a container, high-speed dispersing for 20 min, then using a sander to grind and disperse to a fineness of 1-10 microns, continuously adding potassium aluminosilicate, nano-silicon dioxide and leveling agent, high-speed dispersing for 30 min, finally adding a solvent to adjust the viscosity and solid content to obtain the A component; (3) uniformly mixing amino-terminated polyurea and amine curing agent to obtain the B component.

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