Preparation method of super-wear-resistant low-temperature-resistant glassy hydrophobic coating and coating

Abstract

The application provides a kind of super wear-resistant low-temperature resistant glassy hydrophobic coating, coating preparation method and coating, the preparation method of coating includes the following steps: step 1, using methyl acryloyloxy silane and hydroxyethyl methacrylate as raw material, under the condition of initiator and diluent, modified prepolymer is generated by reaction;Step 2, the prepared modified prepolymer is dissolved in diluent, then mixed with PDES-ran-PTFPMS fluorine-containing copolymer siloxane, isocyanate curing agent, ultraviolet absorber, super wear-resistant low-temperature resistant glassy hydrophobic coating is prepared by solution polycondensation method, the coating is coated on the surface of object, and solidified into film to form coating, the coating prepared by the application has super wear-resistant, low-temperature resistant and hydrophobic properties, can improve the wear of coating under harsh conditions, improve the low-temperature resistant environment ability, reduce the adhesion time of adhered corrosion medium or impurities that can cause coating to be scratched and damaged, prolong the comprehensive protection effect and life of coating.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to an ultra-wear-resistant, low-temperature resistant, glassy hydrophobic coating, a method for preparing the coating, and the coating itself. Background Technology

[0002] Protective films, providing temporary or long-term protection, are used in fields such as automotive transportation, aerospace, electronics, outdoor sports, wind power, medical equipment, and construction. The performance of the protective film plays a decisive role in its surface protection of the substrate. Common protective film materials include PET, PVC, PE, PI, PTFE, PP, and PU leather. With the continuous expansion of protective film applications, in conditions such as windy sandstorms, low temperatures, severe air pollution, and high salt spray, it is necessary to coat the surface of the protective film material with functional coatings to improve its protective effect.

[0003] Unlike functional coatings using microencapsulation technology applied to surfaces such as metals, glass, and ceramics, self-healing coatings currently used on protective films are actually highly resilient polymer resin materials. These self-healing resins are all made of acrylic-modified polyurethane resin, i.e., polyurethane acrylate, which utilizes both the tensile strength and resilience of polyurethane and the resistance to yellowing and weathering of acrylate. For protective film coatings, resistance to sand and gravel abrasion, resistance to high and low temperature environments, and the presence of adhering corrosive media or impurities that can scratch or damage the coating are significant adverse factors affecting the service life of the protective film coating. Existing coatings used on protective films cannot achieve the protective effects of sand and gravel abrasion resistance, low temperature resistance, pollution resistance, self-cleaning, aging resistance, and acid and alkali resistance. Summary of the Invention

[0004] This invention addresses the aforementioned problems by providing an ultra-wear-resistant, low-temperature-resistant, glassy hydrophobic coating, a preparation method for the coating, and the coating itself. The coating prepared by this invention possesses ultra-wear resistance, low-temperature resistance, and hydrophobic properties. It effectively improves the coating's resistance to wear under harsh conditions such as sand and gravel, enhances its resistance to low-temperature environments, and reduces the adhesion time of corrosive media or impurities that could cause scratches or damage to the coating, thereby extending the overall protective effect and lifespan of the coating.

[0005] This invention provides a method for preparing an ultra-wear-resistant, low-temperature-resistant, glassy hydrophobic coating, characterized by the following steps: Step S1, using methacryloxysilane and hydroxyethyl methacrylate as raw materials, reacting them in the presence of an initiator and a diluent to generate a modified prepolymer;

[0006] Step S2: The modified prepolymer prepared in step S1 is dissolved in a diluent, and then mixed with PDES-ran-PTFPMS fluorinated copolysiloxane, isocyanate curing agent, and UV absorber. An ultra-wear-resistant, low-temperature-resistant, glassy hydrophobic coating is prepared using a solution polycondensation method. The structural formula of the PDES-ran-PTFPMS fluorinated copolysiloxane is shown below:

[0007]

[0008] This invention utilizes a modified prepolymer synthesized from KH570, HEMA, and a curing agent. The modified prepolymer molecular chain contains a large number of hydroxyl groups and siloxane groups. The presence of silicon enhances its wear resistance and self-healing ability, resulting in a small wear volume and strong resistance to sand and gravel impact. Furthermore, the hydroxyl groups can react with isocyanate curing agents to form a network of urethane bonds, thus providing conditions for self-repair after coating damage and achieving the coating's ultra-wear-resistant properties. The siloxane groups can hydrolyze with subsequently added fluorinated siloxane polymers to form a glassy silica network structure, further increasing the silicon content of the coating and further improving its wear performance. The fluorine element ensures that the coating has an extremely high water contact angle and low-temperature resistance, thereby ensuring that the coating has glassy superhydrophobic properties.

[0009] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating provided by this invention may also have the following characteristics: the raw materials used to prepare the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating are added in the following mass parts: 25-35 parts of methacryloxysilane, 30-40 parts of hydroxyethyl methacrylate, 1-3 parts of initiator, 5-35 parts of PDES-ran-PTFPMS fluorinated copolysiloxane, 10-30 parts of isocyanate curing agent, 0.5-2.5 parts of ultraviolet absorber, and 10-15 parts of diluent. The effect of the diluent on chemical synthesis is mainly on ease of processing and flow; the amount added in both steps is based on the viscosity observed during the reaction.

[0010] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating provided by the present invention may also have the following characteristics: the method for preparing the modified prepolymer in step S1 is as follows: the initiator, methacryloxysilane, hydroxyethyl methacrylate and diluent are placed in a reaction vessel, nitrogen gas is introduced, and the mixture is stirred and reacted at 78℃~82℃ for 5h~6h to obtain the modified prepolymer.

[0011] When the viscosity of the system is high (when the rotor's rotational force is insufficient, it indicates that the viscosity is high; it is not necessary to determine the viscosity value to be high, and no measurement is required; if the rotor's rotational speed is slow, it is judged that the viscosity is high), add a small amount of diluent and continue the reaction for 3 to 4 hours to obtain the modified prepolymer.

[0012] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating provided by the present invention may also have the following feature: the specific preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating in step S2 is as follows:

[0013] Step S2-1: Cool the temperature of the modified prepolymer solution prepared in step S1 to below 20°C, then pour in the diluent, adjust the solid content to 20% with an error of ±1%, and stir until the modified prepolymer is completely dissolved in the diluent.

[0014] Step S2-2: Dissolve PDES-ran-PTFPMS fluorinated copolysiloxane in dichloromethane to prepare a solution with a mass concentration of 3% to 5%.

[0015] Step S2-3: Slowly add the PDES-ran-PTFPMS fluorinated copolysiloxane solution prepared in step S2-2 to the modified prepolymer prepared in step S2-1, and stir. During the process, the viscosity of the system needs to be observed. If the viscosity is too high (when the rotor rotation force is insufficient, it indicates that the viscosity is too high. It is not necessary to determine the viscosity value as high viscosity. No measurement is required. If the rotor rotation speed is slow, it is judged that the viscosity is too high), an appropriate amount of diluent needs to be added to reduce the viscosity (adjusting the viscosity is mainly for easy processing). After the addition is complete, add the isocyanate curing agent and the ultraviolet absorber, stir, and react for 2 to 3 hours to generate an ultra-wear-resistant, low-temperature resistant, glassy hydrophobic coating.

[0016] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating provided by the present invention may also have the following characteristics: the initiator is azobisisobutyronitrile (AIBN) or azobisisoheptanenitrile (ABVN).

[0017] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating provided by the present invention may also have the following characteristics: the ultraviolet absorber is a triazine ultraviolet absorber, specifically BASF's Tinuvin 622 and / or Tinuvin 400.

[0018] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating provided by the present invention may also have the following characteristics: the diluent is one or more of xylene, ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether, and acetylacetone; when the diluent is a mixture of multiple substances, the multiple substances are mixed in a fixed proportion.

[0019] Furthermore, the preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating provided by the present invention may also have the following feature: the isocyanate curing agent is one or more of Covestro N3600, N3390, and N75.

[0020] The present invention also provides a method for preparing an ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating, characterized in that: the above-mentioned ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating is applied to the surface of an object, and after curing into a film, an ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating is formed.

[0021] Furthermore, the method for preparing the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating provided by this invention may also have the following characteristics: the coating thickness ranges from 4 μm to 25 μm, the thermosetting temperature is from 100℃ to 120℃, and the curing conditions are from 40℃ to 50℃. The curing and curing times depend on the coating temperature and coating thickness.

[0022] The present invention also provides an ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating, characterized in that: the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating is prepared by the above-mentioned preparation method of ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating.

[0023] The present invention has the following advantages:

[0024] This invention employs a step-by-step feeding method. An initiator initiates the polymerization of HEMA,KH570 in a diluent to generate a modified prepolymer. Then, an isocyanate curing agent, a UV absorber, and a fluorinated siloxane polymer are added to this prepolymer to initiate a crosslinking reaction, thereby forming a glassy superhydrophobic property with self-healing and wear-resistant properties. The prepared modified prepolymer molecular chain contains a large number of hydroxyl groups and siloxane groups. The presence of silicon (Si) enhances its wear resistance and self-healing ability, resulting in a small wear volume and strong resistance to sand and gravel impacts. Furthermore, the hydroxyl groups can react with the isocyanate curing agent to form a network of urethane bonds, providing conditions for self-repair after coating damage, thus achieving the coating's ultra-wear-resistant properties. The siloxane groups can hydrolyze with the subsequently added fluorinated siloxane polymer to form a glassy silica network structure, further increasing the silicon content of the coating and improving its wear performance. The fluorine element ensures that the protective film has an extremely high water contact angle and low-temperature resistance, thereby ensuring the coating's glassy superhydrophobic properties. Therefore, the coating of the present invention has ultra-wear-resistant, low-temperature resistant and hydrophobic properties, which can effectively improve the coating's resistance to wear under harsh conditions such as sand and gravel, enhance its resistance to low-temperature environments, reduce the adhesion time of corrosive media or impurities that cause scratches and damage to the coating, thereby extending the overall protective effect and lifespan of the coating. Detailed Implementation

[0025] To make the technical means, creative features, objectives and effects of this invention easy to understand, the following embodiments are used to specifically illustrate the preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating and coating of this invention.

[0026] This invention is mainly used on various protective films.

[0027] Example 1

[0028] In this embodiment, the initiator is DuPont AIBN azobisisobutyronitrile (V60 / VAZO64); PDES-ran-PTFPMS is a fluorinated copolysiloxane prepared by alkaline ring-opening polymerization of phosphazene; the curing agent is Covestro N3600; the ultraviolet absorber is BASF's Tinuvin 622; and the diluent is a mixture of xylene, ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether in a mass ratio of 4:4:1:1.

[0029] The preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating includes the following steps:

[0030] Step S1: Accurately weigh 2g of initiator, 32g of methacryloxysilane, 38g of hydroxyethyl methacrylate and 3g of diluent and place them in a three-necked flask. Purge with nitrogen and stir. React at 80°C for 5 hours. Because the viscosity of the reaction system is high, add another 2g of diluent and continue the reaction for 3 hours to obtain the modified prepolymer.

[0031] In step S2-1, the temperature of the modified prepolymer prepared in step S1 is lowered to 19°C using an ice-water bath. Then, a diluent is added, and the solid content is adjusted to 20% (the solid content is determined by testing). The mixture is stirred until the modified prepolymer is completely dissolved in the diluent.

[0032] Step S2-2: Dissolve 15g of PDES-ran-PTFPMS fluorinated copolysiloxane in dichloromethane to obtain a solution with a mass concentration of 3%.

[0033] In step S2-3, adjust the peristaltic pump speed to 2 r / min and slowly add the PDES-ran-PTFPMS fluorinated copolysiloxane solution prepared in step S2-2 dropwise into a three-necked flask while stirring. During the dropwise addition process, diluent is added again to reduce the viscosity due to its high viscosity. The dropwise addition process takes approximately 2 hours. After the dropwise addition is complete, add 12g of curing agent and 1g of UV absorber to the three-necked flask, stir, and react for 2 hours to generate an ultra-wear-resistant, low-temperature resistant, glassy hydrophobic coating. When using, adjust the prepared coating to a fixed solids content.

[0034] The total amount of diluent used in the preparation process is 15g.

[0035] The preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating includes the following steps: the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating prepared above is coated onto a polyurethane film using a laboratory electric wire bar coater and then placed in an oven for heat curing at 120°C for 5 minutes, and then cured at 45°C for 24 hours to obtain a coating with a dry film thickness of 10 μm.

[0036] Example 2

[0037] In this embodiment, the initiator is DuPont AIBN azobisisobutyronitrile (V60 / VAZO64); PDES-ran-PTFPMS is a fluorinated copolysiloxane prepared by alkaline ring-opening polymerization of phosphazene; the curing agent is Covestro N3390; the ultraviolet absorber is BASF's Tinuvin 622; and the diluent is ethyl acetate.

[0038] The preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating includes the following steps:

[0039] Step S1: Accurately weigh 2g of initiator, 25g of methacryloxysilane, 32g of hydroxyethyl methacrylate and 3g of diluent, place them in a three-necked flask, introduce nitrogen gas, and react at 80°C for 5.5h to obtain the modified prepolymer.

[0040] In step S2-1, the temperature of the modified prepolymer prepared in step S1 is lowered to 18°C ​​using an ice-water bath. Then, a diluent is added, and the solid content is adjusted to 20% (the solid content is determined by testing). The mixture is stirred until the modified prepolymer is completely dissolved in the diluent.

[0041] Step S2-2: Dissolve 20g of PDES-ran-PTFPMS fluorinated copolysiloxane in dichloromethane to obtain a solution with a mass concentration of 5%.

[0042] In step S2-3, adjust the peristaltic pump speed to 2 r / min and slowly add the PDES-ran-PTFPMS fluorinated copolysiloxane solution prepared in step S2-2 dropwise into a three-necked flask while stirring. During the dropwise addition process, diluent is added again to reduce the viscosity due to its high viscosity. The dropwise addition process takes approximately 2 hours. After the dropwise addition is complete, add 12g of curing agent and 1g of UV absorber to the three-necked flask, stir, and react for 2 hours to generate an ultra-wear-resistant, low-temperature resistant, glassy hydrophobic coating. When using, adjust the prepared coating to a fixed solids content.

[0043] The total amount of diluent used in the preparation process is 12g.

[0044] The preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating includes the following steps: the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating prepared above is coated onto a polyurethane film using a laboratory electric wire bar coater and then placed in an oven for heat curing at 120°C for 5 minutes, and then cured at 45°C for 24 hours to obtain a coating with a dry film thickness of 10 μm.

[0045] Example 3

[0046] In this embodiment, the initiator is Huaxiang Kejie azobisisoheptanenitrile 4419-11-8ABVN V65; PDES-ran-PTFPMS is a fluorinated copolysiloxane prepared by alkaline-catalyzed ring-opening polymerization of phosphazene; the curing agent is Covestro N3600; the ultraviolet absorber is BASF's Tinuvin 400; and the diluent is xylene.

[0047] The preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating includes the following steps:

[0048] Step S1: Accurately weigh 3g of initiator, 35g of methacryloxysilane, 30g of hydroxyethyl methacrylate and 3g of diluent, and place them in a three-necked flask. Purge with nitrogen and react at 82°C for 5 hours. Due to the high viscosity of the reaction system, add 1g of diluent and continue the reaction for 3.5 hours to obtain the modified prepolymer.

[0049] In step S2-1, the temperature of the modified prepolymer prepared in step S1 is lowered to 18°C ​​using an ice-water bath. Then, a diluent is added, and the solid content is adjusted to 20% (the solid content is determined by testing). The mixture is stirred until the modified prepolymer is completely dissolved in the diluent.

[0050] Step S2-2: Dissolve 25g of PDES-ran-PTFPMS fluorinated copolysiloxane in dichloromethane to obtain a solution with a mass concentration of 5%.

[0051] In step S2-3, adjust the peristaltic pump speed to 2 r / min and slowly add the PDES-ran-PTFPMS fluorinated copolysiloxane solution prepared in step S2-2 dropwise into a three-necked flask while stirring. During the dropwise addition, diluent is added again to reduce the viscosity due to its high viscosity. The dropwise addition process takes approximately 2 hours. After the dropwise addition is complete, add 20g of curing agent and 2.5g of UV absorber to the three-necked flask, stir, and react for 2.5 hours to generate an ultra-wear-resistant, low-temperature resistant, glassy hydrophobic coating. When using, adjust the prepared coating to a fixed solids content.

[0052] The total amount of diluent used in the preparation process is 15g.

[0053] The preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating includes the following steps: the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating prepared above is coated onto a polyurethane film using a laboratory electric wire bar coater and then placed in an oven for heat curing at 110°C for 7 minutes, and then cured at 50°C for 24 hours to obtain a coating with a dry film thickness of 10 μm.

[0054] Example 4

[0055] In this embodiment, the initiator is Huaxiang Kejie azobisisoheptanenitrile 4419-11-8ABVN V65; PDES-ran-PTFPMS is a fluorinated copolysiloxane prepared by alkaline-catalyzed ring-opening polymerization of phosphazene; the curing agent is Covestro N75; the ultraviolet absorber is BASF's Tinuvin 400; and the diluent is acetylacetone.

[0056] The preparation method of the ultra-wear-resistant and low-temperature-resistant glassy hydrophobic coating includes the following steps:

[0057] Step S1: Accurately weigh 1g of initiator, 27g of methacryloxysilane, 40g of hydroxyethyl methacrylate and 3g of diluent, and place them in a three-necked flask. Purge with nitrogen and react at 78°C for 6 hours. Due to the high viscosity of the reaction system, add another 1g of diluent and continue the reaction for 4 hours to obtain the modified prepolymer.

[0058] In step S2-1, the temperature of the modified prepolymer prepared in step S1 is lowered to 18°C ​​using an ice-water bath. Then, a diluent is added, and the solid content is adjusted to 20% (the solid content is determined by testing). The mixture is stirred until the modified prepolymer is completely dissolved in the diluent.

[0059] Step S2-2: Dissolve 5g of PDES-ran-PTFPMS fluorinated copolysiloxane in dichloromethane to obtain a solution with a mass concentration of 4%.

[0060] In step S2-3, adjust the peristaltic pump speed to 2 r / min and slowly add the PDES-ran-PTFPMS fluorinated copolysiloxane solution prepared in step S2-2 dropwise into a three-necked flask while stirring. The dropwise addition process takes approximately 2 hours. After the dropwise addition is complete, add 30 g of curing agent and 2.0 g of UV absorber to the three-necked flask, stir, and react for 3 hours to generate an ultra-wear-resistant, low-temperature resistant, glassy hydrophobic coating. When using, adjust the prepared coating to a fixed solids content.

[0061] The total amount of diluent used in the preparation process is 10g.

[0062] The preparation method of the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating includes the following steps: the ultra-wear-resistant and low-temperature resistant glassy hydrophobic coating prepared above is coated onto a polyurethane film using a laboratory electric wire bar coater and then placed in an oven for heat curing at 100°C for 6 minutes, and then cured at 40°C for 24 hours to obtain a coating with a dry film thickness of 4 μm.

[0063] Example 5

[0064] The same descriptions as in Example 1 are omitted in Example 5. The difference between Example 5 and Example 1 is that in step S2-2, 20g of PDES-ran-PTFPMS fluorinated copolysiloxane is dissolved in dichloromethane to obtain a solution with a mass concentration of 5%.

[0065] Example 6

[0066] The same descriptions as in Example 1 are omitted in Example 6. The difference between Example 6 and Example 1 is that in step S2-2, 25g of PDES-ran-PTFPMS fluorinated copolysiloxane is dissolved in dichloromethane to obtain a solution with a mass concentration of 5%.

[0067] Example 7

[0068] The same descriptions as in Example 7 and Example 2 are omitted. The difference between Example 7 and Example 2 is that in step S2-2, the amount of PDES-ran-PTFPMS fluorinated copolysiloxane added is 25g.

[0069] Example 8

[0070] The same descriptions as in Example 2 are omitted in Example 8. The difference between Example 8 and Example 2 is that in step S2-2, the amount of PDES-ran-PTFPMS fluorinated copolysiloxane added is 30g.

[0071] Example 9

[0072] The same descriptions as in Example 9 and Example 3 are omitted. The difference between Example 9 and Example 3 is that in step S2-2, the amount of PDES-ran-PTFPMS fluorinated copolysiloxane added is 30g.

[0073] Example 10

[0074] The same descriptions as in Example 10 and Example 3 are omitted. The difference between Example 10 and Example 3 is that in step S2-2, the amount of PDES-ran-PTFPMS fluorinated copolysiloxane added is 35g.

[0075] Comparative Example 1

[0076] The identical descriptions of the parts in Comparative Example 1 and Example 1 are omitted. The difference between Comparative Example 1 and Example 1 is that the raw materials in step S2 do not contain PDES-ran-PTFPMS fluorinated copolysiloxane. Step S2 does not include steps S2-2 and S2-3. After step S2-1, the curing agent and ultraviolet absorber are added directly, and the coating is generated after 2 to 3 hours of reaction.

[0077] Comparative Example 2

[0078] A self-healing coating for automotive paint protection using superhydrophobic TPU material is disclosed. The raw materials for preparing this coating include: 100 parts by weight of aliphatic diisocyanate, 500 parts by weight of hydroxyl polyether polyol, 20 parts by weight of catalyst, 30 parts by weight of chain extender, 5 parts by weight of UV stabilizer, 200 parts by weight of solvent, 10 parts by weight of inert silicone oil, 3 parts by weight of sodium citrate-modified nanoparticles, 5 parts by weight of dispersant, and 10 parts by weight of defoamer. The preparation method differs from that of this invention.

[0079] The amounts of raw materials used in Examples 1 to 10 and Comparative Example 1 are shown in Table 1.

[0080] Table 1.

[0081]

[0082] The coatings prepared in Examples 1-10, Comparative Example 1, and Comparative Example 2 were subjected to abrasion resistance tests, sand and gravel impact abrasion tests, low-temperature resistance tests, and hydrophobicity tests. The test results are shown in Table 3.

[0083] Laboratory abrasion resistance test method: Akron abrasion tester: performed according to GB / T 1689. Results are calculated and evaluated by the change in wear volume before and after wear.

[0084] Gravel impact abrasion test: Gravel impact abrasion tester (refer to ASTM-D-3170-87) [SAE 45°] Equipment: Gravelometer; Test time (impact time): 10 seconds; Gas tank pressure: 60-80 PSI, equivalent to 5-6 kg / cm² 2 500ml of crushed stone was sprayed onto the surface of the sample with the protective film attached under a certain pressure. After the test, the surface of the sample was visually inspected for defects such as scratches, cracks, pits, and breaks, and rated accordingly. The rating method is as follows: The damaged area on the test sample being evaluated is 100×100mm, which is the center of the damaged area. The number of peelings is shown in Table 2, with 10-0 used to represent the number of test areas in the 100×100mm square area. For the rating of the protective film, if there is no obvious damage or puncture to the protective film before and after the test, it can be quantitatively reflected by comparing the smoothness Rq.

[0085] Table 2. Numerical Classification of Damage Grades

[0086] Rank Number of damages (pockmarks / pits) 10 0 9 1 8 2-4 7 5-9 6 10-24 5 25-49 4 50-74 3 75-99 2 100-149 1 150-250 0 >250

[0087] Low-temperature resistance test method: After storage at -40℃ for 1 hour, the film is quickly taken out and bent around a cylinder with a diameter of 40mm. The surface coating of the protective film is then checked for cracks. Results: Obvious cracks are considered poor, slight cracks are considered good, and no cracks are considered excellent.

[0088] Hydrophobicity testing method: The static water contact angle of the material surface was measured at room temperature using a contact angle meter. A Kruss DSA Y-82 contact angle meter (Germany) was used for the contact angle test. The contact medium was deionized water, the droplet size was 50 μl, and the contact time was 60 seconds.

[0089] Table 3. Test Results

[0090]

[0091] As shown in Table 3, the present invention outperforms Comparative Example 2 in terms of sand and gravel impact abrasion resistance and low-temperature resistance. The use of PDES-ran-PTFPMS fluorinated copolysiloxane in the coating formulation of the present invention significantly enhances the coating's low-temperature resistance and hydrophobicity (high water contact angle). Furthermore, without affecting the polymerization viscosity and quality, the higher the weight ratio of PDES-ran-PTFPMS fluorinated copolysiloxane, the better the low-temperature resistance and hydrophobicity. In summary, the coating of the present invention simultaneously improves wear resistance, sand and gravel resistance, low-temperature resistance, and hydrophobicity, exhibiting excellent overall performance and suitable for various protective film surfaces.

[0092] The above embodiments are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention.

Claims

1. A process for the preparation of a super abrasion resistant low temperature resistant glassy hydrophobic coating characterized in that, It comprises the following steps: Step S1, a modified prepolymer is prepared from methacryloyloxysilane and hydroxyethyl methacrylate as raw materials, in the presence of an initiator and a diluent; Step S2, the modified prepolymer prepared in step S1 is dissolved in a diluent, then mixed with PDES-ran-PTFPMS fluorine-containing copolysiloxane, isocyanate curing agent, and ultraviolet absorber to prepare the super wear-resistant low-temperature-resistant glassy hydrophobic coating by solution polycondensation, wherein the structure of PDES-ran-PTFPMS fluorine-containing copolysiloxane is as follows: The raw materials for preparing the super wear-resistant low-temperature-resistant glassy hydrophobic coating are added in the following mass fractions: methacryloyloxysilane 25-35 parts, hydroxyethyl methacrylate 30-40 parts, initiator 1-3 parts, PDES-ran-PTFPMS fluorine-containing copolysiloxane 5-35 parts, isocyanate curing agent 10-30 parts, ultraviolet absorber 0.5-2.5 parts, and diluent 10-15 parts.

2. The preparation method of the super wear-resistant low-temperature-resistant glassy hydrophobic coating according to claim 1, characterized in that: The method for preparing the modified prepolymer in step S1 is as follows: the initiator, methacryloyloxysilane, hydroxyethyl methacrylate, and diluent are placed in a reaction container, nitrogen is introduced, stirring is performed, and the reaction is carried out at 78-82°C for 5-6h to obtain the modified prepolymer; When the viscosity of the system is large, a small amount of diluent is further added, and the reaction is continued for 3-4h to obtain the modified prepolymer.

3. The preparation method of the super wear-resistant low-temperature-resistant glassy hydrophobic coating according to claim 2, characterized in that: The specific preparation method for preparing the super wear-resistant low-temperature-resistant glassy hydrophobic coating in step S2 is as follows: Step S2-1, the temperature of the modified prepolymer solution prepared in step S1 is reduced to below 20°C, then the diluent is poured in, the solid content is adjusted to 20%, with an error of ±1%, and stirring is performed until the modified prepolymer is completely dissolved in the diluent; Step S2-2, the PDES-ran-PTFPMS fluorine-containing copolysiloxane is dissolved in dichloromethane to prepare a solution with a mass concentration of 3%-5%; Step S2-3, the PDES-ran-PTFPMS fluorine-containing copolysiloxane solution prepared in step S2-2 is slowly added to the modified prepolymer prepared in step S2-1, stirring is performed, and the viscosity of the system is observed in the process; if the viscosity is large, an appropriate amount of diluent is added to reduce the viscosity; after the addition is completed, the isocyanate curing agent and the ultraviolet absorber are added, stirring is performed, and the reaction is carried out for 2-3h to obtain the super wear-resistant low-temperature-resistant glassy hydrophobic coating.

4. The preparation method of the super wear-resistant low-temperature-resistant glassy hydrophobic coating according to claim 1, characterized in that: The initiator is azobisisobutyronitrile AIBN or azobisisoheptyl nitrile ABVN.

5. The preparation method of the super wear-resistant low-temperature-resistant glassy hydrophobic coating according to claim 1, characterized in that: The ultraviolet absorber is a triazine ultraviolet absorber, and the model number is Tinuvin 622 and / or Tinuvin 400 of BASF.

6. The method for preparing the super-wear-resistant and low-temperature-resistant glassy hydrophobic coating according to claim 1, characterized in that: the diluent is one or more of xylene, ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether, acetylacetone, and when the diluent is a mixture of multiple substances, the multiple substances are mixed in a fixed ratio.

7. The method for preparing the super-wear-resistant and low-temperature-resistant glassy hydrophobic coating according to claim 1, characterized in that: the isocyanate curing agent is one or more of Covestro N3600, N3390, and N75.

8. A method for preparing a super-wear-resistant and low-temperature-resistant glassy hydrophobic coating layer, characterized in that: the super-wear-resistant and low-temperature-resistant glassy hydrophobic coating prepared according to any one of claims 1-7 is coated on the surface of an object, and after being cured into a film, a super-wear-resistant and low-temperature-resistant glassy hydrophobic coating layer is formed.

9. The method for preparing the super-wear-resistant and low-temperature-resistant glassy hydrophobic coating layer according to claim 8, characterized in that: the coating thickness during coating is in the range of 4 μm to 25 μm, the heat curing temperature is 100°C to 120°C, and the curing condition is 40°C to 50°C.

10. A super-wear-resistant and low-temperature-resistant glassy hydrophobic coating layer, characterized in that: the super-wear-resistant and low-temperature-resistant glassy hydrophobic coating layer is prepared by the method for preparing the super-wear-resistant and low-temperature-resistant glassy hydrophobic coating layer according to claim 8 or 9.

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