High-wear-resistance door and window material and preparation method thereof

Abstract

The invention discloses a high-wear-resistance door and window material and a preparation method thereof, and relates to the technical field of building materials. The preparation method of the high-wear-resistance door and window material comprises the following steps: providing vinyl trimethoxy silane and an alkaline solution, mixing, and carrying out a first reaction to obtain a resin prepolymer; providing bis (3-aminopropyl) terminated poly (dimethyl siloxane) and isocyano ethyl methacrylate, mixing, and carrying out a second reaction to obtain a curing agent; providing an initiator, mixing the initiator with the resin prepolymer and a curing agent, and carrying out curing treatment to obtain a cured product; and carrying out etching treatment on the cured product to obtain the high-wear-resistance door and window material. The high-wear-resistance door and window material obtained by the method provided by the invention has high wear resistance, super-hydrophobic performance and high light transmittance, and has wide prospects in the aspects of extension of high-end application scenes such as high-performance doors and windows, curtain walls and special optical protection components.

Description

Technical Field

[0001] This application relates to the field of building materials technology, and in particular to a high wear-resistant door and window material and its preparation method. Background Technology

[0002] With the development of building energy conservation, smart homes, and high-end equipment, unprecedented high requirements have been placed on the comprehensive performance of door and window materials. Ideal materials must simultaneously possess: excellent light transmittance, outstanding weather resistance, high mechanical strength, good impact toughness, and durable self-cleaning (superhydrophobic) and wear-resistant properties.

[0003] However, existing technologies suffer from the following bottlenecks: Imbalance in mechanical properties: Highly transparent materials often have high hardness but poor toughness, making them brittle. While adding rubber phases or toughening agents can improve toughness, it often leads to a decrease in transparency and a loss of strength. Surface functional layers are prone to failure: To achieve superhydrophobicity, fluorine / silicon nanocoatings or microstructures are typically applied to the surface. These added functional layers have weak adhesion to the substrate and are prone to pulverization, peeling, or structural collapse under outdoor ultraviolet radiation, wind and sand abrasion, rain erosion, and thermal cycling, resulting in rapid functional decay and limited service life. Inability to integrate overall performance: Existing solutions are mostly physical superpositions of "substrate material + surface coating," which have interface defects and cannot achieve synergistic optimization of performance from the substrate to the surface.

[0004] Existing technologies cannot simultaneously meet the aforementioned mutually restrictive performance requirements. Therefore, there is an urgent need for a new type of door and window material that can simultaneously meet these performance requirements. Summary of the Invention

[0005] In view of this, this application provides a high wear-resistant door and window material and a method for preparing the same.

[0006] The embodiments of this application are implemented as follows: Firstly, the embodiments of this application provide a method for preparing a high wear-resistant door and window material, comprising the following steps:

[0007] Vinyltrimethoxysilane and an alkaline solution are provided, mixed, and subjected to a first reaction to obtain a resin prepolymer;

[0008] Bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate are mixed and subjected to a second reaction to obtain a curing agent;

[0009] An initiator is provided, which is mixed with the resin prepolymer and the curing agent, and then cured to obtain a cured product.

[0010] The cured product is etched to obtain a high wear-resistant door and window material.

[0011] Optionally, in some embodiments of this application, the mass ratio of the vinyltrimethoxysilane to the alkaline solution is (30~100):(5~20).

[0012] The molar concentration of the alkali in the alkaline solution ranges from 0.1 mol / L to 0.5 mol / L;

[0013] The alkali in the alkaline solution includes one or more of sodium hydroxide, potassium hydroxide, triethylamine, sodium bicarbonate, and pyridine.

[0014] Optionally, in some embodiments of this application, the first reaction includes a first reaction a and a first reaction b carried out sequentially, wherein the temperature of the first reaction b is greater than the temperature of the first reaction a;

[0015] The reaction temperature of the first reaction a is 50℃~70℃, and the reaction time of the first reaction a is 1h~10h;

[0016] The reaction temperature of the first reaction b is 70℃~90℃, and the reaction time of the first reaction b is 1h~10h.

[0017] Optionally, in some embodiments of this application, the structural formula of the resin prepolymer is shown below:

[0018] .

[0019] Optionally, in some embodiments of this application, the provision of bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate, mixed together, further includes: adding a first solvent; the first solvent is selected from one or more of anhydrous tetrahydrofuran, anhydrous 1,4-dioxane, diethyl ether, dimethylformamide, and dimethyl sulfoxide; the mass concentration of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) in the first solvent is 200 g / L to 600 g / L;

[0020] The mass ratio of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) to the isocyanate methacrylate is (5~80):(0.5~15).

[0021] The reaction temperature of the second reaction is 30℃~80℃, and the reaction time of the second reaction is 1h~10h.

[0022] Optionally, in some embodiments of this application, the curing agent has the following structural formula:

[0023] .

[0024] Optionally, in some embodiments of this application, the initiator is selected from one or more of benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide;

[0025] The mass ratio of the resin prepolymer, the curing agent, and the initiator is (10~80):(2~24):(0.1~1).

[0026] The provision of the initiator, mixed with the resin prepolymer and the curing agent, further includes: adding a second solvent; the second solvent is selected from one or more of benzene, toluene, anhydrous 1,4-dioxane, and methyltetrahydrofuran; the mass ratio of the resin prepolymer to the second solvent is (30~60):(30~70);

[0027] The curing temperature is 60℃~100℃, and the curing time is 3h~10h.

[0028] Optionally, in some embodiments of this application, the etching process includes: etching with an etching gas; the etching gas includes a mixture of oxygen and a fluorine-containing gas;

[0029] The radio frequency power of the etching process is 80W~300W, and the etching time is 0.5min~10min.

[0030] Optionally, in some embodiments of this application, the fluorine-containing gas includes one or more of carbon tetrafluoride, octafluoro-2-butene, and sulfur hexafluoride;

[0031] The volume ratio of the oxygen to the fluorine-containing gas is (1~8):(1~6).

[0032] Secondly, embodiments of this application also provide a high wear-resistant door and window material, which is prepared by the above-described preparation method.

[0033] The method for preparing high wear-resistant door and window materials provided in this application introduces methacryloyloxy groups at both ends of the curing agent using bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate. This allows the curing agent to form a strong covalent cross-linked network when copolymerizing with the resin prepolymer, providing skeletal strength and thermal stability for the high wear-resistant door and window material. Simultaneously, urea bonds generated by the reaction of isocyanate and amino groups are introduced into the curing agent. These units can form a large number of dynamic and reversible multiple hydrogen bond networks between molecules. When the high wear-resistant door and window material is impacted, the hydrogen bonds can preferentially break to dissipate energy, and then recombine under static conditions, thus endowing the high wear-resistant door and window material with excellent toughness, impact resistance, and potential self-healing ability. Furthermore, a long-chain polydimethylsiloxane is introduced at the center of the curing agent. Due to the long chain... The inherently low glass transition temperature of polydimethylsiloxane provides intrinsic segmental flexibility and impact toughness for high-wear-resistant door and window materials. Simultaneously, the dense silicon-methyl bonds on the main chain of long-chain polydimethylsiloxane exhibit higher etching reactivity than silicon-oxygen bonds in an oxygen plasma environment. This makes PDMS segments "preferred etching regions" in subsequent etching processes, guiding the formation of uniform, fine micro / nano rough structures rather than random etching. Mixing and curing the aforementioned curing agent with a vinyl-rich organosilicon resin prepolymer yields a dual-network structure with a covalent bond network as a rigid framework and a dynamic hydrogen bond network as a flexible buffer. This structure achieves interpenetration and synergy between the rigid and flexible phases at the nanoscale, fundamentally resolving the strength-toughness contradiction of the material.

[0034] The high wear-resistant door and window material obtained by the preparation method provided in this application has high wear resistance, superhydrophobic properties and high light transmittance, and has broad prospects for high-end application scenarios such as high-performance doors and windows, curtain walls and special optical protective components. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is a flowchart illustrating a method for preparing a high wear-resistant door and window material according to an embodiment of this application. Detailed Implementation

[0037] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0038] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the orientation shown in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0039] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0040] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0041] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0042] The structural formulas and molecular weights of some of the chemical reagents used in this application are described below:

[0043] Vinyltrimethoxysilane: Molecular weight = 148.23;

[0044] Ethyl isocyanate methacrylate: Molecular weight = 155.15;

[0045] Bis(3-aminopropyl)-terminated poly(dimethylsiloxane): The number average molecular weight is 1000, where n represents the degree of polymerization of bis(3-aminopropyl)-terminated poly(dimethylsiloxane), which is an integer from 5 to 15.

[0046] The technical solution of this application is as follows:

[0047] Firstly, please refer to Figure 1 This application provides a method for preparing a high wear-resistant door and window material, comprising the following steps:

[0048] Step S11: Vinyltrimethoxysilane and an alkaline solution are provided, mixed, and subjected to a first reaction to obtain a resin prepolymer;

[0049] Step S12: Bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate are provided, mixed, and subjected to a second reaction to obtain a curing agent;

[0050] Step S13: Provide an initiator, mix it with the resin prepolymer and the curing agent, and perform a curing treatment to obtain a cured product;

[0051] Step S14: Etch the cured product to obtain a high wear-resistant door and window material.

[0052] The method for preparing high-wear-resistant door and window materials provided in this application introduces methacryloyloxy groups at both ends of the curing agent using bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate. This allows the curing agent to form a strong covalent cross-linked network when copolymerizing with the resin prepolymer, providing skeletal strength and thermal stability for the high-wear-resistant door and window material. Simultaneously, urea bonds generated by the reaction of isocyanate and amino groups are introduced into the curing agent. These units can form a large number of dynamic and reversible hydrogen bond networks between molecules. When the high-wear-resistant door and window material is impacted, these hydrogen bonds can preferentially break to dissipate energy, and then recombine under static conditions, thus endowing the high-wear-resistant door and window material with excellent toughness, impact resistance, and potential self-healing ability. Furthermore, a long-chain polydimethylsiloxane is introduced at the center of the curing agent. Polydimethylsiloxane (PDMS), due to its inherently extremely low glass transition temperature, can provide intrinsic segmental flexibility and impact toughness for high wear-resistant door and window materials. Simultaneously, the dense silicon-methyl bonds on the main chain of long-chain PDMS exhibit higher etching reactivity than silicon-oxygen bonds in an oxygen plasma environment. This makes PDMS segments "preferred etching regions" in subsequent etching processes, guiding the formation of uniform, fine micro / nano rough structures rather than random etching. Mixing and curing the aforementioned curing agent with a vinyl-rich organosilicon resin prepolymer yields a dual-network structure with a covalent bond network as a rigid framework and a dynamic hydrogen bond network as a flexible buffer. This structure achieves interpenetration and synergy between the rigid and flexible phases at the nanoscale, fundamentally resolving the strength-toughness contradiction of the material.

[0053] The high wear-resistant door and window material obtained by the preparation method provided in this application has high wear resistance, superhydrophobic properties and high light transmittance, and has broad prospects for high-end application scenarios such as high-performance doors and windows, curtain walls and special optical protective components.

[0054] In step S11:

[0055] It should be noted that the alkaline solution refers to an aqueous solution formed by dissolving an alkali in water. The first reaction is a hydrolysis reaction, where water in the alkaline solution acts as a reactant (providing hydroxyl groups) and reacts with vinyltrimethoxysilane, while the alkali is used to neutralize the acid generated in the reaction to promote the hydrolysis reaction.

[0056] In some embodiments, the mass ratio of the vinyltrimethoxysilane to the alkaline solution is (30~100):(5~20), for example, it can be 30:6, 40:8, 50:10, 70:15, 90:18, or any range between two of the above ratios. Within the mass ratio range described above, the ratio of the vinyltrimethoxysilane to the alkaline solution is suitable and beneficial for the alkaline solution to catalyze the hydrolysis of the vinyltrimethoxysilane.

[0057] In some embodiments, the alkali in the alkaline solution includes one or more of sodium hydroxide, potassium hydroxide, triethylamine, sodium bicarbonate, and pyridine.

[0058] Furthermore, the molar concentration of the alkali in the alkaline solution can be in the range of 0.1 mol / L to 0.5 mol / L, for example, it can be 0.1 mol / L, 0.3 mol / L, 0.5 mol / L or any two of the above values.

[0059] In some embodiments, the first reaction includes a first reaction a and a first reaction b performed sequentially, wherein the temperature of the first reaction b is higher than the temperature of the first reaction a. The reaction temperature of the first reaction a is 50°C to 70°C, for example, 50°C, 60°C, 70°C, or any two of the above values; the reaction time of the first reaction a is 1 hour to 10 hours, for example, 1 hour, 2 hours, 3 hours, 6 hours, 8 hours, or any two of the above values; the reaction temperature of the first reaction b is 70°C to 90°C, for example, 70°C, 80°C, 90°C, or any two of the above values; the reaction time of the first reaction b is 1 hour to 10 hours, for example, 1 hour, 2 hours, 3 hours, 6 hours, 8 hours, 10 hours, or any two of the above values. Under the reaction conditions described above, the relatively low temperature of the first reaction a mainly promotes sufficient and uniform contact and mixing of the components, avoiding side effects caused by a rapid increase in temperature, while the higher temperature of the first reaction b is beneficial for the complete hydrolysis reaction.

[0060] In some embodiments, after the first reaction, the reaction solution of the first reaction can be subjected to rotary evaporation to remove residual reactants and deionized water, thereby obtaining a resin prepolymer.

[0061] In some embodiments, the resin prepolymer is a linear organosilicon resin prepolymer.

[0062] In some embodiments, the resin prepolymer has the following structural formula:

[0063] .

[0064] In some embodiments, the vinyltrimethoxysilane and the alkaline solution undergo a first reaction to obtain the resin prepolymer via the following synthetic route:

[0065] .

[0066] In step S12:

[0067] In some embodiments, the mass ratio of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) to the isocyanate methacrylate is (5~80):(0.5~15), for example, it can be 10:1.5, 20:3.1, 40:4.7, 50:12, 80:15, or any range between two of the above ratios. Within the mass ratio range described above, the ratio of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) to the isocyanate methacrylate is suitable and conducive to sufficient reaction between the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and the isocyanate methacrylate.

[0068] In some embodiments, a first solvent may be provided to mix the bis(3-aminopropyl)-terminated poly(dimethylsiloxane), the isocyanate methacrylate, and the first solvent to carry out a second reaction.

[0069] The first solvent is selected from one or more of anhydrous tetrahydrofuran (THF), anhydrous 1,4-dioxane, diethyl ether, dimethylformamide, and dimethyl sulfoxide.

[0070] In some embodiments, the mass concentration of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) in the first solvent is 200 g / L to 600 g / L, for example, it can be 200 g / L, 240 g / L, 400 g / L, 550 g / L, 600 g / L, or any range between two of the above values. Within this mass concentration range, it is beneficial for the raw materials to react fully in the system created by the first solvent.

[0071] In some embodiments, the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and the first solvent may be mixed first, and then the isocyanate methacrylate may be added dropwise under ice bath conditions for mixing.

[0072] In some embodiments, stirring can be used to promote uniform mixing of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and the isocyanate methacrylate in the first solvent.

[0073] In some embodiments, the reaction temperature of the second reaction is 30°C to 80°C, for example, 30°C, 40°C, 50°C, 70°C, 80°C or any two of the above values; the reaction time of the second reaction is 1h to 10h, for example, 1h, 2h, 3h, 6h, 8h, 10h or any two of the above values; under the reaction conditions described above, it is beneficial for the second reaction to proceed fully and improve the yield of the curing agent.

[0074] In some embodiments, the curing agent has the following structural formula:

[0075] .

[0076] In some embodiments, the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and the isocyanate methacrylate undergo a second reaction to obtain the curing agent via the following synthetic route:

[0077] .

[0078] Where n represents the degree of polymerization of bis(3-aminopropyl)-terminated poly(dimethylsiloxane), which is an integer from 5 to 15.

[0079] It should be noted that this application does not limit the order of steps S11 and S12. Step S11 can be performed first and then step S12, or step S12 can be performed first and then step S11, or steps S11 and S12 can be performed simultaneously.

[0080] In step S13:

[0081] In some embodiments, the initiator is selected from one or more of benzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP), and methyl ethyl ketone peroxide (MEKP).

[0082] In some embodiments, the mass ratio of the resin prepolymer, the curing agent, and the initiator is (10~80):(2~24):(0.1~1), for example, it can be 10:2:0.1, 18:3.2:0.2, 26:6:0.2, 40:10:0.5, 60:21:0.7, 75:22:0.8, or any range between two of the above ratios. Within the mass ratio range described above, the ratio of the resin prepolymer to the curing agent is suitable and conducive to the full curing of the resin prepolymer and the curing agent.

[0083] In some embodiments, a second solvent may also be provided, which is mixed with the initiator, the resin prepolymer, and the curing agent.

[0084] The second solvent is an organic solvent, which may be selected from one or more of benzene, toluene, anhydrous 1,4-dioxane, and methyltetrahydrofuran.

[0085] In some embodiments, the mass ratio of the resin prepolymer to the second solvent is (30~60):(30~70), for example, it can be 30:30, 40:50, 50:55, 60:70, 90:18, or any range between two of the above ratios. Within the mass ratio range described above, it is beneficial for the resin prepolymer to dissolve sufficiently in the second solvent.

[0086] In some embodiments, the initiator, the resin prepolymer, and the curing agent can be mixed uniformly by methods commonly used in the art, such as heating and stirring; wherein the heating temperature can be 30°C to 60°C, the stirring can be one or more of mechanical stirring, magnetic stirring, or ultrasonic stirring, and the stirring time can be 0.5h to 2h; for example, mechanical stirring can be performed at 50°C for 0.5h.

[0087] In some embodiments, air bubbles and excess solvent generated during stirring can be removed by vacuuming after stirring.

[0088] In some embodiments, the curing temperature is 60°C to 100°C, for example, 60°C, 70°C, 80°C, 90°C, 100°C or any two of the above values; the curing time is 3h to 10h, for example, 3h, 5h, 7h, 9h, 10h or any two of the above values; under the treatment conditions described above, it is beneficial for the resin prepolymer to be fully cured under the action of the curing agent.

[0089] In some embodiments, the curing process can be a stepped curing process; the step curing process involves a gradual increase in processing temperature and a gradual increase in processing time; for example, the stepped curing process can involve curing at 70°C for 2 hours and then curing at 90°C for 4 hours.

[0090] In step S14:

[0091] In some embodiments, the etching process includes: etching with an etching gas, the etching gas comprising a mixture of oxygen and a fluorine-containing gas.

[0092] In some embodiments, the fluorine-containing gas includes one or more of carbon tetrafluoride (CF4), octafluoro-2-butene (C4F8), and sulfur hexafluoride (SF6).

[0093] In some embodiments, the volume ratio of oxygen to fluorine-containing gas is (1~8):(1~6), for example, it can be 1:1, 1:2, 1.5:1, 2:1, 4:3, 7:5, or any range between two of the above ratios. Within the mass ratio range described above, the ratio of oxygen to fluorine-containing gas is suitable and beneficial for etching.

[0094] In some embodiments, the radio frequency power of the etching process is 80W to 300W, for example, it can be 80W, 100W, 180W, 200W or any two of the above values; the etching process time is 0.5min to 10min, for example, it can be 1min, 3min, 6min, 7min or any two of the above values; under the processing conditions described above, it is beneficial for the etching process to be fully carried out.

[0095] In some embodiments, the etching process can be a multi-stage etching process; the radio frequency power and etching time of the multi-stage etching process are gradually reduced; for example, in a deep reactive ion etching (DRIE) chamber (Oxford Instruments Plasmalab 80), an O2 / CF4 mixed gas (volume ratio 2:1) is introduced, the chamber pressure is 10 mTorr, the RF power is 200 W, and the etching time is 3 minutes; subsequently, the O2 / C4F8 mixed gas (volume ratio 1.5:1) is switched, the chamber pressure is 10 mTorr, the RF power is 100 W, and the etching time is 1 minute.

[0096] In the above embodiments, since the etching gas contains oxygen and fluorine-containing gas, the oxygen preferentially oxidizes the methyl groups in the PDMS chain segments, while the fluorine radicals generated by the fluorine-containing gas simultaneously fluorinate the exposed silicon atoms, which helps to form a more ideal nanoscale textured structure. This etching process is not a simple removal of surface material, but rather an in-situ chemical reaction at the outermost layer of the material (for example, at a depth of 100nm~500nm) to generate a novel fluorine-doped silicon-oxygen ceramic layer. This layer is chemically bonded to the material bulk through unbroken Si-O-Si bonds, without a physical interface, thereby achieving a perfect fusion and long-term stability of the surface superhydrophobicity, high wear resistance and the material bulk.

[0097] Secondly, this application provides a high wear-resistant door and window material, which is prepared by the above-described preparation method.

[0098] The high wear-resistant door and window material provided in this application has high wear resistance, superhydrophobic properties and high light transmittance, and has broad prospects for high-end application scenarios such as high-performance doors and windows, curtain walls and special optical protective components.

[0099] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0100] Example 1

[0101] This embodiment provides a high wear-resistant door and window material. The preparation method of the high wear-resistant door and window material includes the following steps:

[0102] Step S1: Weigh 50g of vinyltrimethoxysilane and add it to a 150mL three-necked flask. Start stirring and add 10g of sodium hydroxide aqueous solution (0.1mol / L) at 60℃. Purge with flowing nitrogen for protection and carry out hydrolysis reaction at 60℃ for 2h. Then raise the temperature to 80℃ and carry out hydrolysis reaction at 80℃ for 2h. After the reaction is completed, the reaction solution is rotary evaporated at 85℃ to remove the residual reactants and deionized water in the system, and obtain linear organosilicon resin prepolymer, i.e. resin prepolymer.

[0103] Step S2: Accurately weigh 20g of bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and 50mL of anhydrous THF into a 150mL three-necked flask, stir and mix evenly, purge with flowing nitrogen for protection, and add 3.1g of isocyanate methacrylate dropwise under ice bath conditions. After the addition is complete and the mixture is stirred evenly, raise the temperature to 50℃ and react at a constant temperature for 2h. After the reaction is completed, perform rotary evaporation on the reaction solution to remove residual THF in the system to obtain the curing agent.

[0104] Step S3: Take 40g of the resin prepolymer obtained in Step S1, 10g of the curing agent obtained in Step S2, 0.5g of benzoyl peroxide, and 50g of benzene and add them to a 150mL three-necked flask; mechanically stir at 50℃ for 30 minutes to ensure the reactants are completely and evenly mixed; vacuum at 50℃ for 10 minutes to remove air bubbles and some benzene generated during stirring; pour the reaction solution into a flat glass mold and place it in a vacuum oven for curing: cure at 70℃ for 2 hours and at 90℃ for 4 hours; then allow it to cool naturally and demold to obtain a transparent sheet about 2mm thick, which is the cured product.

[0105] Step S4: Cut the plate obtained in step S3 into sample pieces, place them in the deep reactive ion etching chamber, introduce O2 / CF4 mixed gas (volume ratio 2:1), chamber pressure 10 mTorr, RF power 200W, etching time 3 minutes; then switch to O2 / C4F8 mixed gas (volume ratio 1.5:1), chamber pressure 10 mTorr, RF power 100 W, etching time 1 minute, to obtain high wear-resistant door and window material.

[0106] Example 2

[0107] This embodiment is basically the same as Embodiment 1, except that the amount of resin prepolymer used in step S3 is 35g and the amount of curing agent used is 15g.

[0108] Example 3

[0109] This embodiment is basically the same as Embodiment 1, except that the amount of resin prepolymer used in step S3 is 45g and the amount of curing agent used is 5g.

[0110] Example 4

[0111] This embodiment is basically the same as embodiment 1, except that only a single etching step is performed in step S4. The plate obtained in step S3 is cut into sample pieces and placed in a deep reactive ion etching reaction chamber. O2 / CF4 / C4F8 ternary gas (volume ratio 2:1:1) is used, the chamber pressure is 10 mTorr, the RF power is 150 W, and the etching time is 4 minutes to obtain a high wear-resistant door and window material.

[0112] Comparative Example 1

[0113] This comparative example is basically the same as Example 1, except that in step S3, 10g of ethylene glycol dimethacrylate is used to replace 10g of curing agent.

[0114] Comparative Example 2

[0115] This comparative example is basically the same as Example 1, except that step S4 was not performed, i.e., no etching process was performed.

[0116] Comparative Example 3

[0117] This comparative example is basically the same as Example 1, except that step S4 was not performed, i.e., no etching was performed; at the same time, after step S3, a commercial nano self-cleaning coating (MDH-820, purchased from Hubei Maidehao Biotechnology Co., Ltd.) was applied to its surface by spraying and cured according to the product instructions.

[0118] The optical properties, surface properties, and mechanical properties of the high wear-resistant door and window materials provided in Examples 1-4 and Comparative Examples 1-3 were tested. The test results are shown in Table 1.

[0119] The transmittance and haze tests were conducted in accordance with the national standard GB / T 2410-2008 "Determination of transmittance and haze of transparent plastics", using an integrating sphere haze meter.

[0120] The water contact angle and roll-off angle were tested in accordance with the industry standard ISO 19403-2:2017, using a contact angle measuring instrument, with 5 μL of deionized water as the test solution, and the average value of 5 different locations was taken.

[0121] Pencil hardness testing was performed according to GB / T 6739-2006. Abrasion resistance was tested according to ASTM D1044-2013 using a Taber 5155 abrasion tester equipped with a CS-10 grinding wheel, a 1kg load, and 1000 rpm sample rotation. The changes in light transmittance and water contact angle retention were measured at the same location before and after testing.

[0122] Impact strength testing was conducted according to the national standard GB / T 1843-2008 "Determination of Impact Strength of Plastic Cantilever Beams" using a cantilever beam impact testing machine.

[0123] Table 1

[0124] name Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Light transmittance (%) / Haze (%) 92.5 / 1.2 90.1 / 1.8 93.8 / 0.9 91.3 / 1.5 88.7 / 3.5 93.0 / 1.0 89.5 / 5.2 Water contact angle / roll-off angle 158° / 4° 156° / 5° 155° / 6° 152° / 8° 145° / >30° 78° / No rolling 155° / 6° Pencil hardness 4H 2H 6H 3H 5H 3H <6B Taber light transmittance loss after wear 2.10% 2.80% 1.90% 3.50% 8.70% Untested Coating peeling Water contact angle retention rate after Taber wear 96.20% 94.90% 96.80% 92.70% 81.40% Untested <60% Impact strength 28.5 35.2 18.6 27.1 10.3 27.8 15.4

[0125] The test data above shows that Example 1, while maintaining ultra-high light transmittance (92.5%) and low haze (1.2%), achieves high hydrophobicity (158°), high hardness (4H), excellent wear resistance (light transmittance loss of only 2.1%), and outstanding toughness (28.5 kJ / m²). This data demonstrates that this application successfully breaks through the traditional performance limitations of "high light transmittance but not wear-resistant," "high strength but not impact-resistant," and "superhydrophobicity but not durable."

[0126] Comparative Example 1, using a common crosslinking agent, exhibited some hardness, but its impact strength (10.3 kJ / m²) was only 36% of that of Example 1, demonstrating a lack of dynamic hydrogen bond network and flexible PDMS segments, resulting in significantly increased material brittleness. After the same etching, Comparative Example 1 showed a lower hydrophobic angle (145°) and a larger roll-off angle, exhibiting poor wear resistance (contact angle retention rate 81.4%). This confirms the necessity of the "PDMS segments as etching guiding groups" design in this application—it guides the formation of a more uniform and efficient micro / nano hydrophobic structure. Comparative Example 2 (unetched) was completely non-hydrophobic, proving that the superhydrophobicity originated entirely from the DRIE-constructed surface structure. The catastrophic failure of Comparative Example 3 (conventional coating) was the most convincing: its surface hardness was extremely low (<6B), and the coating was rapidly worn through and peeled off in the Taber abrasion test, resulting in complete loss of hydrophobicity. This comparison highlights the superior wear resistance (hardness 4H, performance retention >96% after wear) and durability of the "integrated fluorinated silicon oxide ceramic layer" of this application, solving the core pain point of easy detachment of the surface functional layer. Furthermore, by adjusting the curing agent ratio (Examples 2 and 3), the mechanical property spectrum of the material can be directionally controlled within a certain range: Example 2 leans towards high toughness (35.2 kJ / m²), suitable for scenarios with higher impact resistance requirements; Example 3 leans towards high hardness (6H), suitable for scenarios with extremely high surface scratch resistance requirements. This demonstrates the flexibility of the design at the molecular level in this application.

[0127] In summary, the high wear-resistant door and window material prepared in this application has high transparency, high strength and toughness, superhydrophobicity and high wear resistance. Its experimental data proves that its various performance indicators are significantly better than those of traditional technical approaches. In particular, the integrated design of surface function and body performance fundamentally solves the technical bottleneck that has long plagued the industry, and has significant advanced features and broad industrialization prospects.

[0128] The high wear-resistant door and window material obtained by the preparation method provided in this application has high wear resistance, superhydrophobic properties and high light transmittance, and has broad prospects for high-end application scenarios such as high-performance doors and windows, curtain walls and special optical protective components.

[0129] The technical solutions provided by the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A method for preparing a high wear-resistant door and window material, characterized in that, Includes the following steps: Vinyltrimethoxysilane and an alkaline solution are provided, mixed, and subjected to a first reaction to obtain a resin prepolymer; Bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate are mixed and subjected to a second reaction to obtain a curing agent; An initiator is provided, which is mixed with the resin prepolymer and the curing agent, and then cured to obtain a cured product. The cured product is etched to obtain a high wear-resistant door and window material.

2. The preparation method according to claim 1, characterized in that, The mass ratio of the vinyltrimethoxysilane to the alkaline solution is (30~100):(5~20); The molar concentration of the alkali in the alkaline solution ranges from 0.1 mol / L to 0.5 mol / L; The alkali in the alkaline solution includes one or more of sodium hydroxide, potassium hydroxide, triethylamine, sodium bicarbonate, and pyridine.

3. The preparation method according to claim 1, characterized in that, The first reaction includes a first reaction a and a first reaction b carried out sequentially, wherein the temperature of the first reaction b is greater than the temperature of the first reaction a; The reaction temperature of the first reaction a is 50℃~70℃, and the reaction time of the first reaction a is 1h~10h; The reaction temperature of the first reaction b is 70℃~90℃, and the reaction time of the first reaction b is 1h~10h.

4. The preparation method according to claim 1, characterized in that, The structural formula of the resin prepolymer is shown below: 。 5. The preparation method according to claim 1, characterized in that, The method of providing bis(3-aminopropyl)-terminated poly(dimethylsiloxane) and isocyanate methacrylate, mixed together, further includes: adding a first solvent; the first solvent is selected from one or more of anhydrous tetrahydrofuran, anhydrous 1,4-dioxane, diethyl ether, dimethylformamide, and dimethyl sulfoxide; the mass concentration of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) in the first solvent is 200 g / L to 600 g / L; The mass ratio of the bis(3-aminopropyl)-terminated poly(dimethylsiloxane) to the isocyanate methacrylate is (5~80):(0.5~15). The reaction temperature of the second reaction is 30℃~80℃, and the reaction time of the second reaction is 1h~10h.

6. The preparation method according to claim 1, characterized in that, The structural formula of the curing agent is shown below: 。 7. The preparation method according to claim 1, characterized in that, The initiator is selected from one or more of benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide; The mass ratio of the resin prepolymer, the curing agent, and the initiator is (10~80):(2~24):(0.1~1). The provision of the initiator, mixed with the resin prepolymer and the curing agent, further includes: adding a second solvent; the second solvent is selected from one or more of benzene, toluene, anhydrous 1,4-dioxane, and methyltetrahydrofuran; the mass ratio of the resin prepolymer to the second solvent is (30~60):(30~70); The curing temperature is 60℃~100℃, and the curing time is 3h~10h.

8. The preparation method according to claim 1, characterized in that, The etching process includes: etching with an etching gas; the etching gas includes a mixture of oxygen and fluorine-containing gas; The radio frequency power of the etching process is 80W~300W, and the etching time is 0.5min~10min.

9. The preparation method according to claim 8, characterized in that, The fluorine-containing gas includes one or more of carbon tetrafluoride, octafluoro-2-butene, and sulfur hexafluoride; The volume ratio of the oxygen to the fluorine-containing gas is (1~8):(1~6).

10. A high wear-resistant door and window material, characterized in that, The high wear-resistant door and window material is prepared by any of the preparation methods described in claims 1-9.

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