Polymer nanometer synthetic ice material and preparation method thereof

Abstract

The application provides a kind of polymer nanometer synthetic ice material and its preparation method, belongs to the technical field of polymer materials;The application enhances the mechanical properties, wear resistance and stability of the material through the double-layer core-shell structure of nano-silicon dioxide and silane coupling agent;Combining the synergistic effect of the disulfide bond of cystamine in dynamic self-repairing prepolymer and the dynamic bond of Schiff base, molecular recombination and self-repairing after damage are realized, and the crosslinking density is increased by the reaction of double amine group and isocyanate, so that the material has excellent toughness, strength and anti-aging performance;In addition, by introducing bisaminopropyl polydimethylsiloxane, perfluorooctyl acrylate and trimethylolpropane triacrylate, the surface energy is synergistically reduced, the sliding performance and stain resistance are enhanced, and the three-dimensional network structure with high crosslinking density further improves the hardness, wear resistance and thermal stability, thereby giving the material excellent comprehensive performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and relates to a polymer nanomaterial for synthesizing ice and its preparation method. Background Technology

[0002] Ice materials, as an important functional material, are widely used in skating rinks, curling, and various ice-related recreational activities. However, traditional real ice rinks face numerous challenges in construction and maintenance, primarily including high construction and maintenance costs, stringent environmental temperature requirements, and significant water consumption. These issues not only increase the economic burden on operators but also, to some extent, limit the popularization and development of ice activities, especially against the backdrop of increasingly pronounced climate change.

[0003] In practical applications, the quality of real ice is easily affected by external environmental factors, especially temperature fluctuations. These fluctuations directly cause changes in the smoothness and hardness of the ice surface, thus affecting the performance of athletes and the experience of participants. For example, in high-temperature environments, the ice surface is prone to softening, deformation, and even water stains, which not only reduces the playability and safety of sports but may also lead to accidents for athletes during competitions. In addition, ice rink maintenance is tedious and requires continuous investment, increasing the complexity and cost of operation.

[0004] With increasing societal emphasis on environmental protection and sustainable development, the development of a high-performance, low-cost, and environmentally friendly synthetic ice material has become an urgent need for the industry. This new material should not only possess performance comparable to traditional real ice but also reduce resource consumption and environmental impact to meet modern society's pursuit of sustainable development.

[0005] While existing synthetic ice materials have addressed some of the problems of real ice, such as reducing water consumption and maintenance costs, they still have significant shortcomings in terms of strength, abrasion resistance, and self-healing capabilities. For example, many current synthetic ice materials are prone to cracking upon impact, and their poor abrasion resistance and short service life make them unsuitable for high-intensity sports activities. Furthermore, the performance of some synthetic materials is not stable enough under extreme temperature conditions, making it difficult to ensure safety and comfort during exercise. Summary of the Invention

[0006] To address the above problems, the present invention aims to provide a polymer nanomaterial for synthesizing ice and its preparation method. In this invention, nano-silica forms a double-layer core-shell structure through a tea polyphenol coating and zirconium dioxide encapsulation, significantly improving the material's mechanical properties, wear resistance, and weather resistance. Simultaneously, surface functionalization with a silane coupling agent enhances the compatibility and bonding force between the filler and the matrix, ensuring the material's long-term stability. The dynamic self-healing prepolymer utilizes the synergistic effect of disulfide bonds and Schiff base dynamic bonds in cystamine molecules to achieve molecular recombination and self-repair after damage. Furthermore, the reaction between diamine groups and isocyanates enhances the material's crosslinking density. Combining the flexibility of polyether segments and the rigidity of isophorone diisocyanate, the material possesses excellent toughness, strength, and anti-aging properties. In addition, the introduction of diaminopropyl polydimethylsiloxane, perfluorooctyl acrylate, and trimethylolpropane triacrylate imparts friction-reducing and wear-resistant properties. The siloxane and perfluoro segments synergistically reduce surface energy, enhancing sliding performance and anti-fouling ability, while the high crosslinking density three-dimensional structure further improves the material's hardness, wear resistance, and thermal stability, enabling it to exhibit excellent comprehensive performance in complex environments.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a method for preparing a polymer nano-synthetic ice material, the method comprising:

[0009] S1: React nano-silica with tea polyphenols to obtain tea polyphenol-coated silica; react it with tetrabutyl zirconate to obtain double-layer coated silica; react the double-layer coated silica with a silane coupling agent to obtain multilayer core-shell structure modified silica;

[0010] S2: Cystamine dihydrochloride was added to an alkaline aqueous solution to obtain a diamine powder; it was then added to N,N-dimethylformamide with polyether diol to obtain dispersion E, which was then added to isophorone diisocyanate solution and reacted. After that, p-methylbenzaldehyde and hexamethylenediamine were added to react and obtain a dynamic self-healing prepolymer.

[0011] S3: Isophorone diisocyanate was added to a toluene dispersion of diaminopropyl polydimethylsiloxane and reacted, followed by the addition of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to obtain a friction-reducing and wear-resistant prepolymer.

[0012] S4: Polytetrafluoroethylene micro powder, antioxidant and light stabilizer are added to polyurethane acrylate matrix, and after uniform dispersion, dynamic self-healing prepolymer is added to obtain the first mixture; polyvinyl alcohol, polyethylene glycol and glycerol are dispersed in ethanol to obtain a dispersion solution, and then added to the first mixture to obtain the second mixture. After uniform dispersion, multilayer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and thermosetting agent are added in sequence and mixed. After thermosetting and curing, polymer nano-synthetic ice material is obtained.

[0013] Specifically, S1: Disperse nano-silica in a tea polyphenol solution to obtain dispersion A, adjust its pH with a buffer solution to obtain reaction solution B, react at room temperature, filter, wash, and dry to obtain tea polyphenol-coated silica; prepare a tea polyphenol-coated silica dispersion, add tetrabutyl zirconate to obtain reaction solution C, react at a constant temperature, filter, wash, and dry to obtain double-layer coated silica; disperse it with a silane coupling agent in anhydrous ethanol aqueous solution to obtain dispersion D, reflux at a constant temperature, filter, wash, and dry to obtain multilayer core-shell structure modified silica;

[0014] S2: Cystamine dihydrochloride was added to an alkaline aqueous solution, stirred, filtered, washed, and dried to obtain diamine powder; it was then added to N,N-dimethylformamide with polyether diol and mixed evenly to obtain dispersion E; it was then added dropwise to isophorone diisocyanate solution to obtain reaction solution F; under an inert atmosphere, under constant temperature reflux, a mixed solution of p-methylbenzaldehyde and hexamethylenediamine was added dropwise to obtain reaction solution G; under constant temperature, after stirring, filtered, and vacuum distilled, a dynamic self-healing prepolymer was obtained.

[0015] S3: Prepare a toluene dispersion of diaminopropyl polydimethylsiloxane. After stirring at a constant temperature under an inert atmosphere, add isophorone diisocyanate to obtain the first reaction solution. After continuing to stir and react, add a mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to obtain the second reaction solution. Stir at a constant temperature, filter, and distill under reduced pressure to obtain the friction-reducing and wear-resistant prepolymer.

[0016] S4: Polytetrafluoroethylene micro powder, antioxidant and light stabilizer are added to polyurethane acrylate matrix, and after uniform dispersion, dynamic self-healing prepolymer is added at constant temperature to obtain the first mixture. Polyvinyl alcohol, polyethylene glycol and glycerol are dispersed in ethanol to obtain a dispersion solution, which is then added to the first mixture to obtain the second mixture. After uniform dispersion, multilayer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and thermosetting agent are added in sequence. After uniform dispersion, a pretreated mixture is obtained. After cooling to room temperature, vacuum defoaming and thermosetting are performed, and then the mixture is left to mature at room temperature to obtain polymer nano-synthetic ice material.

[0017] As a preferred technical solution of the present invention, in S1, the mass ratio of tea polyphenols to nano silica is (0.05-0.1):1, for example, it can be 0.05:1, 0.055:1, 0.06:1, 0.065:1, 0.07:1, 0.075:1, 0.08:1, 0.085:1, 0.09:1, 0.095:1 or 0.1:1, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0018] In some alternative embodiments, the dispersion A is adjusted to pH 8-8.5 with a buffer solution, such as 8, 8.1, 8.2, 8.3, 8.4 or 8.5, but not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0019] In some optional embodiments, the reaction solution B is reacted at room temperature for 8-12 hours, for example, 8 hours, 8.4 hours, 8.8 hours, 9.2 hours, 9.6 hours, 10 hours, 10.4 hours, 10.8 hours, 11.2 hours, 11.6 hours or 12 hours, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0020] In some optional embodiments, the mass fraction of the tea polyphenol-coated silica dispersion is 20-30 wt.%, for example, it can be 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0021] In some optional embodiments, the mass ratio of the tetrabutyl zirconate to the polyphenol-coated silica is (0.2-0.4):1, for example, it can be 0.2:1, 0.22:1, 0.24:1, 0.26:1, 0.28:1, 0.3:1, 0.32:1, 0.34:1, 0.36:1, 0.38:1 or 0.4:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0022] In some optional embodiments, the temperature of the isothermal reaction of the reaction solution C is 30-40°C, for example, it can be 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C or 40°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0023] In some optional embodiments, the reaction time of the reaction solution C at a constant temperature is 2-3 hours, for example, it can be 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0024] In some optional embodiments, the mass ratio of the silane coupling agent to the bilayer coated silica is (0.05-0.1):1, for example, it can be 0.05:1, 0.055:1, 0.06:1, 0.065:1, 0.07:1, 0.075:1, 0.08:1, 0.085:1, 0.09:1, 0.095:1 or 0.1:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0025] In some optional embodiments, the temperature of the dispersion D under isothermal reflux is 60-70°C, for example, it can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C or 70°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0026] In some optional embodiments, the dispersion D isothermal reflux time is 2-3 hours, for example, it can be 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0027] As a preferred technical solution of the present invention, in S2, the pH value of the alkaline aqueous solution is 10-11, for example, it can be 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 or 11, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0028] In some optional embodiments, the molar ratio of the diamine powder to the polyether diol is (0.1-0.3):1, for example, it can be 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, 0.22:1, 0.24:1, 0.26:1, 0.28:1 or 0.2:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0029] In some optional embodiments, the total mass fraction of the diamine powder and polyether diol in the dispersion E is 30-40 wt.%, for example, it can be 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, or 40 wt.%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0030] In some optional embodiments, the isophorone diisocyanate solution has a mass fraction of 20-30 wt.%, for example, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0031] In some optional embodiments, the total molar ratio of the isophorone diisocyanate to the polyether diol and the diamine powder is (1-1.2):1, for example, it can be 0.3:1, 0.32:1, 0.34:1, 0.36:1, 0.38:1, 0.4:1, 0.42:1, 0.44:1, 0.46:1, 0.48:1 or 0.5:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0032] In some optional embodiments, the reaction solution F is refluxed under an inert atmosphere at a temperature of 50-60°C, for example, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0033] In some optional embodiments, the reaction solution F is refluxed at an inert atmosphere for 2-3 hours, for example, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, or 3 hours, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0034] In some optional embodiments, the total mass of p-methylbenzaldehyde and hexamethylenediamine is 5-10% of dispersion E, for example, it can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0035] In some optional embodiments, the mass fraction of the mixed solution of p-tolualdehyde and hexamethylenediamine is 10-20 wt.%, for example, it can be 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, or 20 wt.%, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0036] In some optional embodiments, the temperature of the reaction solution G being stirred at a constant temperature is 40-50°C, for example, it can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0037] In some optional embodiments, the reaction solution G is stirred at a constant temperature for 1-2 hours, for example, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2 hours, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0038] As a preferred embodiment of the present invention, in S3, the mass fraction of the toluene dispersion of diaminopropyl polydimethylsiloxane is 30-40 wt.%, for example, it can be 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, or 40 wt.%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0039] In some optional embodiments, the temperature at which the toluene dispersion of diaminopropyl polydimethylsiloxane is stirred is 50-60°C, for example, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0040] In some optional embodiments, the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is (0.2-0.3):1, for example, it can be 0.2:1, 0.21:1, 0.22:1, 0.23:1, 0.24:1, 0.25:1, 0.26:1, 0.27:1, 0.28:1, 0.29:1 or 0.3:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0041] In some optional embodiments, the first reaction solution is stirred and reacted for 1-2 hours, for example, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2 hours, but not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0042] In some optional embodiments, the mass ratio of 1H,1H-perfluorooctyl acrylate to trimethylolpropane triacrylate is (1-1.5):1, for example, it can be 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1 or 1.5:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0043] In some optional embodiments, the total mass of the 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 30-40% of the mass of the toluene dispersion of diaminopropyl polydimethylsiloxane, for example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0044] In some optional embodiments, the mass fraction of H in the mixed solution of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 20-30 wt.%, for example, it can be 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0045] In some optional embodiments, the temperature at which the second reaction solution is stirred is 40-50°C, for example, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0046] In some optional embodiments, the second reaction solution is stirred at a constant temperature for 2-3 hours, for example, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0047] As a preferred technical solution of the present invention, in S4, the amount of polytetrafluoroethylene micro powder is 0.5-2% of the mass of the polyurethane acrylate matrix, for example, it can be 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9% or 2%, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0048] In some optional embodiments, the amount of antioxidant added is 0.1-0.5% of the mass of the polyurethane acrylate matrix, for example, it can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0049] In some optional embodiments, the amount of light stabilizer is 0.1-0.5% of the mass of the polyurethane acrylate matrix, for example, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0050] In some alternative embodiments, the temperature at which the dynamic self-healing prepolymer is added to the first mixture and stirred is 40-50°C, for example, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0051] In some optional embodiments, the amount of polyvinyl alcohol fed is 1-5% of the mass of the polyurethane acrylate matrix, for example, it can be 1%, 1.4%, 1.8%, 2.2%, 2.6%, 3%, 3.4%, 3.8%, 4.2%, 4.6% or 5%, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0052] In some optional embodiments, the amount of polyethylene glycol added is 1-5% of the mass of the polyurethane acrylate matrix, for example, it can be 1%, 1.4%, 1.8%, 2.2%, 2.6%, 3%, 3.4%, 3.8%, 4.2%, 4.6% or 5%, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0053] In some alternative embodiments, the amount of glycerol added is 0.5-2% of the mass of the polyurethane acrylate matrix, for example, it can be 0.5%, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9% or 2%, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0054] In some alternative embodiments, the thermosetting temperature is 60-80°C, for example, 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C or 80°C, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0055] In some alternative embodiments, the thermosetting time is 2-4 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours or 4 hours, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0056] In some optional embodiments, the room temperature curing time is 20-24 hours, for example, 20 hours, 20.4 hours, 20.8 hours, 21.2 hours, 21.6 hours, 22 hours, 22.4 hours, 22.8 hours, 23.2 hours, 23.6 hours or 24 hours, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0057] Secondly, the present invention provides a polymer nano-synthetic ice material. The polymer nano-synthetic ice material comprises a polyurethane acrylate matrix, a dynamic self-healing prepolymer, a multilayer core-shell modified silica, a friction-reducing and wear-resistant prepolymer, and a thermosetting agent, wherein the mass ratio of the polyurethane acrylate matrix, the dynamic self-healing prepolymer, the multilayer core-shell modified silica, the friction-reducing and wear-resistant prepolymer, and the thermosetting agent is (45-55):(15-25):(10-15):(15-20):(1-2).

[0058] This invention introduces nano-silica as a filler and significantly enhances its functional performance and overall properties in composite materials through multi-step modification. Nano-silica is a common inorganic nanomaterial with excellent physicochemical properties. First, nano-silica has a highly dispersed structure and extremely high specific surface area, which allows it to fully contact the matrix in composite materials, forming a uniform distribution and maximizing its reinforcing effect. Second, the silica surface is rich in hydroxyl groups, giving it tunable surface reactivity and enabling the introduction of various functional groups through chemical modification, greatly expanding its application range in complex systems. Furthermore, nano-silica exhibits good thermal stability and excellent mechanical properties, remaining stable under high temperature or high stress environments. Its high hardness makes it a significant reinforcing agent in composite materials, effectively improving the mechanical, thermal, and wear-resistant properties of the composite material through filling. Therefore, nano-silica is selected as the core reinforcing phase in the composite material of this invention and is key to achieving high-performance materials.

[0059] To further enhance the functionality and compatibility with the matrix of nano-silica, this invention employs a multilayer surface modification strategy. Tea polyphenols are a class of natural polyphenolic compounds containing a large number of phenolic hydroxyl groups, exhibiting excellent chemical activity and antioxidant capacity. The surface of nano-silica is rich in hydroxyl groups, which interact with tea polyphenol molecules through electrostatic interactions, hydrogen bonds, and surface adsorption forces, enabling the tea polyphenols to be uniformly adsorbed onto the surface of the silica particles. When the pH of the system is adjusted to alkaline using a buffer solution, the phenolic hydroxyl groups in the tea polyphenols are partially oxidized, generating quinone structures. These quinone groups then form a uniform tea polyphenol polymer layer on the silica surface through further self-polymerization.

[0060] The polyphenol polymer layer is firmly bonded to the silica surface through hydrogen bonds and covalent bonds, providing reactive sites for subsequent functionalization. Secondly, the polyphenol structure in the tea polyphenol has antioxidant properties, which can effectively inhibit the oxidative degradation of the material during subsequent use. In addition, the coating of tea polyphenols reduces the aggregation between silica particles and improves its dispersion stability in solution.

[0061] Building upon this foundation, tetrabutyl zirconate was further used to coat the tea polyphenol-coated nano-silica, forming a double-layer core-shell structure. Tetrabutyl zirconate generates zirconium alkoxide intermediates during hydrolysis and alcoholysis, which then undergo further polycondensation to form nano-sized zirconium oxide. Because the surface of the tea polyphenol coating layer contains abundant phenolic hydroxyl and quinone groups, these active groups can complex with the zirconium oxide precursor, allowing zirconium oxide to be uniformly deposited on the surface of the tea polyphenol coating layer, thus forming a double-layer coating structure. Zirconia possesses high hardness and rigidity, significantly enhancing the overall mechanical properties of the composite material after deposition on the silica surface. Secondly, the high hardness and low coefficient of friction of zirconium oxide effectively reduce wear during friction. Simultaneously, zirconium oxide exhibits excellent thermal stability, significantly improving the durability of modified silica under high-temperature conditions. Furthermore, the chemical inertness and UV resistance of zirconium oxide enhance the environmental stability of the material, mitigating performance degradation caused by photoaging and chemical corrosion during long-term use.

[0062] To further enhance the interfacial bonding between the double-layer coated nano-silica and the matrix, this invention employs a silane coupling agent to functionalize its surface. Silane coupling agents are molecules possessing both inorganic and organic functional groups, and their compatible design allows them to bridge inorganic fillers with organic matrices. Specifically, the siloxane groups in the silane coupling agent molecule undergo a condensation reaction with the hydroxyl groups on the surface of the nano-silica, generating stable Si-O-Si chemical bonds. Simultaneously, the organic functional groups in the silane coupling agent molecule are exposed on the filler surface, enabling further chemical reactions with the organic matrix or the formation of hydrogen bonds. This bifunctional structure allows the double-layer coated nano-silica to form a strong interfacial bond with the organic matrix, significantly improving the interfacial strength and compatibility of the composite material. Through silane coupling agent modification, a surface-functionalized multilayer core-shell structured nano-silica filler is ultimately obtained. In composite materials, this filler not only provides excellent reinforcement but also effectively prevents filler aggregation and detachment, thereby ensuring the long-term stability and durability of the material.

[0063] This invention introduces a dynamic self-healing prepolymer, which provides the material with a balance of self-healing function, flexibility and mechanical strength, as well as excellent anti-aging properties and heat resistance.

[0064] Cystamine is the core component of the dynamic self-healing prepolymer of this invention. Its molecular structure contains two amine groups and one disulfide bond, endowing it with unique chemical reactivity and dynamic function. Under alkaline conditions, the hydrochloride anion of cystamine dihydrochloride is neutralized, releasing the cystamine molecule with a diamine group. This pretreatment step not only ensures the chemical activity of cystamine but also provides free amine sites for subsequent reactions. The diamine group in cystamine can undergo a classic addition reaction with the isocyanate group to generate a urea bond with high stability and strong mechanical properties. Simultaneously, the disulfide bond in the cystamine molecule is not broken during the reaction.

[0065] The dynamic properties of disulfide bonds are the core chemical basis for the self-healing function of the materials in this invention. Under the influence of external forces or environmental stimuli, disulfide bonds can undergo reversible breakage, generating active sulfur free radicals. After the stress is relieved or the stimulus is removed, these sulfur free radicals can recombine, restoring the disulfide bond form. This dynamic breakage-reorganization mechanism ensures that the material can rapidly repair its structure through molecular rearrangement after microcracks or damage occur, thereby extending the material's service life. This characteristic is particularly important for wear-resistant materials, as it can compensate for surface damage and slow down material aging and performance degradation.

[0066] In addition to the unique function of dynamic disulfide bonds, the diamine groups of cystamine also participate in the construction of polyurethane segments. The urea bonds formed by the reaction with isocyanate groups not only increase the crosslinking density of the material but also enhance its mechanical properties, enabling it to exhibit excellent strength and rigidity under high stress or complex environments. This molecular design allows the dynamic self-healing prepolymer to maintain its self-healing function while possessing both high strength and high stability.

[0067] To further optimize the performance of dynamic self-healing materials, this invention introduces polyether diol and isophorone diisocyanate, and generates polyurethane segments with a balance of flexibility and rigidity through their reaction.

[0068] The hydroxyl groups in polyether diol molecules can react with isocyanate groups to form soft segments in the polyurethane chain. These polyether segments exhibit high molecular chain flexibility, endowing the material with excellent low-temperature performance and toughness. When the material is subjected to external force or friction, the flexible polyether segments can absorb some of the stress through the stretching and bending of the molecular chain, dispersing the external force over a larger molecular range, thereby effectively reducing material wear. This stress relief mechanism significantly improves the service life of the material under extreme conditions such as high-speed friction or impact.

[0069] The isocyanate groups in isophorone diisocyanate react with polyether diols to form hard segments in the polyurethane chain. These hard segments provide rigidity and heat resistance, enhancing the overall mechanical properties of the material. Furthermore, the isophorone diisocyanate molecule exhibits significant steric hindrance, a structural feature that not only improves the material's thermal stability but also enhances its anti-aging properties. This means that the material can effectively resist thermal degradation and environmental aging under high-temperature or long-term use conditions, maintaining its performance stability.

[0070] Through the synergistic effect of polyether segments and isophorone diisocyanate segments, the dynamic self-healing prepolymer of this invention achieves a balance of rigidity and flexibility. The material exhibits both flexibility and toughness under dynamic conditions while maintaining high strength and stability, making it particularly suitable for use in complex environments.

[0071] To further improve the dynamic properties and stability of the material, this invention also introduces Schiff base dynamic bonds. Schiff base bonds are formed through the amine-aldehyde condensation reaction between p-methylbenzaldehyde and hexamethylenediamine. Schiff base bonds are dynamic chemical bonds with the ability to reversibly break and reform under external stimuli. This dynamic characteristic complements the dynamic behavior of disulfide bonds, providing the material with a more complex and flexible self-healing capability. When the material is damaged, Schiff base bonds can break and recombine rapidly, repairing damaged molecular chain segments and further enhancing the material's dynamic self-healing ability.

[0072] Meanwhile, the aromatic ring structure in the p-methylbenzaldehyde molecule provides a rigid framework for the material. The introduction of the aromatic ring significantly improves the chemical stability and antioxidant properties of the chain segments, while also increasing the material's hardness and heat resistance. This allows the material to maintain good mechanical properties under high temperature and high strength conditions.

[0073] This invention introduces diaminopropyl polydimethylsiloxane and combines it with other functional modifiers to construct a high-performance friction-reducing and wear-resistant system. Diaminopropyl polydimethylsiloxane is a multifunctional compound containing siloxane segments and a diamine structure. Its molecule contains siloxane segments and amine groups. The amine groups can undergo addition reactions with isocyanate groups to form urea bonds. The siloxane segments are integrated into the polyurethane segments to form a network structure that combines flexibility and rigidity. The siloxane segments have extremely low surface energy and excellent molecular flexibility, which endows the material with significant friction-reducing properties. Its low surface energy reduces the coefficient of friction between the material and the external environment, thereby significantly improving the sliding performance of the material. At the same time, the molecular flexibility can absorb external forces and disperse stress during friction, effectively reducing the surface wear of the material. This self-lubricating property also improves the wear resistance of the material, making it exhibit better stability and a longer service life in long-term use.

[0074] To further optimize the surface properties and functional characteristics of the material, this invention also introduces 1H,1H-perfluorooctyl acrylate, integrating perfluorinated segments into the material network through a chemical reaction. These perfluorinated segments possess extremely low surface energy, forming a superhydrophobic outer layer on the material surface, significantly reducing the surface energy and further improving the sliding performance of the ice material. Furthermore, the introduction of perfluorinated segments gives the material excellent hydrophobicity and antifouling properties, not only reducing the interaction between water molecules and the material surface but also effectively preventing the adhesion of contaminants. The chemical inertness and environmental stability of the perfluorinated segments further enhance the material's weather resistance, enabling it to exhibit good performance stability in complex environments.

[0075] To enhance the overall mechanical and wear resistance of the material, this invention specifically introduces trimethylolpropane triacrylate (TMT) as a crosslinking agent. The TMT molecule contains three acrylate groups, which can chemically react with the material's molecular chains to form a highly crosslinked three-dimensional network structure. This high crosslinking density significantly enhances the material's hardness and rigidity, giving it stronger resistance to deformation under high stress environments. Simultaneously, it restricts the mobility of the molecular chains, thereby reducing chain breakage and wear during friction, further improving the material's wear resistance. Furthermore, the three-dimensional network structure formed by TMT crosslinking significantly improves the material's thermal stability and anti-aging properties, enabling it to maintain structural integrity and performance stability under high-temperature or long-term use conditions.

[0076] Synergistic effects also exist in this invention. The introduction of the dynamic self-healing prepolymer primarily endows the material with self-healing capabilities through the dynamic behavior of disulfide bonds and Schiff base bonds in cystamine. Disulfide bonds can break and recombine under external forces or environmental stimuli, while Schiff base bonds can also undergo dynamic breakage and recombination under specific conditions. The synergistic effect of these two dynamic bonds enables the material to rapidly repair itself after microcracks or surface damage occur, and restore its mechanical properties.

[0077] Siloxane segments possess low surface energy and high flexibility, forming a lubricating and flexible molecular layer on the material surface, thereby reducing the coefficient of friction and enhancing sliding performance. Perfluorinated segments further reduce the surface energy of the material through their extremely low surface energy, while also imparting excellent hydrophobicity and antifouling properties. The synergistic effect of the two segments results in a material surface that simultaneously possesses an extremely low coefficient of friction and excellent hydrophobic and antifouling properties.

[0078] The introduction of trimethylolpropane triacrylate increases the crosslinking density of the material, thereby enhancing its mechanical properties. This high crosslinking density, combined with the flexibility of dynamic bonds, creates a synergistic effect: under high stress or high friction environments, the high crosslinking density restricts excessive movement of molecular chains, enhancing the material's resistance to deformation and wear; simultaneously, the breaking and recombination behavior of dynamic bonds provides the material with molecular-level stress release and structural repair capabilities. This synergistic effect enables the material to maintain high strength and hardness while possessing dynamic self-healing capabilities, thus exhibiting excellent durability and stability during long-term use.

[0079] In terms of sliding properties, the siloxane segments provide molecular flexibility and lubricity, reducing the coefficient of friction; the extremely low surface energy of the perfluorinated segments further reduces sliding friction, while their hydrophobic properties reduce the adhesion of water or moisture to the surface of the ice material; and the nano-silica, after being modified with tea polyphenols and zirconium dioxide coating, has enhanced hardness and interfacial bonding, effectively reducing wear during sliding. These components work together to enable the material to exhibit lower frictional resistance, higher wear resistance, and longer service life in complex sliding environments.

[0080] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0081] This invention significantly improves the performance of composite materials by introducing nano-silica through multi-step modification. Nano-silica, with its high specific surface area and surface hydroxyl groups, provides excellent reinforcement, enhancing the material's mechanical, thermal stability, and wear resistance. The self-polymerization effect of the tea polyphenol coating strengthens the bond between the filler and the matrix, and the introduction of a zirconium dioxide coating layer forms a double-core-shell structure, further improving hardness, wear resistance, and weather resistance. Finally, the surface functionalization of the silane coupling agent optimizes interfacial compatibility and bonding force, ensuring uniform filler distribution and preventing detachment, thereby endowing the composite material with excellent comprehensive performance and long-term stability.

[0082] This invention introduces a dynamic self-healing prepolymer. The disulfide bonds in the cystamine molecule endow the material with a dynamic fracture-recombination self-healing ability. The diamine group reacts with the isocyanate to generate urea bonds, enhancing the crosslinking density and mechanical properties. The polyether segment provides molecular flexibility and toughness, absorbing stress and reducing wear, while the isophorone diisocyanate segment provides rigidity and heat resistance, enhancing the material's anti-aging ability. The Schiff base dynamic bond further enhances the material's self-healing performance. Its reversible properties synergistically work with the disulfide bonds to provide a flexible molecular repair mechanism for the material. At the same time, the aromatic ring structure of p-methylbenzaldehyde enhances the material's rigid framework and antioxidant properties.

[0083] This invention constructs a high-performance friction-reducing and wear-resistant system by introducing diaminopropyl polydimethylsiloxane, 1H,1H-perfluorooctyl acrylate, and trimethylolpropane triacrylate. The siloxane segments and amino groups in diaminopropyl polydimethylsiloxane react with isocyanate to form urea bonds, which are then integrated into the polyurethane network, endowing the material with low surface energy and high flexibility, thereby significantly reducing the coefficient of friction and improving sliding performance. Simultaneously, it reduces wear by dispersing stress, extending service life. Perfluorooctyl acrylate further introduces perfluorinated segments, forming a superhydrophobic outer layer, reducing surface energy and enhancing stain resistance and weather resistance, enabling the material to exhibit excellent stability in complex environments. Trimethylolpropane triacrylate acts as a crosslinking agent, forming a highly crosslinked three-dimensional network structure, significantly enhancing hardness, rigidity, and anti-aging properties, allowing the material to maintain stable structure and performance under high temperature and long-term use conditions. Attached Figure Description

[0084] Figure 1 A flowchart illustrating the preparation method of polymer nano-synthetic ice material provided in this embodiment of the invention. Detailed Implementation

[0085] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include those that make any obvious substitutions and modifications to the embodiments described herein.

[0086] The chemical reagents used in the embodiments and comparative examples of this invention are all commercially available products and have not undergone further purification or processing.

[0087] Example 1

[0088] This embodiment provides a polymer nanomaterial for synthesizing ice and its preparation method;

[0089] See Figure 1 The preparation method of polymer nanomaterials for synthesizing ice specifically includes the following steps:

[0090] S1: Dispersion A was obtained by dispersing nano-silica in a tea polyphenol solution, wherein the mass ratio of tea polyphenol to silica was 0.08:1. The pH was adjusted to 8.2 with a buffer solution to obtain reaction solution B. After reacting at room temperature for 8 hours, the solution was filtered, washed, and dried to obtain tea polyphenol-coated silica. A dispersion of tea polyphenol-coated silica with a mass fraction of 20 wt.% was prepared, and tetrabutyl zirconate was added dropwise to obtain reaction solution C, wherein the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica was 0.3:1. The solution was reacted at a constant temperature of 30℃ for 2.2 hours, and then filtered, washed, and dried to obtain double-layer coated silica. The solution was then dispersed with a silane coupling agent in anhydrous ethanol aqueous solution to obtain dispersion D, wherein the mass ratio of silane coupling agent to double-layer coated silica was 0.07:1. The solution was refluxed at a constant temperature of 60℃ for 2 hours, and then filtered, washed, and dried to obtain multilayer core-shell structure modified silica.

[0091] S2: Cystamine dihydrochloride was added to an alkaline aqueous solution with a pH of 10, stirred, filtered, washed, and dried to obtain diamine powder. This powder was then added to N,N-dimethylformamide along with polyether diol and mixed uniformly to obtain dispersion E, where the molar ratio of diamine powder to polyether diol was 0.2:1, and the total mass fraction of diamine powder and polyether diol in dispersion E was 30.wt%. This dispersion was then added dropwise to a 20 wt.% isophorone diisocyanate solution to obtain reaction solution F. The total molar ratio of isocyanate to polyether diol and diamine powder is 1.1:1. After reflux at 50℃ for 2.5 h under an inert atmosphere, a mixed solution of p-tolualdehyde and hexamethylenediamine is added dropwise to obtain reaction solution G, in which the mass ratio of p-tolualdehyde to hexamethylenediamine is 1:1, the total mass of p-tolualdehyde and hexamethylenediamine is 8% of that of dispersion E, and the mass fraction of the mixed solution of p-tolualdehyde and hexamethylenediamine is 15 wt.%. After stirring at 40℃ for 1.5 h, the mixture is filtered and distilled under reduced pressure to obtain a dynamic self-healing prepolymer.

[0092] S3: Prepare a toluene dispersion of diaminopropyl polydimethylsiloxane with a mass fraction of 40 wt.%. After stirring at a constant temperature of 50°C under an inert atmosphere, add isophorone diisocyanate to obtain the first reaction solution, wherein the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is 0.25:1. Continue stirring and reacting for 1 h, then add dropwise a mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate with a mass fraction of 25 wt.% to obtain the second reaction solution, wherein the mass ratio of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 1.2:1, and the total mass of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 35% of the mass of the toluene dispersion of diaminopropyl polydimethylsiloxane. Stir at a constant temperature of 40°C for 2 h, filter, and distill under reduced pressure to obtain a friction-reducing and wear-resistant prepolymer.

[0093] S4: Polytetrafluoroethylene (PTFE) micropowder, antioxidant 1010, and UV absorber UV-531 are added to a polyurethane acrylate matrix. The amount of PTFE micropowder is 0.5% of the mass of the polyurethane acrylate matrix, the amount of antioxidant is 0.2% of the mass of the polyurethane acrylate matrix, and the amount of light stabilizer is 0.3% of the mass of the polyurethane acrylate matrix. After uniform dispersion, a dynamic self-healing prepolymer is added at a constant temperature of 40°C to obtain a first mixture. Polyvinyl alcohol, polyethylene glycol, and glycerol are dispersed in ethanol to obtain a dispersion solution, which is then added to the first mixture to obtain a second mixture. The amount of polyvinyl alcohol is 3% of the mass of the polyurethane acrylate matrix, the amount of polyethylene glycol is 2% of the mass of the polyurethane acrylate matrix, and the amount of glycerol is 1% of the mass of the polyurethane acrylate matrix.

[0094] After being evenly dispersed, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and N,N-dimethylbenzylamine were added sequentially. After being evenly dispersed, a pretreated mixture was obtained. After cooling to room temperature, the mixture was defoamed under vacuum, heat-cured at 60°C for 2 hours, and then left at room temperature for 20 hours to mature, resulting in a polymer nano-synthetic ice material. The mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and thermosetting agent was 50:20:12:17:1.8.

[0095] Example 2

[0096] This embodiment provides a polymer nano-synthetic ice material and its preparation method. The preparation method of the polymer nano-synthetic ice material specifically includes the following steps:

[0097] S1: Dispersion A was obtained by dispersing nano-silica in a tea polyphenol solution, wherein the mass ratio of tea polyphenol to silica was 0.05:1. The pH was adjusted to 8 with a buffer solution to obtain reaction solution B. After reacting at room temperature for 10 h, the solution was filtered, washed, and dried to obtain tea polyphenol-coated silica. A dispersion of tea polyphenol-coated silica with a mass fraction of 25 wt.% was prepared, and tetrabutyl zirconate was added dropwise to obtain reaction solution C, wherein the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica was 0.2:1. The solution was reacted at a constant temperature of 35℃ for 2.5 h, and then filtered, washed, and dried to obtain double-layer coated silica. The solution was then dispersed with a silane coupling agent in anhydrous ethanol aqueous solution to obtain dispersion D, wherein the mass ratio of silane coupling agent to double-layer coated silica was 0.08:1. The solution was refluxed at a constant temperature of 65℃ for 2.8 h, and then filtered, washed, and dried to obtain multilayer core-shell structure modified silica.

[0098] S2: Cystamine dihydrochloride was added to an alkaline aqueous solution with a pH of 10.5, stirred, filtered, washed, and dried to obtain diamine powder. This powder was then added to N,N-dimethylformamide along with polyether diol and mixed uniformly to obtain dispersion E, where the molar ratio of diamine powder to polyether diol was 0.1:1, and the total mass fraction of diamine powder and polyether diol in dispersion E was 35 wt.%. This dispersion was then added dropwise to a 25 wt.% isophorone diisocyanate solution to obtain reaction solution F. The total molar ratio of phorone diisocyanate to polyether diol and diamine powder is 1:1. After reflux at 55°C for 2 hours under an inert atmosphere, a mixed solution of p-tolualdehyde and hexamethylenediamine is added dropwise to obtain reaction solution G, in which the mass ratio of p-tolualdehyde to hexamethylenediamine is 1:1, the total mass of p-tolualdehyde and hexamethylenediamine is 5% of that of dispersion E, and the mass fraction of the mixed solution of p-tolualdehyde and hexamethylenediamine is 10 wt.%. After stirring at 48°C for 1 hour, the mixture is filtered and distilled under reduced pressure to obtain a dynamic self-healing prepolymer.

[0099] S3: Prepare a toluene dispersion of diaminopropyl polydimethylsiloxane with a mass fraction of 30 wt.%. After stirring at a constant temperature of 60°C under an inert atmosphere, add isophorone diisocyanate to obtain the first reaction solution, wherein the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is 0.28:1. Continue stirring and reacting for 1.5 h, then add dropwise a mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate with a mass fraction of 28 wt.% to obtain the second reaction solution, wherein the mass ratio of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 1.5:1, and the total mass of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 30% of the mass of the toluene dispersion of diaminopropyl polydimethylsiloxane. Stir at a constant temperature of 48°C for 2.8 h, filter, and distill under reduced pressure to obtain a friction-reducing and wear-resistant prepolymer.

[0100] S4: Polytetrafluoroethylene (PTFE) micropowder, antioxidant 1010, and UV absorber UV-531 are added to a polyurethane acrylate matrix. The amount of PTFE micropowder is 1% of the mass of the polyurethane acrylate matrix, the amount of antioxidant is 0.1% of the mass of the polyurethane acrylate matrix, and the amount of light stabilizer is 0.1% of the mass of the polyurethane acrylate matrix. After uniform dispersion, a dynamic self-healing prepolymer is added at a constant temperature of 45°C to obtain a first mixture. Polyvinyl alcohol, polyethylene glycol, and glycerol are dispersed in ethanol to obtain a dispersion solution, which is then added to the first mixture to obtain a second mixture. The amount of polyvinyl alcohol is 4% of the mass of the polyurethane acrylate matrix, the amount of polyethylene glycol is 3% of the mass of the polyurethane acrylate matrix, and the amount of glycerol is 0.5% of the mass of the polyurethane acrylate matrix.

[0101] After being evenly dispersed, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and benzoyl peroxide were added sequentially. After being evenly dispersed, a pretreated mixture was obtained. After cooling to room temperature, the mixture was defoamed under vacuum, heat-cured at 70°C for 3 hours, and then left at room temperature for 22 hours to mature, resulting in a polymer nano-synthetic ice material. The mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and heat-curing agent was 45:22:15:20:1.5.

[0102] Example 3

[0103] This embodiment provides a polymer nano-synthetic ice material and its preparation method. The preparation method of the polymer nano-synthetic ice material specifically includes the following steps:

[0104] S1: Dispersion A was obtained by dispersing nano-silica in a tea polyphenol solution, wherein the mass ratio of tea polyphenol to silica was 0.075:1. The pH was adjusted to 8.4 with a buffer solution to obtain reaction solution B. After reacting at room temperature for 11 h, the solution was filtered, washed, and dried to obtain tea polyphenol-coated silica. A dispersion of tea polyphenol-coated silica with a mass fraction of 28 wt.% was prepared, and tetrabutyl zirconate was added dropwise to obtain reaction solution C, wherein the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica was 0.35:1. The solution was reacted at a constant temperature of 38℃ for 2 h, and then filtered, washed, and dried to obtain double-layer coated silica. The solution was then dispersed with a silane coupling agent in anhydrous ethanol aqueous solution to obtain dispersion D, wherein the mass ratio of silane coupling agent to double-layer coated silica was 0.05:1. The solution was refluxed at a constant temperature of 68℃ for 2.6 h, and then filtered, washed, and dried to obtain multilayer core-shell structure modified silica.

[0105] S2: Cystamine dihydrochloride was added to an alkaline aqueous solution with a pH of 10.7, stirred, filtered, washed, and dried to obtain diamine powder. This powder was then added to N,N-dimethylformamide along with polyether diol and mixed uniformly to obtain dispersion E, where the molar ratio of diamine powder to polyether diol was 0.3:1, and the total mass fraction of diamine powder and polyether diol in dispersion E was 38 wt.%. This dispersion was then added dropwise to a 28 wt.% isophorone diisocyanate solution to obtain reaction solution F, where isophorone... The total molar ratio of diisocyanate to polyether diol and diamine powder is 1.2:1. After reflux at 58°C for 2.8 h under an inert atmosphere, a mixed solution of p-tolualdehyde and hexamethylenediamine is added dropwise to obtain reaction solution G, in which the mass ratio of p-tolualdehyde to hexamethylenediamine is 1:1, the total mass of p-tolualdehyde and hexamethylenediamine is 7% of that of dispersion E, and the mass fraction of the mixed solution of p-tolualdehyde and hexamethylenediamine is 18 wt.%. After stirring at 45°C for 2 h, the mixture is filtered and distilled under reduced pressure to obtain a dynamic self-healing prepolymer.

[0106] S3: Prepare a toluene dispersion of diaminopropyl polydimethylsiloxane with a mass fraction of 35 wt.%. After stirring at a constant temperature of 55°C under an inert atmosphere, add isophorone diisocyanate to obtain the first reaction solution, wherein the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is 0.2:1. Continue stirring and reacting for 1.8 h, then add dropwise a mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate with a mass fraction of 20 wt.% to obtain the second reaction solution, wherein the mass ratio of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 1:1, and the total mass of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 40% of the mass of the toluene dispersion of diaminopropyl polydimethylsiloxane. Stir at a constant temperature of 50°C for 2.5 h, filter, and distill under reduced pressure to obtain a friction-reducing and wear-resistant prepolymer.

[0107] S4: Polytetrafluoroethylene (PTFE) micropowder, antioxidant 1010, and UV absorber UV-531 are added to a polyurethane acrylate matrix, wherein the amount of PTFE micropowder is 1.5% of the mass of the polyurethane acrylate matrix, the amount of antioxidant is 0.4% of the mass of the polyurethane acrylate matrix, and the amount of light stabilizer is 0.5% of the mass of the polyurethane acrylate matrix. After uniform dispersion, a dynamic self-healing prepolymer is added at a constant temperature of 48°C to obtain a first mixture. Polyvinyl alcohol, polyethylene glycol, and glycerol are dispersed in ethanol to obtain a dispersion solution, which is then added to the first mixture to obtain a second mixture, wherein the amount of polyvinyl alcohol is 1% of the mass of the polyurethane acrylate matrix, the amount of polyethylene glycol is 5% of the mass of the polyurethane acrylate matrix, and the amount of glycerol is 2% of the mass of the polyurethane acrylate matrix.

[0108] After being evenly dispersed, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and N,N-dimethylbenzylamine were added sequentially. After being evenly dispersed, a pretreated mixture was obtained. After cooling to room temperature, the mixture was defoamed under vacuum, heat-cured at 75°C for 3.5 hours, and then left at room temperature for 23 hours to mature, resulting in a polymer nano-synthetic ice material. The mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and thermosetting agent was 52:15:10:18:2.

[0109] Example 4

[0110] This embodiment provides a polymer nano-synthetic ice material and its preparation method. The preparation method of the polymer nano-synthetic ice material specifically includes the following steps:

[0111] S1: Dispersion A was obtained by dispersing nano-silica in a tea polyphenol solution, wherein the mass ratio of tea polyphenol to silica was 0.1:1. The pH was adjusted to 8.5 with a buffer solution to obtain reaction solution B. After reacting at room temperature for 12 h, the solution was filtered, washed, and dried to obtain tea polyphenol-coated silica. A dispersion of tea polyphenol-coated silica with a mass fraction of 30 wt.% was prepared, and tetrabutyl zirconate was added dropwise to obtain reaction solution C, wherein the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica was 0.4:1. The solution was reacted at a constant temperature of 40℃ for 3 h, and then filtered, washed, and dried to obtain double-layer coated silica. The solution was then dispersed with a silane coupling agent in anhydrous ethanol aqueous solution to obtain dispersion D, wherein the mass ratio of silane coupling agent to double-layer coated silica was 0.1:1. The solution was refluxed at a constant temperature of 70℃ for 3 h, and then filtered, washed, and dried to obtain multilayer core-shell structure modified silica.

[0112] S2: Cystamine dihydrochloride was added to an alkaline aqueous solution with a pH of 11, stirred, filtered, washed, and dried to obtain diamine powder. This powder was then added to N,N-dimethylformamide along with polyether diol and mixed uniformly to obtain dispersion E, where the molar ratio of diamine powder to polyether diol was 0.26:1, and the total mass fraction of diamine powder and polyether diol in dispersion E was 40 wt.%. This dispersion was then added dropwise to a 30 wt.% isophorone diisocyanate solution to obtain reaction solution F. The total molar ratio of isocyanate to polyether diol and diamine powder was 1.12:1. After reflux at 60°C for 3 hours under an inert atmosphere, a mixed solution of p-tolualdehyde and hexamethylenediamine was added dropwise to obtain reaction solution G, in which the mass ratio of p-tolualdehyde to hexamethylenediamine was 1:1, the total mass of p-tolualdehyde and hexamethylenediamine was 10% of that of dispersion E, and the mass fraction of the mixed solution of p-tolualdehyde and hexamethylenediamine was 20 wt.%. After stirring at 50°C for 1.8 hours, the mixture was filtered and distilled under reduced pressure to obtain a dynamic self-healing prepolymer.

[0113] S3: Prepare a toluene dispersion of diaminopropyl polydimethylsiloxane with a mass fraction of 38 wt.%. After stirring at a constant temperature of 58°C under an inert atmosphere, add isophorone diisocyanate to obtain the first reaction solution, wherein the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is 0.3:1. Continue stirring and reacting for 2 hours, then add dropwise a mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate with a mass fraction of 30 wt.% to obtain the second reaction solution, wherein the mass ratio of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 1.3:1, and the total mass of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 38% of the mass of the toluene dispersion of diaminopropyl polydimethylsiloxane. Stir at a constant temperature of 45°C for 3 hours, filter, and distill under reduced pressure to obtain a friction-reducing and wear-resistant prepolymer.

[0114] S4: Polytetrafluoroethylene (PTFE) micropowder, antioxidant 1010, and UV absorber UV-531 are added to a polyurethane acrylate matrix, wherein the amount of PTFE micropowder is 2% of the mass of the polyurethane acrylate matrix, the amount of antioxidant is 0.5% of the mass of the polyurethane acrylate matrix, and the amount of light stabilizer is 0.4% of the mass of the polyurethane acrylate matrix. After uniform dispersion, a dynamic self-healing prepolymer is added at a constant temperature of 50°C to obtain a first mixture. Polyvinyl alcohol, polyethylene glycol, and glycerol are dispersed in ethanol to obtain a dispersion solution, which is then added to the first mixture to obtain a second mixture, wherein the amount of polyvinyl alcohol is 5% of the mass of the polyurethane acrylate matrix, the amount of polyethylene glycol is 1% of the mass of the polyurethane acrylate matrix, and the amount of glycerol is 1.5% of the mass of the polyurethane acrylate matrix.

[0115] After being evenly dispersed, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and benzoyl peroxide were added sequentially. After being evenly dispersed, a pretreated mixture was obtained. After cooling to room temperature, the mixture was defoamed under vacuum, heat-cured at 80°C for 4 hours, and then left at room temperature for 24 hours to mature, resulting in a polymer nano-synthetic ice material. The mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer, and thermosetting agent was 55:25:14:15:1.

[0116] Comparative Example 1

[0117] This comparative example provides a polymer nano-synthetic ice material. The difference between this method and the preparation method of the polymer nano-synthetic ice material disclosed in Example 1 is that in S3, the mass ratio of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 2:1. Other operating steps and process parameters are exactly the same as in Example 1.

[0118] Comparative Example 2

[0119] This comparative example provides a polymer nano-synthetic ice material. The difference between this method and the preparation method of the polymer nano-synthetic ice material disclosed in Example 1 is that in S3, the mass ratio of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 0.5:1. Other operating steps and process parameters are exactly the same as in Example 1.

[0120] Comparative Example 3

[0121] This comparative example provides a polymer nano-synthetic ice material. The difference between this method and the preparation method of the polymer nano-synthetic ice material disclosed in Example 1 is that, in S1, the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.8:1. Other operating steps and process parameters are exactly the same as in Example 1.

[0122] Comparative Example 4

[0123] This comparative example provides a polymer nano-synthetic ice material. The difference between this method and the preparation method of the polymer nano-synthetic ice material disclosed in Example 1 is that, in S1, the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.1:1. Other operating steps and process parameters are exactly the same as in Example 1.

[0124] Comparative Example 5

[0125] This comparative example provides a polymer nano-synthetic ice material. The difference between this method and the preparation method of the polymer nano-synthetic ice material disclosed in Example 1 is that in S4, the mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer and thermosetting agent is 50:30:12:17:1.8. Other operating steps and process parameters are exactly the same as in Example 1.

[0126] Comparative Example 6

[0127] This comparative example provides a polymer nano-synthetic ice material. The difference between this method and the preparation method of the polymer nano-synthetic ice material disclosed in Example 1 is that in S4, the mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer and thermosetting agent is 50:10:12:17:1.8. Other operating steps and process parameters are exactly the same as in Example 1.

[0128] The performance of the polymer nano-synthetic ice materials of Examples 1-4 and Comparative Examples 1-6 was tested, and the specific process is as follows:

[0129] The sliding friction coefficient of polymer nano-synthetic ice materials was tested according to GB / T 10006-2021.

[0130] The hardness of polymer nano-synthetic ice materials was tested according to GB / T 531.1-2008;

[0131] The tensile strength of the polymer nano-synthetic ice material in its initial state and its tensile strength after self-healing (the ice material was cut and the fracture surface was contacted and allowed to heal at room temperature for 24 hours) were tested using a universal tensile testing machine.

[0132] Self-healing efficiency = [stress after self-healing / stress in the initial state] × 100%.

[0133] The test results are shown in Table 1.

[0134] Table 1: Performance test results of polymer nanomaterials synthesized into ice in Examples 1-4 and Comparative Examples 1-6

[0135]

[0136] The test results from Example 1 and Comparative Examples 1 and 2 show that when the mass ratio of 1H,1H-perfluorooctyl acrylate to trimethylolpropane triacrylate is too high, the excessive fluorine component accumulates on the material surface to form a dense low surface energy layer, resulting in a decrease in the sliding friction coefficient to 0.018. Simultaneously, the excessive flexible segments of the fluorine component damage the internal network structure of the material, causing the Shore hardness to decrease to 68 HD and the tensile strength to decrease to 11.2 MPa. Furthermore, the excessive fluorine component interferes with the formation and recombination of dynamic bonds, resulting in a self-healing rate of only 80.4%. When the mass ratio is too low, insufficient surface fluorination leads to incomplete lubrication layer formation, increasing the sliding friction coefficient to 0.038. Although the increase in rigid crosslinking points raises the Shore hardness to 85 HD and the tensile strength to 14.2, the material becomes brittle overall, its self-healing performance decreases, and the repair rate is only 84.5%.

[0137] The test results from Example 1 and Comparative Examples 3 and 4 show that when the mass ratio of tetrabutyl zirconate to polyphenol-coated silica is too high, excessive tetrabutyl zirconate forms a thick coating on the silica surface, causing agglomeration between nanoparticles, disrupting the material's uniformity, and increasing the sliding friction coefficient to 0.032. Although the inorganic bonding reinforcement increases the Shore hardness to 83HD, internal stress concentration causes the tensile strength to decrease to 12.3MPa. Excessive inorganic phase coating restricts the movement of molecular chains, leading to a decrease in self-healing performance. When the mass ratio is too low, the tetrabutyl zirconate coating layer is too thin to effectively improve the interfacial compatibility between nanoparticles and the matrix, resulting in insufficient interfacial bonding. The Shore hardness of the material decreases to 73HD, and the tensile strength decreases to 12.2MPa. Due to the moderate degree of surface modification, the impact on the sliding friction coefficient and self-healing performance is relatively small.

[0138] The test results from Example 1 and Comparative Examples 5 and 6 show that when the amount of dynamic self-healing prepolymer added is too high, the excessive Schiff base bonds and hydrogen bonds in the dynamic self-healing prepolymer increase the mobility of the material, resulting in a loose network structure and a sliding friction coefficient of 0.033; the increased soft segment content reduces the overall rigidity of the material, causing the Shore hardness to drop to 72HD; the excessive dynamic bonds reduce the structural stability of the material, causing the tensile strength to drop to 11.5MPa; however, the increased dynamic bond content provides more self-healing active sites, significantly improving the self-healing performance, with a repair rate of 94.8%; when the amount added is too low, the insufficient dynamic bond content causes the material network structure to tend to be fixed. Although the Shore hardness increases to 85HD and the tensile strength increases to 14.8MPa, the low reversible dynamic bond density makes the material lack sufficient self-healing ability, with a repair rate of only 75.0%; the sliding friction coefficient remains at 0.026.

[0139] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a polymer nanomaterial for synthesizing ice, characterized in that, The preparation method includes: S1: React nano-silica with tea polyphenols to obtain tea polyphenol-coated silica; react it with tetrabutyl zirconate to obtain double-layer coated silica; react the double-layer coated silica with a silane coupling agent to obtain multilayer core-shell structure modified silica; S2: Cystamine dihydrochloride was added to an alkaline aqueous solution to obtain a diamine powder; it was then added to N,N-dimethylformamide with polyether diol to obtain dispersion E, which was then added to isophorone diisocyanate solution and reacted. After that, p-methylbenzaldehyde and hexamethylenediamine were added to react and obtain a dynamic self-healing prepolymer. S3: Isophorone diisocyanate was added to a toluene dispersion of diaminopropyl polydimethylsiloxane and reacted, followed by the addition of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to obtain a friction-reducing and wear-resistant prepolymer. S4: Polytetrafluoroethylene micro powder, antioxidant and light stabilizer are added to polyurethane acrylate matrix, and after uniform dispersion, dynamic self-healing prepolymer is added to obtain the first mixture; polyvinyl alcohol, polyethylene glycol and glycerol are dispersed in ethanol to obtain a dispersion solution, and then added to the first mixture to obtain the second mixture. After uniform dispersion, multilayer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and thermosetting agent are added in sequence and mixed. After thermosetting and curing, polymer nano-synthetic ice material is obtained.

2. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S1: The mass ratio of tea polyphenols to nano-silica is (0.05-0.1):1; The mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is (0.2-0.4):

1.

3. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S1: The silane coupling agent is any one or a combination of two of KH550 or KH560; The mass ratio of the silane coupling agent to the double-layer coated silica is (0.05-0.1):

1.

4. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S2: The pH value of the alkaline aqueous solution is 10-11; The molar ratio of the diamine powder to the polyether diol is (0.1-0.3):1; The total molar ratio of isophorone diisocyanate to polyether diol and diamine powder is (1-1.2):

1.

5. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S2: The mass ratio of p-methylbenzaldehyde to hexamethylenediamine is 1:1; The total mass of p-methylbenzaldehyde and hexamethylenediamine is 5-10% of dispersion E.

6. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S3: the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is (0.2-0.3):

1.

7. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S3: The mass ratio of 1H,1H-perfluorooctyl acrylate to trimethylolpropane triacrylate is (1-1.5):1; The total mass of the 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate is 30-40% of the mass of the toluene dispersion of diaminopropyl polydimethylsiloxane.

8. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S4: The amount of polytetrafluoroethylene micro powder fed into the feed is 0.5-2% of the mass of the polyurethane acrylate matrix; The antioxidant is antioxidant 1010, and the amount of antioxidant added is 0.1-0.5% of the mass of the polyurethane acrylate matrix; The light stabilizer is UV-531, an ultraviolet absorber, and the amount of light stabilizer added is 0.1-0.5% of the mass of the polyurethane acrylate matrix.

9. The method for preparing a polymer nano-synthetic ice material according to claim 1, characterized in that, In S4: The amount of polyvinyl alcohol added is 1-5% of the mass of the polyurethane acrylate matrix; The amount of polyethylene glycol added is 1-5% of the mass of the polyurethane acrylate matrix; The amount of glycerol added is 0.5-2% of the mass of the polyurethane acrylate matrix; The thermosetting agent is benzoyl peroxide.

10. A polymeric nano-synthetic ice material prepared by the preparation method according to any one of claims 1-9, characterized in that, The mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell modified silica, friction-reducing and wear-resistant prepolymer and thermosetting agent in the polymer nano-synthetic ice material is (45-55):(15-25):(10-15):(15-20):(1-2).

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