Polymer nano synthetic ice material and preparation method thereof

Abstract

The invention provides a polymer nano synthetic ice material and a preparation method thereof, and belongs to the technical field of polymer materials. The mechanical property, the wear resistance and the stability of the material are enhanced through the double-layer core-shell structure of the nano silicon dioxide and the silane coupling agent; according to the present invention, with the combination of the synergistic effect of the disulfide bond of cystamine and the Schiff base dynamic bond in the dynamic self-repairing prepolymer, the molecular recombination and the self-repairing after the damage are achieved, and the reaction of the diamine and the isocyanate improves the crosslinking density so as to make the material have excellent toughness, excellent strength and excellent aging resistance; besides, by introducing bis (aminopropyl) polydimethylsiloxane, perfluorooctyl acrylate and trimethylolpropane triacrylate, the surface energy is synergistically reduced, the sliding performance and the anti-fouling performance are enhanced, and meanwhile, the hardness, the wear resistance and the thermal stability are further improved through a three-dimensional network structure with high crosslinking density, so that the material is endowed with excellent comprehensive performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and relates to a polymer nano synthetic ice material and a preparation method thereof. Background Art

[0002] As an important functional material, ice materials are widely used in skating rinks, curling, and various ice entertainment activities. However, traditional real ice venues face many challenges in construction and maintenance, mainly including high construction and maintenance costs, stringent requirements for environmental temperature, and consumption of a large amount of water resources. These problems not only increase the economic burden on operators but also limit the popularization and development of ice activities to a certain extent, especially in the context of increasingly significant climate change.

[0003] In practical applications, the quality of real ice is easily affected by external environmental factors, especially temperature fluctuations. Such fluctuations directly lead to changes in the flatness and hardness of the ice surface, thereby affecting the performance of athletes and the experience of participants. For example, in a high-temperature environment, the ice surface is prone to softening, deformation, and even water stains, which not only reduces the playability and safety of the sport but also may cause accidents to athletes during the competition. In addition, the maintenance work of ice rinks is cumbersome and requires continuous investment, increasing the complexity and cost of operation.

[0004] With the increasing emphasis on environmental protection and sustainable development in society, the development of a synthetic ice material with excellent performance, low cost, and environmental friendliness has become an urgent need in the industry. This new material should not only have performance comparable to that of traditional real ice but also reduce resource consumption and environmental impact to meet the pursuit of sustainable development in modern society.

[0005] Although existing synthetic ice materials have solved some problems of real ice to a certain extent, such as reducing water resource consumption and maintenance costs, there are still obvious deficiencies in terms of strength, wear resistance, and self-healing ability. For example, many current synthetic ice materials are prone to cracking when subjected to impact, and their wear resistance is poor, with a short service life, making it difficult to meet the requirements in high-intensity sports venues. In addition, the performance of some synthetic materials under extreme temperature conditions is also not stable enough to ensure safety and comfort during sports. Summary of the Invention

[0006] In view of the above problems, the object of the present invention is to provide a polymer nano synthetic ice material and a preparation method thereof. In the present invention, nano-silica forms a double-layer core-shell structure through tea polyphenol coating and zirconia coating, significantly improving the mechanical properties, wear resistance and weather resistance of the material. At the same time, the surface functionalization of silane coupling agent enhances the compatibility and binding force between the filler and the matrix, thus ensuring the long-term stability of the material; 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-healing functions after damage. At the same time, the crosslinking density of the material is enhanced by the reaction of diamino groups and isocyanates. Combining the flexibility of polyether segments and the rigidity of isophorone diisocyanate, the material has excellent toughness, strength and anti-aging properties; in addition, by introducing diaminopropyl polydimethylsiloxane, perfluorooctyl acrylate and trimethylolpropane triacrylate, the material is given anti-friction and wear-resistant characteristics. Among them, the siloxane segment and the perfluorinated segment synergistically reduce the surface energy, enhance the sliding performance and anti-fouling ability, and the three-dimensional structure with high crosslinking density further improves the hardness, wear resistance and thermal stability of the material, making it exhibit excellent comprehensive performance in complex environments.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a preparation method of a polymer nano synthetic ice material, and the preparation method of the polymer nano synthetic ice material includes:

[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 multi-layer core-shell structure modified silica;

[0010] S2: Add cystamine dihydrochloride to an alkaline aqueous solution for treatment to obtain a diamine powder; add it and polyether diol to N,N-dimethylformamide to obtain a dispersion E, add it to an isophorone diisocyanate solution for reaction, and then add p-tolualdehyde and hexamethylenediamine for reaction to obtain a dynamic self-healing prepolymer;

[0011] S3: Add isophorone diisocyanate to a toluene dispersion of diaminopropyl polydimethylsiloxane for reaction, and then add 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate for reaction to obtain an anti-friction and wear-resistant prepolymer;

[0012] S4: Add polytetrafluoroethylene micro powder, antioxidant and light stabilizer into the polyurethane acrylate matrix. After uniform dispersion, add the dynamic self-healing prepolymer to obtain the first mixture. Disperse polyvinyl alcohol, polyethylene glycol and glycerol in ethanol to obtain a dispersion solution, and add it to the first mixture to obtain the second mixture. After uniform dispersion, sequentially add the multi-layer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and heat curing agent, mix them, and obtain the high-molecular nano synthetic ice material after heat curing and aging.

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

[0014] S2: Add cystamine dihydrochloride into an alkaline aqueous solution, stir, filter, wash and dry to obtain diamine powder; Add it and polyether diol into N,N-dimethylformamide, mix uniformly to obtain dispersion liquid E, and add it dropwise to the isophorone diisocyanate solution to obtain reaction liquid F. After constant temperature reflux in an inert atmosphere, add a mixed solution of p-methylbenzaldehyde and hexamethylenediamine dropwise to obtain reaction liquid G, stir at a constant temperature, filter and distill under reduced pressure to obtain the dynamic self-healing prepolymer;

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

[0016] S4: Add polytetrafluoroethylene micro powder, antioxidant and light stabilizer into the polyurethane acrylate matrix. After uniform dispersion, add the dynamic self-healing prepolymer at a constant temperature to obtain the first mixture. Disperse polyvinyl alcohol, polyethylene glycol and glycerol in ethanol to obtain a dispersion solution, and add it to the first mixture to obtain the second mixture. After uniform dispersion, sequentially add the multi-layer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and heat curing agent, uniformly disperse to obtain a pretreated mixture, reduce the temperature to room temperature, defoam under vacuum, cure by heat, and then place at room temperature for aging to obtain the high-molecular nano synthetic ice material.

[0017] As a preferred technical solution of the present invention, in S1, the mass ratio of the tea polyphenol to the 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. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0018] In some alternative embodiments, the pH of the dispersion A is adjusted to 8 - 8.5 with a buffer solution. For example, it can be 8, 8.1, 8.2, 8.3, 8.4 or 8.5. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0019] In some alternative embodiments, the reaction solution B reacts at room temperature for 8 - 12 h. For example, it can be 8 h, 8.4 h, 8.8 h, 9.2 h, 9.6 h, 10 h, 10.4 h, 10.8 h, 11.2 h, 11.6 h or 12 h. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0020] In some alternative 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.%. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0021] In some alternative embodiments, the mass ratio of tetrabutyl zirconate to the tea 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. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0022] In some alternative embodiments, the temperature for the constant-temperature 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. However, it is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0023] In some alternative embodiments, the reaction solution C is kept at a constant temperature for 2 - 3 h. For example, it can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h, or 3 h. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0024] In some alternative embodiments, the mass ratio of the silane coupling agent to the double-layer 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. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0025] In some alternative embodiments, the temperature of the dispersion D during constant-temperature 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. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0026] In some alternative embodiments, the reaction time of the dispersion D during constant-temperature reflux is 2 - 3 h. For example, it can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h, or 3 h. However, it is not limited to the listed values, and other unlisted values within this range are equally 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. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0028] In some alternative 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 0.3:1. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0029] In some alternative embodiments, the total mass fraction of the diamine powder and the polyether diol in the dispersion liquid 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, and other unlisted values within this numerical range are equally applicable.

[0030] In some alternative embodiments, the mass fraction of the isophorone diisocyanate solution 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, and other unlisted values within this numerical range are equally applicable.

[0031] In some alternative embodiments, the molar ratio of the isophorone diisocyanate to the total moles of 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, and other unlisted values within this numerical range are equally applicable.

[0032] In some alternative embodiments, the temperature of the constant temperature reflux of the reaction liquid F in an inert atmosphere is 50-60 °C, for example, it can be 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 numerical range are equally applicable.

[0033] In some alternative embodiments, the time of the constant temperature reflux of the reaction liquid F in an inert atmosphere is 2-3 h, for example, it can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h or 3 h, but is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0034] In some alternative embodiments, the total mass of the p-methylbenzaldehyde and the hexamethylenediamine is 5-10% of the dispersion liquid 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 numerical range are equally applicable.

[0035] In some alternative embodiments, the mass fraction of the mixed solution of p-methylbenzaldehyde 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 numerical range are equally applicable.

[0036] In some alternative embodiments, the temperature for the constant temperature stirring of the reaction solution G 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 numerical range are equally applicable.

[0037] In some alternative embodiments, the time for the constant temperature stirring of the reaction solution G is 1-2 h, for example, it can be 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2 h, but is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.

[0038] As a preferred technical solution of the present invention, in S3, the mass fraction of the toluene dispersion of bis(aminopropyl)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, and other unlisted values within this numerical range are equally applicable.

[0039] In some alternative embodiments, the temperature for the constant temperature stirring of the toluene dispersion of bis(aminopropyl)polydimethylsiloxane is 50-60 °C, for example, it can be 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 numerical range are equally applicable.

[0040] In some alternative embodiments, the mass ratio of isophorone diisocyanate to bis(aminopropyl)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, and other unlisted values within this numerical range are equally applicable.

[0041] In some alternative embodiments, the first reaction solution is continuously stirred for 1 - 2 h. For example, it can be 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, or 2 h. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0042] In some alternative 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. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0043] In some alternative embodiments, the total mass of 1H,1H - perfluorooctyl acrylate and trimethylolpropane triacrylate is 30 - 40% of the mass of the toluene dispersion of bis(aminopropyl)polydimethylsiloxane. For example, it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0044] In some alternative embodiments, the mass fraction of the mixed solution H 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.%. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0045] In some alternative embodiments, the temperature for the second reaction solution to be 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. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0046] In some alternative embodiments, the time for the second reaction solution to be stirred at a constant temperature is 2 - 3 h. For example, it can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h, or 3 h. However, it is not limited to the listed values, and other unlisted values within this range are equally applicable.

[0047] As a preferred technical solution of the present invention, in S4, the feeding amount of the polytetrafluoroethylene micropowder 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. Other unlisted values within this numerical range are equally applicable.

[0048] In some alternative embodiments, the feeding amount of the antioxidant 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 numerical range are equally applicable.

[0049] In some alternative embodiments, the feeding amount of the light stabilizer 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 numerical range are equally applicable.

[0050] In some alternative embodiments, the temperature for stirring the dynamic self-healing prepolymer into the first mixture 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. Other unlisted values within this numerical range are equally applicable.

[0051] In some alternative embodiments, the feeding amount of the polyvinyl alcohol 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. Other unlisted values within this numerical range are equally applicable.

[0052] In some alternative embodiments, the feeding amount of the polyethylene glycol 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. Other unlisted values within this numerical range are equally applicable.

[0053] In some alternative embodiments, the feeding amount of the glycerol 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. Other unlisted values within this numerical range are equally applicable.

[0054] In some alternative embodiments, the temperature of the thermal curing is 60-80 °C. For example, it can be 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. Other unlisted values within this numerical range are equally applicable.

[0055] In some alternative embodiments, the time of the thermal curing is 2-4 h. For example, it can be 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h or 4 h, but is not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0056] In some alternative embodiments, the time of the room-temperature aging is 20-24 h. For example, it can be 20 h, 20.4 h, 20.8 h, 21.2 h, 21.6 h, 22 h, 22.4 h, 22.8 h, 23.2 h, 23.6 h or 24 h, but is not limited to the listed values. Other unlisted values within this numerical range are equally applicable.

[0057] In a second aspect, the present invention provides a polymer nano synthetic ice material. The polymer nano synthetic ice material includes a polyurethane acrylate matrix, a dynamic self-healing prepolymer, a multi-layer core-shell structure modified silica, a friction-reducing and wear-resistant prepolymer and a thermal curing agent, wherein the mass ratio of the polyurethane acrylate matrix, the dynamic self-healing prepolymer, the multi-layer core-shell structure modified silica, the friction-reducing and wear-resistant prepolymer and the thermal curing agent is (45-55):(15-25):(10-15):(15-20):(1-2).

[0058] In the present invention, nano-silica is introduced as a filler, and its functional performance and comprehensive properties in the composite material are significantly enhanced through multi-step modification. Nano-silica is a common inorganic nano-material with excellent physical and chemical properties. Firstly, nano-silica has a highly dispersed structure and an extremely high specific surface area. This property enables it to come into full contact with the matrix in the composite material, forming a uniform distribution and maximizing its reinforcement effect. Secondly, the surface of silica is rich in hydroxyl groups, which endows it with adjustable surface reactivity and enables the introduction of various functional groups through chemical modification, greatly expanding its application scope in complex systems. In addition, nano-silica has good thermal stability and excellent mechanical properties, and can remain stable under high-temperature or high-stress environments. Its high hardness property enables it to play a significant reinforcement role in the composite material, and the mechanical properties, thermal properties, and wear resistance of the composite material can be effectively improved through filling. Therefore, nano-silica is selected as the core reinforcement phase of the composite material in the present invention and is the key to achieving high-performance materials.

[0059] In order to further enhance the functionality of nano-silica and its compatibility with the matrix, a multi-layer surface modification strategy is adopted in the present invention. Tea polyphenols are a class of natural polyphenolic compounds containing a large number of phenolic hydroxyl groups, with excellent chemical activity and antioxidant ability. The surface of nano-silica is rich in hydroxyl groups, and these hydroxyl groups interact with tea polyphenol molecules through electrostatic forces, hydrogen bonds, and surface adsorption forces, enabling tea polyphenols to be evenly adsorbed on the surface of silica particles. When the pH value of the buffer solution is adjusted to alkaline, the phenolic hydroxyl groups in tea polyphenols are partially oxidized to form quinone structures. These quinone groups form a uniform tea polyphenol polymer layer on the surface of silica through further self-polymerization reactions.

[0060] The tea 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 tea polyphenols has antioxidant properties, which can effectively inhibit the oxidative degradation of the material during subsequent use. In addition, through the coating of tea polyphenols, the agglomeration between silica particles is reduced, and its dispersion stability in the solution is improved.

[0061] On this basis, tetrabutyl zirconate was further used to perform secondary coating on the tea polyphenol-coated nano-silica to form a double-layer core-shell structure. Tetrabutyl zirconate generates zirconium alkoxide intermediates during hydrolysis and alcoholysis reactions, and then further undergoes a polycondensation reaction to form nano-scale zirconia. Since the surface of the tea polyphenol coating layer contains abundant phenolic hydroxyl groups and quinone groups, these active groups can complex with the zirconia precursor, enabling the uniform deposition of zirconia on the surface of the tea polyphenol coating layer, thus forming a double-layer coating structure. Zirconia has high hardness and high rigidity, which significantly enhances the overall mechanical properties of the composite material after being deposited on the silica surface; secondly, the high hardness and low friction coefficient of zirconia effectively reduce the wear of the material during the friction process; at the same time, zirconia has excellent thermal stability, which can significantly improve the durability of the modified silica under high-temperature conditions; in addition, the chemical inertness and ultraviolet resistance of zirconia enhance the environmental stability of the material and slow down the performance degradation caused by photoaging and chemical corrosion during the long-term use of the material.

[0062] In order to further enhance the interfacial bonding force between the double-layer coated nano-silica and the matrix, the present invention uses a silane coupling agent to functionalize its surface. Silane coupling agents are a class of molecules with both inorganic and organic functional groups, and their compatibility design enables them to bridge inorganic fillers and 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 to form stable Si-O-Si chemical bonds; at the same time, the organic functional groups in the silane coupling agent molecule are exposed on the filler surface and can further undergo chemical reactions or form hydrogen bonds with the organic matrix. This bifunctional structure enables 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 the modification with silane coupling agent, a surface-functionalized multi-layer core-shell structured nano-silica filler is finally obtained, which can not only provide excellent reinforcement in the composite material, but also effectively avoid the agglomeration and shedding of the filler, thus ensuring the long-term stability and durability of the material.

[0063] In the present invention, a dynamic self-healing prepolymer is introduced, providing the material with a balance of self-healing function, flexibility and mechanical strength, as well as excellent anti-aging performance and heat resistance.

[0064] The cystamine molecule is the core component of the dynamic self-healing prepolymer of the present invention. Its molecular structure contains two amine groups and a disulfide bond simultaneously, endowing it with unique chemical reactivity and dynamic functions. Under alkaline conditions, the hydrochloride radical of cystamine dihydrochloride is neutralized, releasing the cystamine molecule with diamine groups. This pretreatment step not only ensures the chemical activity of cystamine but also provides free amine sites for subsequent reactions. The diamine groups in cystamine can undergo a classical addition reaction with isocyanate groups to form ureylene bonds with high stability and strong mechanical properties. Meanwhile, the disulfide bond in the cystamine molecule is not broken during the reaction.

[0065] The dynamic property of the disulfide bond is the core chemical basis for the self-healing function endued to the material by the present invention. Under the action of external force or environmental stimuli, the disulfide bond can undergo reversible cleavage to generate reactive sulfur free radicals. After the stress is relieved or the stimulus stops, these sulfur free radicals can recombine again to restore to the form of the disulfide bond. This dynamic cleavage-recombination mechanism ensures that after microcracks or damages appear in the material, its structure can be rapidly repaired through molecular rearrangement, thereby prolonging the service life of the material. This property is particularly important for wear-resistant materials because it can compensate for surface damages and slow down the aging and performance degradation of the material.

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

[0067] To further optimize the performance of the dynamic self-healing material, the present invention introduces polyether diol and isophorone diisocyanate, and a polyurethane segment with a balance of flexibility and rigidity is generated through their reaction.

[0068] The hydroxyl groups contained in the polyether diol molecule can react with isocyanate groups to form the soft segments in the polyurethane segment. The polyether segments have a high degree of 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 part of the stress through the stretching and bending of the molecular chains, dispersing the external force to a larger molecular range, thereby effectively reducing the wear of the material. This stress release 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 diol to form the hard segments in the polyurethane chain segments. These hard segments provide the rigidity and heat resistance of the material, enhancing the overall mechanical properties of the material. In addition, the isophorone diisocyanate molecule structure has a large steric hindrance effect. This structural feature not only improves the thermal stability of the material but also enhances its anti-aging performance. This means that the material can effectively resist thermal degradation and environmental aging under high-temperature or long-term use conditions and maintain its performance stability.

[0070] Through the synergistic effect of the polyether chain segments and isophorone diisocyanate chain segments, the dynamic self-healing prepolymer in the present invention realizes the characteristics of combining rigidity and flexibility. The material is both flexible and tough under dynamic conditions and maintains high strength and stability, especially suitable for use in complex environments.

[0071] In order to further improve the dynamic performance and stability of the material, the present invention also introduces Schiff base dynamic bonds. The Schiff base bonds are formed by the amine-aldehyde condensation reaction between p-methylbenzaldehyde and hexamethylenediamine. The Schiff base bond is a dynamic chemical bond 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 ability. When the material is damaged, the Schiff base bonds can quickly break and recombine to repair the damaged molecular chain segments, further enhancing the dynamic self-healing ability of the material.

[0072] At the same time, the aromatic ring structure in the p-methylbenzaldehyde molecule provides a rigid skeleton for the material. The introduction of the aromatic ring significantly improves the chemical stability and antioxidant performance of the chain segments, while increasing the hardness and heat resistance of the material. This enables the material to maintain good mechanical properties under high-temperature and high-strength conditions.

[0073] In the present invention, bis(aminopropyl)polydimethylsiloxane is introduced and combined with other functional modifiers to construct a high-performance friction-reducing and wear-resistant system. Bis(aminopropyl)polydimethylsiloxane is a multifunctional compound containing siloxane chain segments and having a diamine structure. Its molecule contains siloxane chain segments and amine groups. The amine groups can undergo an addition reaction with isocyanate groups to form urethane bonds; the siloxane chain segments are integrated into the polyurethane chain segments to form a network structure with both flexibility and rigidity. The siloxane chain 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 friction coefficient between the material and the outside world, thus significantly improving the sliding performance of the ice material. At the same time, the molecular flexibility can absorb external forces and disperse stress during the friction process, effectively reducing the surface wear of the material. This self-lubricating characteristic also improves the wear resistance of the material, enabling it to show better stability and longer service life during long-term use.

[0074] In order to further optimize the surface properties and functional characteristics of the material, the present invention also introduces 1H,1H-perfluorooctyl acrylate, and integrates the perfluorinated chain segment into the material network through chemical reactions. This perfluorinated chain segment has an extremely low surface energy, forming a superhydrophobic outer layer on the material surface, significantly reducing the surface energy of the material, and further enhancing the sliding performance of the ice material. In addition, the introduction of the perfluorinated chain segment endows the material with excellent hydrophobicity and anti-fouling properties, not only reducing the interaction between water molecules and the material surface, but also effectively preventing the adhesion of pollutants. The chemical inertness and environmental stability of the perfluorinated chain segment further enhance the weather resistance of the material, enabling it to exhibit good performance stability in complex environments.

[0075] To improve the overall mechanical properties and wear resistance of the material, the present invention particularly introduces trimethylolpropane triacrylate as a crosslinking agent. The trimethylolpropane triacrylate molecule contains three acrylate groups, which can form a three-dimensional network structure with a high crosslinking density through chemical reactions with the material molecular chains. This high crosslinking density significantly enhances the hardness and rigidity of the material, enabling it to exhibit stronger anti-deformation ability in high-stress environments, while restricting the mobility of the molecular chains, thereby reducing the breakage and wear of the molecular chains during friction and further improving the wear resistance of the material. In addition, the three-dimensional network structure formed by the crosslinking of trimethylolpropane triacrylate significantly improves the thermal stability and anti-aging performance of the material, enabling it to maintain structural integrity and performance stability under high-temperature or long-term use conditions.

[0076] There is also a synergistic effect in the present invention. The introduction of the dynamic self-healing prepolymer endows the material with self-healing ability mainly through the dynamic behavior of the disulfide bonds and Schiff base bonds in cystamine. The disulfide bonds can be broken and recombined under external force or environmental stimuli, while the 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 quickly repair after the appearance of microcracks or surface damage and restore its mechanical properties.

[0077] The siloxane chain segment has a low surface energy and high flexibility, forming a lubricating and flexible molecular layer on the material surface, thereby reducing the friction coefficient and enhancing the sliding performance; the perfluorinated chain segment further reduces the surface energy of the material through its extremely low surface energy, while endowing the material with excellent hydrophobicity and anti-fouling properties. The synergistic effect of the two chain segments enables the material surface to simultaneously possess an extremely low friction coefficient and excellent hydrophobic and anti-fouling properties.

[0078] By introducing trimethylolpropane triacrylate, the crosslinking density of the material is increased, thereby enhancing the mechanical properties of the material. This high crosslinking density and the flexibility of the dynamic bonds form a synergistic effect: in a high-stress or high-friction environment, the high crosslinking density restricts the excessive movement of molecular chains, enhancing the anti-deformation ability and wear resistance of the material; at the same time, the fracture-recombination behavior of the dynamic bonds provides the material with stress release and structural repair capabilities at the molecular level. This synergistic effect enables the material to possess dynamic self-healing ability while maintaining high strength and high hardness, thus showing excellent durability and stability during long-term use.

[0079] In terms of sliding performance, the siloxane chain segments provide molecular flexibility and lubricity, reducing the friction coefficient; the extremely low surface energy of the perfluorinated chain segments further reduces sliding friction, and at the same time its hydrophobic property reduces the adhesion of water or moisture to the surface of the ice material; after the nano-silica is coated and modified with tea polyphenols and zirconia, its hardness and interfacial bonding force are enhanced, effectively reducing wear during the sliding process. The combined action of these components enables the material to exhibit lower frictional resistance, higher wear resistance, and longer service life in a complex sliding environment.

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

[0081] The present invention significantly improves the performance of the composite material by introducing nano-silica through multi-step modification. The nano-silica provides good reinforcement with its high specific surface area and surface hydroxyl groups, enhancing the mechanical, thermal stability, and wear resistance of the material; the self-polymerization of the tea polyphenol coating enhances the bonding force between the filler and the matrix, and a double-layer core-shell structure is formed by introducing a zirconia coating layer, further improving hardness, wear resistance, and weather resistance; finally, the surface functionalization of the silane coupling agent optimizes the interfacial compatibility and bonding force, ensuring uniform distribution of the filler and preventing it from falling off easily, thereby endowing the composite material with excellent comprehensive performance and long-term stability;

[0082] The present invention introduces a dynamic self-healing prepolymer. The disulfide bonds in the cystamine molecule endow the material with dynamic fracture-recombination self-healing ability. The diamino groups react with isocyanates to form ureylene bonds, enhancing the crosslinking density and mechanical properties; the polyether chain segments provide molecular flexibility and toughness, absorbing stress and reducing wear, while the isophorone diisocyanate chain segments provide rigidity and heat resistance, enhancing the anti-aging ability of the material; the Schiff base dynamic bonds further improve the self-healing performance of the material. Their reversible characteristics cooperate with the disulfide bonds to provide a flexible molecular repair mechanism for the material, and at the same time the aromatic ring structure of p-methylbenzaldehyde enhances the rigid skeleton and antioxidant performance of the material;

[0083] The present invention constructs a high-performance anti-friction and wear-resistant system by introducing bis(aminopropyl)polydimethylsiloxane, 1H,1H-perfluorooctyl acrylate, and trimethylolpropane triacrylate. The siloxane segments and amine groups in bis(aminopropyl)polydimethylsiloxane react with isocyanate to form ureido bonds and are integrated into the polyurethane network, endowing the material with low surface energy and high flexibility, thus significantly reducing the friction coefficient, improving the sliding performance, reducing wear by dispersing stress, and extending the service life. 1H,1H-perfluorooctyl acrylate further introduces perfluoro segments to form a superhydrophobic outer layer, reducing the surface energy and enhancing the anti-fouling and weather resistance, enabling the material to exhibit excellent stability in complex environments. Trimethylolpropane triacrylate acts as a crosslinking agent to form a three-dimensional network structure with a high crosslinking density, significantly enhancing the hardness, rigidity, and anti-aging performance, and enabling the material to maintain a stable structure and performance under high temperature and long-term use conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 It is a flowchart of the preparation method of the polymer nanocomposite synthetic ice material provided by the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0085] The technical solution of the present invention will be described in detail below in conjunction with specific embodiments and their accompanying drawings. The embodiments described herein are specific specific embodiments of the present invention and are used to illustrate the concept of the present invention; these descriptions are all explanatory and exemplary, and should not be construed as a limitation on the embodiments of the present invention and the protection scope of the present invention. Except for the embodiments described herein, those skilled in the art can also adopt other obvious technical solutions based on the content disclosed in the claims and the specification of the present application, and these technical solutions include technical solutions that make any obvious substitutions and modifications to the embodiments described herein.

[0086] The chemical reagents used in the embodiments and comparative examples of the present invention are all commercially available products and have not been further purified or processed.

[0087] Example 1

[0088] This example provides a polymer nanocomposite synthetic ice material and its preparation method;

[0089] See Figure 1 , the preparation method of the polymer nanocomposite synthetic ice material specifically includes the following steps:

[0090] S1: Disperse nano-silica in a tea polyphenol solution to obtain dispersion A, where the mass ratio of tea polyphenol to silica is 0.08:1. Adjust its pH to 8.2 with a buffer solution to obtain reaction solution B. After reacting at room temperature for 8 h, filter, wash, and dry to obtain tea polyphenol-coated silica. Prepare a 20 wt.% dispersion of tea polyphenol-coated silica, and add tetrabutyl zirconate dropwise to obtain reaction solution C, where the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.3:1. React at a constant temperature of 30 °C for 2.2 h, filter, wash, and dry to obtain double-layer coated silica. Disperse it and a silane coupling agent in an aqueous ethanol solution to obtain dispersion D, where the mass ratio of the silane coupling agent to the double-layer coated silica is 0.07:1. Reflux at a constant temperature of 60 °C for 2 h, filter, wash, and dry to obtain multi-layer core-shell structure modified silica;

[0091] S2: Add cystamine dihydrochloride to an alkaline aqueous solution with a pH of 10, stir, filter, wash, and dry to obtain diamine powder. Add it and polyether diol to N,N-dimethylformamide and mix evenly to obtain dispersion E, where the molar ratio of diamine powder to polyether diol is 0.2:1, and the total mass fraction of diamine powder and polyether diol in dispersion E is 30 wt%. Drop it into a 20 wt.% isophorone diisocyanate solution to obtain reaction solution F, where the molar ratio of isophorone diisocyanate to the total moles of polyether diol and diamine powder is 1.1:1. After refluxing at a constant temperature of 50 °C for 2.5 h under an inert atmosphere, dropwise add a mixed solution of p-methylbenzaldehyde and hexamethylenediamine to obtain reaction solution G, where the mass ratio of p-methylbenzaldehyde to hexamethylenediamine is 1:1, the total mass of p-methylbenzaldehyde and hexamethylenediamine is 8% of dispersion E, and the mass fraction of the mixed solution of p-methylbenzaldehyde and hexamethylenediamine is 15 wt%. Stir at a constant temperature of 40 °C for 1.5 h, then filter and perform vacuum distillation to obtain a dynamic self-healing prepolymer;

[0092] S3: Prepare a toluene dispersion of 40 wt.% diaminopropyl polydimethylsiloxane, stir at a constant temperature of 50 °C under an inert atmosphere, and add isophorone diisocyanate to obtain the first reaction solution, where the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is 0.25:1. Continue stirring and reacting for 1 h, then dropwise add a mixed solution H of 25 wt.% 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to obtain the second reaction solution, where the mass ratio of 1H,1H-perfluorooctyl acrylate to 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 perform vacuum distillation to obtain an anti-friction and wear-resistant prepolymer;

[0093] S4: Add polytetrafluoroethylene micro powder, antioxidant 1010 and ultraviolet absorber UV-531 into the polyurethane acrylate matrix. The feeding amount of the polytetrafluoroethylene micro powder is 0.5% of the mass of the polyurethane acrylate matrix, the feeding amount of the antioxidant is 0.2% of the mass of the polyurethane acrylate matrix, and the feeding amount of the light stabilizer is 0.3% of the mass of the polyurethane acrylate matrix. After uniform dispersion, add the dynamic self-healing prepolymer at a constant temperature of 40°C to obtain a first mixture. Disperse polyvinyl alcohol, polyethylene glycol and glycerol in ethanol to obtain a dispersion solution and add it to the first mixture to obtain a second mixture, where the feeding amount of polyvinyl alcohol is 3% of the mass of the polyurethane acrylate matrix, the feeding amount of polyethylene glycol is 2% of the mass of the polyurethane acrylate matrix, and the feeding amount of glycerol is 1% of the mass of the polyurethane acrylate matrix;

[0094] After uniform dispersion, successively add multilayer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer and N,N-dimethylbenzylamine. After uniform dispersion, obtain a pretreated mixture. After cooling to room temperature, defoam under vacuum and cure at 60°C for 2 h, then place at room temperature for 20 h for aging to obtain a high molecular nano synthetic ice material, where the mass ratio of the polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer and heat curing agent is 50:20:12:17:1.8.

[0095] Example 2

[0096] This example provides a high molecular nano synthetic ice material and its preparation method. The preparation method of the high molecular nano synthetic ice material specifically includes the following steps:

[0097] S1: Disperse nano silica in a tea polyphenol solution to obtain a dispersion liquid A, where the mass ratio of tea polyphenol to silica is 0.05:1. Adjust its pH to 8 with a buffer solution to obtain a reaction liquid B. After reacting at room temperature for 10 h, filter, wash and dry to obtain tea polyphenol-coated silica; Prepare a dispersion liquid of tea polyphenol-coated silica with a mass fraction of 25 wt.%, and dropwise add tetrabutyl zirconate to obtain a reaction liquid C, where the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.2:1. React at a constant temperature of 35°C for 2.5 h, filter, wash and dry to obtain double-layer coated silica; Disperse it and a silane coupling agent in an aqueous solution of absolute ethanol to obtain a dispersion liquid D, where the mass ratio of the silane coupling agent to the double-layer coated silica is 0.08:1. Reflux at a constant temperature of 65°C for 2.8 h, filter, wash and dry to obtain multilayer core-shell structured modified silica;

[0098] S2: Add cystamine dihydrochloride into an alkaline aqueous solution with a pH value of 10.5, stir, filter, wash, and dry to obtain diamine powder; add it and polyether diol into N,N-dimethylformamide, and uniformly mix to obtain dispersion E, where the molar ratio of diamine powder to polyether diol is 0.1:1, and the total mass fraction of diamine powder and polyether diol in dispersion E is 35 wt.%. Drop it into an isophorone diisocyanate solution with a mass fraction of 25 wt.% to obtain reaction solution F, where the molar ratio of isophorone diisocyanate to the total moles of polyether diol and diamine powder is 1:1. After refluxing at a constant temperature of 55 °C for 2 h under an inert atmosphere, dropwise add a mixed solution of p-methylbenzaldehyde and hexamethylenediamine to obtain reaction solution G, where the mass ratio of p-methylbenzaldehyde to hexamethylenediamine is 1:1, the total mass of p-methylbenzaldehyde and hexamethylenediamine is 5% of dispersion E, and the mass fraction of the mixed solution of p-methylbenzaldehyde and hexamethylenediamine is 10 wt.%. Stir at a constant temperature of 48 °C for 1 h, filter, and perform vacuum distillation to obtain a dynamic self-healing prepolymer;

[0099] S3: Prepare a toluene dispersion of 30 wt.% bis(3-aminopropyl)polydimethylsiloxane, stir at a constant temperature of 60 °C under an inert atmosphere, and then add isophorone diisocyanate to obtain the first reaction solution, where the mass ratio of isophorone diisocyanate to bis(3-aminopropyl)polydimethylsiloxane is 0.28:1. Continue to stir and react for 1.5 h, then dropwise add a mixed solution H of 28 wt.% 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to obtain the second reaction solution, where the mass ratio of 1H,1H-perfluorooctyl acrylate to 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 bis(3-aminopropyl)polydimethylsiloxane. Stir at a constant temperature of 48 °C for 2.8 h, filter, and perform vacuum distillation to obtain an antifriction and wear-resistant prepolymer;

[0100] S4: Add polytetrafluoroethylene micropowder, antioxidant 1010, and ultraviolet absorber UV-531 into a polyurethane acrylate matrix, where the feeding amount of polytetrafluoroethylene micropowder is 1% of the mass of the polyurethane acrylate matrix, the feeding amount of the antioxidant is 0.1% of the mass of the polyurethane acrylate matrix, and the feeding amount of the light stabilizer is 0.1% of the mass of the polyurethane acrylate matrix. After uniformly dispersing, add the dynamic self-healing prepolymer at a constant temperature of 45 °C to obtain the first mixture. Disperse polyvinyl alcohol, polyethylene glycol, and glycerol in ethanol to obtain a dispersion solution and add it to the first mixture to obtain the second mixture, where the feeding amount of polyvinyl alcohol is 4% of the mass of the polyurethane acrylate matrix, the feeding amount of polyethylene glycol is 3% of the mass of the polyurethane acrylate matrix, and the feeding amount of glycerol is 0.5% of the mass of the polyurethane acrylate matrix;

[0101] After being evenly dispersed, multi-layer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer, and benzoyl peroxide are added in sequence. After being evenly dispersed, a pretreatment mixture is obtained. After cooling to room temperature, it is defoamed under vacuum and thermally cured at 70 °C for 3 h, and then left at room temperature for 22 h for curing to obtain a polymer nano synthetic ice material, where the mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multi-layer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer, and thermal curing agent is 45:22:15:20:1.5.

[0102] Example 3

[0103] This example 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: Nano-silica is dispersed in a tea polyphenol solution to obtain dispersion liquid A, where the mass ratio of tea polyphenol to silica is 0.075:1. Its pH is adjusted to 8.4 with a buffer solution to obtain reaction liquid B. After reacting at room temperature for 11 h, it is filtered, washed, and dried to obtain tea polyphenol-coated silica; A 28 wt.% dispersion liquid of tea polyphenol-coated silica is prepared, and tetrabutyl zirconate is added dropwise to obtain reaction liquid C, where the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.35:1. React at a constant temperature of 38 °C for 2 h, filter, wash, and dry to obtain double-layer coated silica; It and a silane coupling agent are dispersed in an aqueous ethanol solution to obtain dispersion liquid D, where the mass ratio of the silane coupling agent to the double-layer coated silica is 0.05:1. Reflux at a constant temperature of 68 °C for 2.6 h, filter, wash, and dry to obtain multi-layer core-shell structured modified silica;

[0105] S2: Cystamine dihydrochloride is added to an alkaline aqueous solution with a pH of 10.7, stirred, filtered, washed, and dried to obtain a diamine powder; It and polyether diol are added to N,N-dimethylformamide and evenly mixed to obtain dispersion liquid E, where the molar ratio of the diamine powder to the polyether diol is 0.3:1, and the total mass fraction of the diamine powder and the polyether diol in dispersion liquid E is 38 wt.%. It is added dropwise to a 28 wt.% isophorone diisocyanate solution to obtain reaction liquid F, where the molar ratio of isophorone diisocyanate to the total moles of polyether diol and diamine powder is 1.2:1. After refluxing at a constant temperature of 58 °C for 2.8 h under an inert atmosphere, a mixed solution of p-methylbenzaldehyde and hexamethylenediamine is added dropwise to obtain reaction liquid G, where the mass ratio of p-methylbenzaldehyde to hexamethylenediamine is 1:1, the total mass of p-methylbenzaldehyde and hexamethylenediamine is 7% of dispersion liquid E, and the mass fraction of the mixed solution of p-methylbenzaldehyde and hexamethylenediamine is 18 wt.%. After stirring at a constant temperature of 45 °C for 2 h, it is filtered and vacuum distilled to obtain a dynamic self-healing prepolymer;

[0106] S3: Prepare a toluene dispersion of bis(aminopropyl)polydimethylsiloxane with a mass fraction of 35 wt.%. After stirring at a constant temperature of 55 °C under an inert atmosphere, isophorone diisocyanate is added to obtain a first reaction solution, where the mass ratio of isophorone diisocyanate to bis(aminopropyl)polydimethylsiloxane is 0.2:1. After continuing to stir and react for 1.8 h, a mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate with a mass fraction of 20 wt.% is added dropwise to obtain a second reaction solution, where the mass ratio of 1H,1H-perfluorooctyl acrylate to 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 bis(aminopropyl)polydimethylsiloxane. Stir at a constant temperature of 50 °C for 2.5 h, filter, and perform vacuum distillation to obtain a friction-reducing and wear-resistant prepolymer;

[0107] S4: Add polytetrafluoroethylene micropowder, antioxidant 1010, and ultraviolet absorber UV-531 to the polyurethane acrylate matrix, where the feeding amount of polytetrafluoroethylene micropowder is 1.5% of the mass of the polyurethane acrylate matrix, the feeding amount of the antioxidant is 0.4% of the mass of the polyurethane acrylate matrix, and the feeding amount of the 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, where the feeding amount of polyvinyl alcohol is 1% of the mass of the polyurethane acrylate matrix, the feeding amount of polyethylene glycol is 5% of the mass of the polyurethane acrylate matrix, and the feeding amount of glycerol is 2% of the mass of the polyurethane acrylate matrix;

[0108] After uniform dispersion, multilayer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer, and N,N-dimethylbenzylamine are added in sequence. After uniform dispersion, a pretreatment mixture is obtained. After cooling to room temperature, vacuum defoaming is performed, and it is thermally cured at 75 °C for 3.5 h and then placed at room temperature for 23 h for curing to obtain a polymer nanocomposite ice material, where the mass ratio of the polyurethane acrylate matrix, dynamic self-healing prepolymer, multilayer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer, and thermal curing agent is 52:15:10:18:2.

[0109] Example 4

[0110] This example provides a polymer nanocomposite ice material and its preparation method. The preparation method of the polymer nanocomposite ice material specifically includes the following steps:

[0111] S1: Disperse nano-silica in the tea polyphenol solution to obtain dispersion liquid A, where the mass ratio of tea polyphenol to silica is 0.1:1. Adjust its pH to 8.5 with a buffer solution to obtain reaction liquid B. After reacting at room temperature for 12 h, filter, wash, and dry to obtain tea polyphenol-coated silica. Prepare a dispersion liquid of tea polyphenol-coated silica with a mass fraction of 30 wt.%, and add tetrabutyl zirconate dropwise to obtain reaction liquid C, where the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.4:1. React at a constant temperature of 40 °C for 3 h, filter, wash, and dry to obtain double-layer coated silica. Disperse it and a silane coupling agent in an aqueous ethanol solution to obtain dispersion liquid D, where the mass ratio of the silane coupling agent to the double-layer coated silica is 0.1:1. Reflux at a constant temperature of 70 °C for 3 h, filter, wash, and dry to obtain multi-layer core-shell structure modified silica;

[0112] S2: Add cystamine dihydrochloride to an alkaline aqueous solution with a pH of 11, stir, filter, wash, and dry to obtain diamine powder. Add it and polyether diol to N,N-dimethylformamide and mix evenly to obtain dispersion liquid E, where the molar ratio of diamine powder to polyether diol is 0.26:1, and the total mass fraction of diamine powder and polyether diol in dispersion liquid E is 40 wt.%. Drop it into a 30 wt.% isophorone diisocyanate solution to obtain reaction liquid F, where the molar ratio of isophorone diisocyanate to the total moles of polyether diol and diamine powder is 1.12:1. After refluxing at a constant temperature of 60 °C for 3 h under an inert atmosphere, dropwise add a mixed solution of p-methylbenzaldehyde and hexamethylenediamine to obtain reaction liquid G, where the mass ratio of p-methylbenzaldehyde to hexamethylenediamine is 1:1, the total mass of p-methylbenzaldehyde and hexamethylenediamine is 10% of dispersion liquid E, and the mass fraction of the mixed solution of p-methylbenzaldehyde and hexamethylenediamine is 20 wt.%. Stir at a constant temperature of 50 °C for 1.8 h, filter, and perform vacuum distillation to obtain a dynamic self-healing prepolymer;

[0113] S3: Prepare a toluene dispersion liquid of 38 wt.% diaminopropyl polydimethylsiloxane, stir at a constant temperature of 58 °C under an inert atmosphere, and add isophorone diisocyanate to obtain the first reaction liquid, where the mass ratio of isophorone diisocyanate to diaminopropyl polydimethylsiloxane is 0.3:1. Continue to stir and react for 2 h, then dropwise add a 30 wt.% mixed solution H of 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to obtain the second reaction liquid, where the mass ratio of 1H,1H-perfluorooctyl acrylate to 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 liquid of diaminopropyl polydimethylsiloxane. Stir at a constant temperature of 45 °C for 3 h, filter, and perform vacuum distillation to obtain an anti-friction and wear-resistant prepolymer;

[0114] S4: Add polytetrafluoroethylene micropowder, antioxidant 1010, and ultraviolet absorber UV-531 to the polyurethane acrylate matrix. The feeding amount of polytetrafluoroethylene micropowder is 2% of the mass of the polyurethane acrylate matrix, the feeding amount of the antioxidant is 0.5% of the mass of the polyurethane acrylate matrix, and the feeding amount of the light stabilizer is 0.4% of the mass of the polyurethane acrylate matrix. After uniform dispersion, add the dynamic self-healing prepolymer at a constant temperature of 50°C to obtain the first mixture. Disperse polyvinyl alcohol, polyethylene glycol, and glycerol in ethanol to obtain a dispersion solution and add it to the first mixture to obtain the second mixture. The feeding amount of polyvinyl alcohol is 5% of the mass of the polyurethane acrylate matrix, the feeding amount of polyethylene glycol is 1% of the mass of the polyurethane acrylate matrix, and the feeding amount of glycerol is 1.5% of the mass of the polyurethane acrylate matrix;

[0115] After uniform dispersion, add multi-layer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer, and benzoyl peroxide in sequence. After uniform dispersion, obtain the pretreated mixture. After cooling to room temperature, defoam under vacuum and cure thermally at 80°C for 4h, then place at room temperature for 24h for curing to obtain the polymer nano synthetic ice material. The mass ratio of the polyurethane acrylate matrix, dynamic self-healing prepolymer, multi-layer core-shell structured modified silica, friction-reducing and wear-resistant prepolymer, and thermosetting agent is 55:25:14:15:1.

[0116] Comparative Example 1

[0117] This comparative example provides a polymer nano synthetic ice material. The difference from 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 to trimethylolpropane triacrylate is 2:1, and other operation steps and process parameters are exactly the same as those in Example 1.

[0118] Comparative Example 2

[0119] This comparative example provides a polymer nano synthetic ice material. The difference from 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 to trimethylolpropane triacrylate is 0.5:1, and other operation steps and process parameters are exactly the same as those in Example 1.

[0120] Comparative Example 3

[0121] This comparative example provides a polymer nano synthetic ice material. The difference from 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, and other operation steps and process parameters are exactly the same as those in Example 1.

[0122] Comparative Example 4

[0123] This comparative example provides a polymer nano synthetic ice material, which is different from the preparation method of the polymer nano synthetic ice material disclosed in Example 1. In S1, the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is 0.1:1, and other operation steps and process parameters are exactly the same as those in Example 1.

[0124] Comparative Example 5

[0125] This comparative example provides a polymer nano synthetic ice material, which is different from the preparation method of the polymer nano synthetic ice material disclosed in Example 1. In S4, the mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multi-layer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and thermal curing agent is 50:30:12:17:1.8, and other operation steps and process parameters are exactly the same as those in Example 1.

[0126] Comparative Example 6

[0127] This comparative example provides a polymer nano synthetic ice material, which is different from the preparation method of the polymer nano synthetic ice material disclosed in Example 1. In S4, the mass ratio of polyurethane acrylate matrix, dynamic self-healing prepolymer, multi-layer core-shell structure modified silica, friction-reducing and wear-resistant prepolymer and thermal curing agent is 50:10:12:17:1.8, and other operation steps and process parameters are exactly the same as those in Example 1.

[0128] Perform performance tests on the polymer nano synthetic ice materials of the above Examples 1-4 and Comparative Examples 1-6. The specific process is as follows:

[0129] Test the sliding friction coefficient of the polymer nano synthetic ice material according to GB / T 10006-2021;

[0130] Test the hardness of the polymer nano synthetic ice material according to GB / T 531.1-2008;

[0131] Use a universal tensile testing machine to test the tensile strength of the polymer nano synthetic ice material in the initial state and the tensile strength after self-healing (after cutting the ice material, contacting the cut surface and healing at room temperature for 24 h);

[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 the polymer nano synthetic ice materials of Examples 1-4 and Comparative Examples 1-6

[0135]

[0136] From the test results of Example 1 and Comparative Example 1 and Comparative Example 2, it can be seen 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 the sliding friction coefficient dropping to 0.018; at the same time, due to the excessive flexible chain segments of the fluorine component, the internal network structure of the material is damaged, the Shore hardness drops to 68 HD, the tensile strength drops to 11.2 MPa, and 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, the insufficient surface fluorination degree leads to an incomplete formation of the lubricating layer, and the sliding friction coefficient rises to 0.038. Although the increase in rigid cross-linking points raises the Shore hardness to 85 HD and the tensile strength to 14.2, the material becomes brittle as a whole, the self-healing performance deteriorates, and the repair rate is only 84.5%.

[0137] From the test results of Example 1 and Comparative Example 3 and Comparative Example 4, it can be seen that when the mass ratio of tetrabutyl zirconate to tea polyphenol-coated silica is too high, the excessive tetrabutyl zirconate forms a thick coating on the silica surface, resulting in agglomeration between nanoparticles, destroying the uniformity of the material, and causing the sliding friction coefficient to rise to 0.032; although the enhancement of inorganic phase combination raises the Shore hardness to 83 HD, the internal stress concentration of the material causes the tensile strength to drop to 12.3 MPa; the excessive inorganic phase coating restricts the mobility of molecular chains, leading to a decline in self-healing performance; when the mass ratio is too low, the tetrabutyl zirconate coating 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 drops to 73 HD, and the tensile strength drops to 12.2 MPa; due to the moderate surface modification degree, the influence on the sliding friction coefficient and self-healing performance is small.

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

[0139] The above are only specific embodiments 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 thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A preparation method of a polymer nano synthetic ice material, 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-coated silica; react the double-coated silica with a silane coupling agent to obtain multi-layer core-shell structure modified silica; S2: Add cystamine dihydrochloride to an alkaline aqueous solution for treatment to obtain diamine powder; add it and polyether diol to N,N-dimethylformamide to obtain dispersion E, add it to isophorone diisocyanate solution, react, and then add p-methylbenzaldehyde and hexamethylenediamine to react to obtain a dynamic self-healing prepolymer; S3: Add isophorone diisocyanate to the toluene dispersion of diaminopropyl polydimethylsiloxane, react, and then add 1H,1H-perfluorooctyl acrylate and trimethylolpropane triacrylate to react to obtain an antifriction and wear-resistant prepolymer; S4: Add polytetrafluoroethylene micropowder, antioxidant, and light stabilizer to the polyurethane acrylate matrix, uniformly disperse, and then add the dynamic self-healing prepolymer to obtain a first mixture; disperse polyvinyl alcohol, polyethylene glycol, and glycerol in ethanol to obtain a dispersion solution, add it to the first mixture to obtain a second mixture, uniformly disperse, and then sequentially add multi-layer core-shell structure modified silica, antifriction and wear-resistant prepolymer, and heat curing agent and mix. After heat curing and aging, a polymer nano synthetic ice material is obtained.

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

1.

3. The preparation method of 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-coated silica is (0.05 - 0.1):

1.

4. The preparation method of 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 molar ratio of the isophorone diisocyanate to the total molar amount of the polyether diol and the diamine powder is (1 - 1.2):

1.

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

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

1.

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

8. The preparation method of a polymer nano synthetic ice material according to claim 1, characterized in that, In S4: The feeding amount of the polytetrafluoroethylene micropowder is 0.5 - 2% of the mass of the polyurethane acrylate matrix; The antioxidant is antioxidant 1010, and the feeding amount of the antioxidant is 0.1 - 0.5% of the mass of the polyurethane acrylate matrix; The light stabilizer is ultraviolet absorber UV-531, and the feeding amount of the light stabilizer is 0.1 - 0.5% of the mass of the polyurethane acrylate matrix.

9. The preparation method of a polymer nano synthetic ice material according to claim 1, characterized in that, In S4: The feeding amount of the polyvinyl alcohol is 1-5% of the mass of the polyurethane acrylate matrix; The feeding amount of the polyethylene glycol is 1-5% of the mass of the polyurethane acrylate matrix; The feeding amount of the glycerol is 0.5-2% of the mass of the polyurethane acrylate matrix; The thermal curing agent is any one or a combination of two of N,N-dimethylbenzylamine or benzoyl peroxide.

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

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