A fast self-healing dual-network anti-icing organic gel and a preparation method and application thereof

Abstract

The application discloses a kind of quick self-healing double-network anti-icing organic gel and its preparation method and application, using polyurea elastomer crosslinking network and norbornene group fluorine-containing alkyl ester crosslinking network blending preparation, by constructing interpenetrating network, form stable double-network structure.The double-network structure is not easy to be destroyed, not only mechanical performance is superior, also has pressure response effect, namely under stress, lubricant overflow, lubricant can re-enter gel interior in short time after stress removal, can prolong its service life.The application introduces disulfide bond in molecular chain and hydrogen bond between molecular chains, the material has high efficient self-healing efficiency at room temperature, improves the durability of material, simultaneously has excellent anti-icing performance, and has wide application prospect in the field of ice prevention.

Description

Technical Field

[0001] This invention relates to an organic gel, specifically a rapid self-healing dual-network anti-icing organic gel, its preparation method, and its applications. It belongs to the field of functional polymer materials technology. Background Technology

[0002] Icing causes significant harm in human production and daily life. For example, ice on aircraft, power transmission lines, and wind turbine blades not only results in economic losses but also poses a high risk of catastrophic accidents. Traditional active de-icing methods to remove unnecessary ice include chemical de-icing, thermal de-icing, and mechanical de-icing. Examples include spraying antifreeze on aircraft surfaces and spreading salt on highways to melt ice and snow. Manual mechanical de-icing is also used on power transmission lines. However, de-icing processes increase costs, waste energy, and can even have adverse environmental impacts.

[0003] To address this issue, a series of passive anti-icing surfaces have been developed that can repel water, inhibit ice formation, and reduce ice adhesion without requiring external energy input. Passive anti-icing surfaces are mainly divided into three categories: superhydrophobic surfaces, liquid-injected surfaces, and gels. However, in practical applications, once superhydrophobic surfaces freeze, a mechanical chain reaction occurs. Worse still, the surface structure may be damaged during de-icing or abrasion, leading to a loss of anti-icing properties. Liquid-injected surfaces, due to the easy flow of the injected lubricant, are easily removed by ice and water at the interface, resulting in compromised anti-icing properties. Gels, on the other hand, are semi-solid materials composed of at least one cross-linked network and a liquid. They can stably and continuously release and recycle the lubricant in the cross-linked network, exhibiting good durability. They have significant advantages in reducing ice adhesion, inhibiting ice nucleus formation, regulating ice growth, and limiting ice propagation, and are currently among the most promising anti-icing materials.

[0004] In practical applications, anti-icing coatings are often subjected to damage such as friction, cutting, and impact, leading to a decrease in their mechanical properties and increased ice adhesion strength, resulting in a loss of their anti-icing properties. Therefore, endowing anti-icing coatings with self-healing properties is particularly important. Zhang et al. (Small2022, 2206075) developed a self-healing anti-icing coating resistant to extreme environments by integrating fluorinated graphene (FG) into a supramolecular polymer matrix. This coating exhibited an ice shear strength of 48.7 kPa and a tensile strength of less than 0.7 MPa. However, anti-icing coatings that simultaneously possess certain mechanical strength, rapid self-healing properties, and excellent anti-icing resistance are currently rare. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a rapid self-healing dual-network anti-icing organic gel, its preparation method, and its applications. The raw materials used in this invention are readily available, the preparation method is simple to operate, has low technical requirements, and is environmentally friendly and pollution-free, making it suitable for large-scale industrial production and possessing high practical application value.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] 1. A rapid self-healing dual-network anti-icing organic gel, which is obtained by blending a polyurea elastomer crosslinking network and a norbornene-based fluoroalkyl ester crosslinking network; wherein the structural formula of the polyurea elastomer crosslinking network is shown in Formula I:

[0008] Formula I;

[0009] In Formula I, m is a natural number from 20 to 120, n is a natural number from 10 to 100, and the number-average molecular weight is 10,000 to 100,000.

[0010] The structural formula of the norborneol alkenyl fluorinated alkyl ester crosslinking network is shown in Formula II:

[0011]

[0012] Formula II

[0013] In Formula II, a is a natural number from 120 to 420, b is a natural number from 3 to 35, and the number-average molecular weight is 25,000 to 260,000.

[0014] R is selected from any of the following:

[0015] .

[0016] 2. The specific steps of the aforementioned method for preparing a rapid self-healing dual-network anti-icing organic gel are as follows:

[0017] (1) First, a polyurea elastomer crosslinking network was prepared using isophorone diisocyanate and aminopropyl double-terminated polysiloxane as monomers and 2,2-diaminodiphenyl disulfide as a chain extender; the reaction formula is shown in Formula III:

[0018]

[0019] Formula III;

[0020] (2) Then, using norbornene-based fluoroalkyl ester as a monomer, dinorbornene-based isophorone diisocyanate as a crosslinking agent, Grubbs as a catalyst, and dimethyl silicone oil as a lubricant, a norbornene-based fluoroalkyl ester crosslinking network was prepared and blended with a polyurea elastomer crosslinking network; the reaction formula for preparing the norbornene-based fluoroalkyl ester crosslinking network is shown in Formula IV:

[0021]

[0022] Formula IV.

[0023] Preferably, step (1) employs solution polymerization, specifically as follows: isophorone diisocyanate, aminopropyl biterminated polysiloxane, and 2,2-diaminodiphenyl disulfide are dissolved in a solvent, stirred thoroughly, and mixed evenly to obtain isophorone diisocyanate solution with a mass percentage concentration of 10-20%, aminopropyl biterminated polysiloxane solution with a mass percentage concentration of 12-25%, and 2,2-diaminodiphenyl disulfide solution with a mass percentage concentration of 15-25%. Then, under room temperature and a nitrogen atmosphere, the aminopropyl biterminated polysiloxane solution is slowly added dropwise to the isophorone diisocyanate solution. After the addition is complete, the reaction is stirred for 4-6 hours. Then, the 2,2-diaminodiphenyl disulfide solution is slowly added dropwise. After the addition is complete, the reaction is stirred for 6-12 hours. The solvent is tetrahydrofuran.

[0024] More preferably, the molar ratio of the main raw materials is: 50% isophorone diisocyanate, 35-45% aminopropyl dimethylsiloxane, and 5-15% 2,2-diaminodiphenyl disulfide; the weight-average molecular weight of the aminopropyl dimethylsiloxane is 1000-5000.

[0025] Further preferred drying process conditions are: drying in an oven at 60–80°C until constant weight.

[0026] Preferably, in step (2), the norbornene fluoroalkyl ester is selected from any one or more of norbornene trifluoroethyl ester, norbornene tetrafluoropropyl ester, norbornene octafluoropentyl ester, norbornene perfluorobutylhexyl ester, norbornene dodecylfluoroheptyl ester, and norbornene perfluorooctyl ethyl ester.

[0027] Preferably, in step (2), the structural formula of the dinorbornen-isophorone diisocyanate is shown in formula V:

[0028]

[0029] Formula V.

[0030] Preferably, in step (2), the viscosity of the dimethyl silicone oil is 10-1000 mPa·s.

[0031] Preferably, the specific method of step (2) is as follows: first, mix norbornene fluoroalkyl ester, dinorbornene isophorone diisocyanate, polyurea elastomer crosslinking network and dimethyl silicone oil with solvent evenly, then add Grubbs catalyst, mix evenly to obtain polymer solution, cast into shape, stand, dry, and obtain the organic gel.

[0032] More preferably, the amount of dinorbornen-1,4-isophorone diisocyanate is 3-8 wt% of norbornen-1,4-isophorone fluorinated alkyl ester, the amount of Grubbs catalyst is 1-3 wt% of norbornen-1,4-isophorone fluorinated alkyl ester, the amount of polyurea elastomer crosslinking network is 10-1000 wt% of norbornen-1,4-isophorone fluorinated alkyl ester, and the amount of dimethyl silicone oil is 50-200 wt% of the total mass of norbornen-1,4-isophorone fluorinated alkyl ester and polyurea elastomer crosslinking network; the mass percentage concentration of the polymer solution is 40-70%.

[0033] More preferably, the solvent is selected from any one or a mixture of two of dichloromethane, tetrahydrofuran, xylene, chloroform, diethyl ether, acetone, and N,N-dimethylacetamide.

[0034] More preferably, the Grubbs catalyst is selected from any one of Gruubs I, Gruubs II, or Gruubs III.

[0035] A further preferred method involves mixing the gel thoroughly, casting it into a polytetrafluoroethylene mold, allowing it to stand at room temperature for 5–8 hours, and then drying it in an oven at 40–60°C for 4–10 hours until constant weight is achieved to obtain a rapid self-healing dual-network anti-icing organic gel with a gel thickness of 180–220 μm.

[0036] 3. Application of the aforementioned rapid self-healing dual-network anti-icing organic gel in the preparation of anti-icing coatings.

[0037] The beneficial effects of this invention are:

[0038] This invention prepares a rapid self-healing dual-network anti-icing organic gel by blending a polyurea elastomer crosslinking network and a norbornene-based fluorinated alkyl ester crosslinking network. A stable dual-network structure is formed through the construction of an interpenetrating network. This dual-network structure is not easily damaged, exhibiting not only superior mechanical properties but also a pressure-responsive effect. Under stress, the lubricant overflows, and after stress relief, the lubricant can quickly re-enter the gel, extending its service life. By introducing disulfide bonds within the molecular chain and hydrogen bonds between molecular chains, this invention achieves high self-healing efficiency at room temperature, improving the material's durability and providing excellent anti-icing properties, thus showing broad application prospects in the anti-icing field.

[0039] Compared with existing technologies, the advantages of this invention are mainly reflected in the following aspects:

[0040] 1) The rapid self-healing dual-network anti-icing organic gel prepared by this invention has the characteristics of tensile strength of 0.7-4MPa, room temperature treatment for 1-6h, self-repair efficiency of more than 90%, contact angle greater than 100°, and ice shear strength less than 10kPa. Its comprehensive performance is better than most anti-icing materials at present.

[0041] 2) This invention uses a simple method to synthesize a self-healing anti-icing organic gel. The raw materials are readily available, the preparation method is simple and efficient, the reaction conditions are mild and controllable, the gelation time is short, and it is environmentally friendly and pollution-free, which is conducive to large-scale production. Attached Figure Description

[0042] Figure 1 The reaction equation for the synthesis of polyurea elastomer crosslinking networks;

[0043] Figure 2 The reaction equation for the synthesis of norbornene-based fluoroalkyl ester crosslinked networks;

[0044] Figure 3 The structural formula of dinorbornenylisophorone diisocyanate;

[0045] Figure 4 The structural formula of norbornene trifluoroethyl ester;

[0046] Figure 5 The structural formula of norbornene dodecafluoroheptyl ester;

[0047] Figure 6 The NMR spectrum of the polyurea elastomer crosslinked network;

[0048] Figure 7 The NMR spectrum of dinorbornenylisophorone diisocyanate;

[0049] Figure 8 The NMR spectrum of norbornene trifluoroethyl ester;

[0050] Figure 9 The NMR spectrum of norbornenyl dodecafluoroheptyl ester;

[0051] Figure 10 The ice shear strength diagrams are for Examples 1, 2, and 3. Detailed Implementation

[0052] The present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that the following description is only for explaining the present invention and does not limit its content.

[0053] Example 1

[0054] Preparation of polyurea elastomer / norbornene trifluoroethyl ester dual-network anti-icing organic gel

[0055] Preparation of polyurea elastomers:

[0056] Isophorone diisocyanate (0.67 g) was dissolved in 4 ml of tetrahydrofuran and transferred to a 100 ml three-necked flask. The mixture was stirred and purged with nitrogen at room temperature for 30 min. Then, aminopropyl diterminated polysiloxane (2.1 g) with a weight-average molecular weight of 1000 was dissolved in 10 ml of tetrahydrofuran and transferred to a 50 ml constant-pressure dropping funnel. The solution was slowly added dropwise to the three-necked flask, and the reaction was allowed to proceed at room temperature for 6 h after the addition was complete. Next, 2,2-diaminodiphenyl disulfide (0.23 g) was dissolved in 1 ml of tetrahydrofuran and transferred to a 50 ml constant-pressure dropping funnel. The solution was slowly added dropwise to the three-necked flask, and the reaction was allowed to proceed at room temperature for 10 h after the addition was complete. After the reaction was complete, the solution was dried in a 60 °C oven to constant weight, and the solvent was removed. The reaction formula is shown below. Figure 1 See the NMR spectrum. Figure 6 . Figure 6 The proton of -CO-NH- is at a peak at δ(ppm)=7.5, indicating that the polyurea elastomer crosslinking network has been successfully prepared.

[0057] Preparation of norbornene-enyl trifluoroethyl ester:

[0058] 5-norbornene-2-carboxylic acid (13.82 g), trifluoroethanol (9.80 g), trimethylacetic anhydride (TA) (18.80 g), and 4-dimethylaminopyridine (DMAP) (120.12 mg) were added to a 250 ml single-necked flask, followed by 80 ml of tetrahydrofuran (THF). The mixture was stirred at room temperature and purged with nitrogen for 30 min. The temperature was then gradually increased to 60 °C and reacted for 24 h. After cooling to room temperature, the tetrahydrofuran was removed by rotary evaporation under reduced pressure at 40 °C. The resulting product was then transferred to a separatory funnel. Add 30 ml of dichloromethane, wash three times with 100 ml of saturated sodium bicarbonate solution, allowing the mixture to stand for 30 minutes after each wash, and then collect the lower layer. Wash three times with 100 ml of saturated sodium chloride solution, allowing the mixture to stand for 30 minutes after each wash, and then collect the lower layer. Wash three times with 100 ml of distilled water, allowing the mixture to stand for 30 minutes after each wash, and then collect the lower layer. The resulting organic phase is dried overnight with anhydrous magnesium sulfate, filtered, and the solvent is removed by rotary evaporation under reduced pressure at room temperature. After drying at 40 °C, a white viscous liquid is obtained, namely norbornene trifluoroethyl ester, the structural formula of which is shown in [link to structural formula]. Figure 4 See the NMR spectrum. Figure 8 . Figure 8The proton peaks at 0.8 ppm and 1.0 ppm are for the hydrogen in the -CH2- group of the norbornene ring. The double bond signal peak of the norbornene ring is located at 5.8-6.3 ppm, and the proton peaks at 1.9 ppm, 2.9 ppm, and 3.3 ppm are for the -CH group of the norbornene ring. The proton of -O-CH2-CF3 in NF is the peak at δ (ppm) = 4.5, and the proton peaks of the hydrogen in the carboxyl and hydroxyl groups do not appear in the spectrum, proving that norbornene trifluoroethyl ester was successfully prepared.

[0059] Preparation of dinorborneol-enylisophorone diisocyanate:

[0060] At room temperature, 5-norbornen-2-methanol (5 g) was added to a 250 mL three-necked flask, followed by 60 mL of N,N-dimethylacetamide. The mixture was stirred and purged with nitrogen for 30 min at room temperature, then slowly heated to 80 °C. Isophorone diisocyanate (4.45 g) and dibutyltin dilaurate (0.095 g) were dissolved in 10 mL of N,N-dimethylacetamide and transferred to a 50 mL constant-pressure dropping funnel. The solution was then slowly added dropwise to the three-necked flask. After the addition was complete, the reaction was carried out at 80 °C for 24 h. After the reaction was complete, the solvent was removed by vacuum distillation at 80 °C to obtain dinorbornenylisophorone diisocyanate. The structural formula is shown below. Figure 3 See the NMR spectrum. Figure 7 , Figure 7 The proton of -CO-NH- is the peak at δ (ppm) = 7.3, indicating that dinorbornen-isophorone diisocyanate was successfully prepared.

[0061] Preparation of norborneol-based trifluoroethyl ester / polyurea dual-network anti-icing organic gel:

[0062] Norborneol-based trifluoroethyl ester (0.5g), dinorborneol-based isophorone diisocyanate (15mg), polyurea elastomer (5g), and dimethyl silicone oil (10mPa.s) (2.8g) were dissolved in 15ml of tetrahydrofuran and mixed thoroughly. Then, Grubbs II (3mg) purchased from Aladdin was added and mixed thoroughly. The mixture was then cast into a polytetrafluoroethylene mold and left at room temperature for 6 hours. Finally, it was transferred to an oven at 60℃ for 6 hours to obtain a rapid self-healing double-network anti-icing organic gel with a gel thickness of 200μm.

[0063] The reaction formula for preparing the norbornene-based fluoroalkyl ester crosslinking network is shown in [reference needed]. Figure 2 .

[0064] The static water contact angle (CA) of the sample surface was measured using an optical contact angle meter system (Data-physics OCA40). The contact angle was observed and recorded by adding a 2 μL water droplet (injection rate 0.5 μL / s) to the sample surface. Each data point is the average of more than five measurements.

[0065] At room temperature, the double-network gel was stretched at 100 mm / s using an Instron 5569 electronic universal testing machine to measure tensile strength, elongation at break, and elastic modulus (length 50 mm, width 5 mm, thickness 200 ± 20 μm). The self-healing efficiency was calculated as tensile strength after self-healing / initial tensile strength * 100%.

[0066] The sample was placed on a semiconductor thermostat, and then a cylindrical glass tube was placed on the sample surface. 900 μL of deionized water was added to the cylindrical glass tube. Simultaneously, the thermostat temperature was lowered to -20°C at a rate of 2 °C / min under a dry nitrogen gas flow and maintained for 3 hours. Next, the tip of a push-pull gauge (IMADA DST-50N) was moved forward at a speed of 0.5 mm / s, close to the interface between the glass tube and the sample (<1 mm), causing the ice column to detach from the gel surface. The ice shear strength τ was calculated using the following formula:

[0067] τ=F / S

[0068] Where F is the maximum shear force required to remove the icicle from the surface, and S is the contact area between the icicle and the gel surface. All ice shear strength values ​​in this paper are the average of five independent measurements.

[0069] The contact angle of the polyurea elastomer / norborneol-based trifluoroethyl ester dual-network anti-icing organic gel is 102.96°, the ice shear strength is 9.8 kPa, the dimethyl silicone oil overflows under a pressure of 2 kPa and returns to the gel within 5 seconds, the tensile strength is 3.3 MPa, and it self-heals at room temperature for 2 hours after being cut, with the tensile strength recovering to 91.0%.

[0070] Example 2

[0071] Preparation of polyurea elastomer / norbornene dodecafluoroheptyl ester dual-network anti-icing organic gel

[0072] Preparation of polyurea elastomers

[0073] Isophorone diisocyanate (0.67 g) was dissolved in 4 ml of tetrahydrofuran and transferred to a 100 ml three-necked flask. The mixture was stirred and purged with nitrogen at room temperature for 30 min. Then, aminopropyl di-terminated polysiloxane (5.4 g) with a weight-average molecular weight of 3000 was dissolved in 20 ml of tetrahydrofuran and transferred to a 50 ml constant-pressure dropping funnel. The solution was slowly added dropwise to the three-necked flask, and the reaction was allowed to proceed at room temperature for 6 h after the addition was complete. Next, 2,2-diaminodiphenyl disulfide (0.29 g) was dissolved in 2 ml of tetrahydrofuran and transferred to a 50 ml constant-pressure dropping funnel. The solution was slowly added dropwise to the three-necked flask, and the reaction was allowed to proceed at room temperature for 10 h after the addition was complete. Finally, the solution was dried in a 60 °C oven to constant weight to remove the solvent.

[0074] Preparation of norbornene dodecafluoroheptyl ester:

[0075] 5-norbornene-2-carboxylic acid (13.90 g), dodecafluoroheptanol (32.58 g), trimethylacetic anhydride (TA) (19.88 g), and 4-dimethylaminopyridine (DMAP) (119.98 mg) were added to a 250 ml single-necked flask, followed by 80 ml of tetrahydrofuran (THF). The mixture was stirred at room temperature and purged with nitrogen for 30 min. The temperature was then gradually increased to 60 °C and reacted for 24 h. After cooling to room temperature, the tetrahydrofuran was removed by rotary evaporation under reduced pressure at 40 °C. The resulting product was then transferred to a separatory funnel. Add 30 ml of dichloromethane to the container, wash three times with 100 ml of saturated sodium bicarbonate solution, allowing it to stand for 30 min after each wash, and then collect the lower layer. Wash three times with 100 ml of saturated sodium chloride solution, allowing it to stand for 30 min after each wash, and then collect the lower layer. Wash three times with 100 ml of distilled water, allowing it to stand for 30 min after each wash, and then collect the lower layer. The resulting organic phase is dried overnight with anhydrous magnesium sulfate, filtered, and the solvent is removed by rotary evaporation under reduced pressure at room temperature. After drying at 40 °C, a white viscous liquid is obtained, namely norbornenyl dodecafluoroheptyl ester, the structural formula of which is shown in [link to structural formula]. Figure 5 See the NMR spectrum. Figure 9 , Figure 9 The proton peak at 1.0 ppm corresponds to the hydrogen atom in the -CH2- group of the norbornene ring; the peaks at 1.9 ppm, 2.9 ppm, and 3.3 ppm correspond to the hydrogen atom in the -CH- group of the norbornene ring; and the peak at 6.2 ppm corresponds to the hydrogen atom in the double bond of the norbornene ring. Furthermore, the proton peaks at the carboxyl and hydroxyl groups did not appear in the spectrum, indicating that the hydroxyl and carboxyl groups were completely consumed, and norbornene dodecafluoroheptyl ester was successfully prepared.

[0076] The preparation of dinorbornene isophorone diisocyanate is the same as in Example 1.

[0077] Preparation of polyurea elastomer / norbornene dodecafluoroheptyl ester dual-network anti-icing organic gel:

[0078] The following ingredients were dissolved in 3 ml of tetrahydrofuran: norbornel-dodecylfluoroheptyl ester (0.5 g), dinorbornel-isophorone diisocyanate (40 mg), polyurea elastomer (0.05 g), and dimethyl silicone oil (50 mPa.s) (1.0 g). The mixture was thoroughly mixed, and then Grubbs II (2.8 mg) purchased from Aladdin was added. The mixture was then cast into a polytetrafluoroethylene mold and left at room temperature for 6 h. After being transferred to an oven at 60 °C for 6 h, a rapid self-healing double-network anti-icing organic gel with a gel thickness of 200 μm was obtained.

[0079] The contact angle, ice shear strength, mechanical properties and self-healing efficiency of the dual-network gel were tested using the methods described in Example 1.

[0080] The contact angle of the dual-network gel is 105.84°, the ice shear strength is 8.5 kPa, the dimethyl silicone oil overflows under a pressure of 1.8 kPa and returns to the gel within 5 seconds, the tensile strength is 0.7 MPa, and it self-heals at room temperature for 3 hours after being cut, with the tensile strength recovering to 95.3%.

[0081] Example 3

[0082] Preparation of polyurea elastomer / norbornene trifluoroethyl ester copolymerized norbornene dodecafluoroheptyl ester dual-network anti-icing organic gel

[0083] Preparation of polyurea elastomers

[0084] Isophorone diisocyanate (0.67 g) was dissolved in 4 ml of tetrahydrofuran and transferred to a 100 ml three-necked flask. The mixture was stirred and purged with nitrogen at room temperature for 30 min. Then, aminopropyl di-terminated polysiloxane (8.2 g) with a weight-average molecular weight of 3000 was dissolved in 30 ml of tetrahydrofuran and transferred to a 50 ml constant-pressure dropping funnel. The solution was slowly added dropwise to the three-necked flask, and the reaction was allowed to proceed at room temperature for 6 h after the addition was complete. Next, 2,2-diaminodiphenyl disulfide (0.08 g) was dissolved in 1 ml of tetrahydrofuran and transferred to a 50 ml constant-pressure dropping funnel. The solution was slowly added dropwise to the three-necked flask, and the reaction was allowed to proceed at room temperature for 10 h after the addition was complete. Finally, the solution was dried in a 60 °C oven to constant weight to remove the solvent.

[0085] The preparation of norbornene trifluoroethyl ester is the same as in Example 1.

[0086] The preparation of norbornene dodecafluoroheptyl ester is the same as in Example 1.

[0087] The preparation of dinorbornene isophorone diisocyanate is the same as in Example 1.

[0088] Preparation of a polyurea elastomer / norbornene-trifluoroethyl ester copolymerized norbornene-dodecylfluoroheptyl ester dual-network anti-icing organic gel:

[0089] Norbornel trifluoroethyl ester (0.2g), norbornel dodecafluoroheptyl ester (0.3g), dinorbornel isophorone diisocyanate (25mg), polyurea elastomer (0.5g), and dimethyl silicone oil (50mPa.s) (0.5g) were dissolved in 3ml of tetrahydrofuran and mixed evenly. Then, Grubbs II (3.87mg) purchased from Aladdin was added and mixed evenly. The mixture was then cast into a polytetrafluoroethylene mold and left at room temperature for 6 hours. After being transferred to an oven at 60℃ for 6 hours, a rapid self-healing double-network anti-icing organic gel with a gel thickness of 200μm was obtained.

[0090] The contact angle, ice shear strength, mechanical properties and self-healing efficiency of the dual-network gel were tested using the methods described in Example 1.

[0091] The contact angle of the dual-network gel is 108.37°, the ice shear strength is 7.93 kPa, the dimethyl silicone oil overflows under a pressure of 1.6 kPa and returns to the gel within 5 seconds, the tensile strength is 3.99 MPa, and it self-heals at room temperature for 1.5 hours after being cut, with the tensile strength recovering to 98.8%.

[0092] Figure 10 The ice shear strength diagrams for Examples 1, 2, and 3 are shown in Figure 1; Table 1 shows the mechanical properties and self-healing efficiency of Examples 1, 2, and 3. Figure 10 As can be seen from Table 1,

[0093] Table 1. Mechanical properties and self-healing efficiency of dual-network gels

[0094] Elastic modulus (MPa) Elongation at break (%) Tensile strength (MPa) Self-healing efficiency (%) Example 1 3.00 596.88 3.30 91.00 Example 2 0.77 524.18 0.70 95.30 Example 3 3.50 690.00 3.99 98.80

[0095] While the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, this is not intended to limit the scope of protection of the present invention. Based on the technical solutions of the present invention, various modifications or variations that can be made by those skilled in the art without creative effort are still within the scope of protection of the present invention.

Claims

1. A fast self-healing dual-network anti-icing organic gel, characterized in that, It is obtained by blending a polyurea elastomer crosslinking network and a norbornene-based fluoroalkyl ester crosslinking network; wherein, the structural formula of the polyurea elastomer crosslinking network is shown in Formula I: Formula I; In Formula I, m is a natural number from 20 to 120, n is a natural number from 10 to 100, and the number-average molecular weight is 10,000 to 100,000. The structural formula of the norborneol alkenyl fluorinated alkyl ester crosslinking network is shown in Formula II: Formula II In Formula II, a is a natural number from 120 to 420, b is a natural number from 3 to 35, and the number-average molecular weight is 25,000 to 260,000. R is selected from any one of the following: trifluoroethyl ester, tetrafluoropropyl ester, octafluoropentyl ester, perfluorobutylhexyl ester, dodecylfluoroheptyl ester, perfluorooctylethyl ester; The specific steps for preparing this organic gel are as follows: (1) First, a polyurea elastomer crosslinking network was prepared using isophorone diisocyanate and aminopropyl double-terminated polysiloxane as monomers and 2,2-diaminodiphenyl disulfide as a chain extender; the reaction formula is shown in Formula III: Formula III; (2) Then, using norbornene-based fluoroalkyl ester as a monomer, dinorbornene-based isophorone diisocyanate as a crosslinking agent, Grubbs as a catalyst, and dimethyl silicone oil as a lubricant, a norbornene-based fluoroalkyl ester crosslinking network was prepared and blended with a polyurea elastomer crosslinking network; the reaction formula for preparing the norbornene-based fluoroalkyl ester crosslinking network is shown in Formula IV: Formula IV.

2. The method for preparing a rapid self-healing dual-network anti-icing organic gel according to claim 1, characterized in that, The specific steps are as follows: (1) First, a polyurea elastomer crosslinking network was prepared using isophorone diisocyanate and aminopropyl double-terminated polysiloxane as monomers and 2,2-diaminodiphenyl disulfide as a chain extender; the reaction formula is shown in Formula III: Formula III; (2) Then, using norbornene-based fluoroalkyl ester as a monomer, dinorbornene-based isophorone diisocyanate as a crosslinking agent, Grubbs as a catalyst, and dimethyl silicone oil as a lubricant, a norbornene-based fluoroalkyl ester crosslinking network was prepared and blended with a polyurea elastomer crosslinking network; the reaction formula for preparing the norbornene-based fluoroalkyl ester crosslinking network is shown in Formula IV: Formula IV.

3. The preparation method according to claim 2, characterized in that, Step (1) employs solution polymerization, specifically as follows: Isophorone diisocyanate, aminopropyl biterminated polysiloxane, and 2,2-diaminodiphenyl disulfide are dissolved in a solvent, stirred thoroughly, and mixed evenly to obtain isophorone diisocyanate solution with a mass percentage concentration of 10-20%, aminopropyl biterminated polysiloxane solution with a mass percentage concentration of 12-25%, and 2,2-diaminodiphenyl disulfide solution with a mass percentage concentration of 15-25%. Then, under room temperature and a nitrogen atmosphere, the aminopropyl biterminated polysiloxane solution is slowly added dropwise to the isophorone diisocyanate solution. After the addition is complete, the reaction is stirred for 4-6 hours. Then, the 2,2-diaminodiphenyl disulfide solution is slowly added dropwise, and the reaction is stirred for 6-12 hours after the addition is complete. The solvent is tetrahydrofuran.

4. The preparation method according to claim 2, characterized in that, In step (2), the norbornel fluoroalkyl ester is selected from any one or more of norbornel trifluoroethyl ester, norbornel tetrafluoropropyl ester, norbornel octafluoropentyl ester, norbornel perfluorobutylhexyl ester, norbornel dodecafluoroheptyl ester, and norbornel perfluorooctylethyl ester.

5. The preparation method according to claim 2, characterized in that, In step (2), the viscosity of the dimethyl silicone oil is 10-1000 mPa·s.

6. The preparation method according to claim 2, characterized in that, The specific method of step (2) is as follows: first, mix norbornene fluoroalkyl ester, dinorbornene isophorone diisocyanate, polyurea elastomer crosslinking network and dimethyl silicone oil with solvent evenly, then add Grubbs catalyst, mix evenly to obtain polymer solution, cast into shape, stand, dry, and obtain the organic gel.

7. The application of the rapid self-healing dual-network anti-icing organic gel of claim 1 in the preparation of anti-icing coatings.

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