Deep eutectic ionic gel with anti-swelling property, preparation method and application thereof

Abstract

The application discloses a deep eutectic ionic gel with anti-swelling property and a preparation method and application thereof. The preparation method of the deep eutectic ionic gel with anti-swelling property comprises the following steps: preparing a deep eutectic solvent; then mixing a hydrophobic monomer, a comonomer, the deep eutectic solvent prepared in step S1, a crosslinking agent and a photoinitiator to obtain a mixed solution, stirring, pouring the pre-polymer solution into a mold, solidifying, demolding and obtaining the deep eutectic ionic gel; the hydrophobic monomer comprises lauryl methacrylate, and the comonomer comprises glycidyl methacrylate. The deep eutectic ionic gel prepared by the application has high mechanical strength and excellent anti-swelling property, and also has good self-healing, antibacterial and anti-fatigue properties, thereby providing a new direction and candidate material for the development of flexible electronic devices in harsh environments such as high humidity and underwater.

Description

Technical Field

[0001] This invention relates to the field of gel preparation technology, and in particular to a deep eutectic ionic gel with anti-swelling properties, its preparation method, and its application. Background Technology

[0002] In recent years, with the rapid development of flexible electronics and wearable devices, flexible ionic conductive gels with high ionic conductivity, excellent environmental tolerance, and multiple functions have become a key research focus in the field of intelligent sensing and energy conversion. However, the inherent physical defects of conventional hydrogels limit their applications. They are prone to freezing at low temperatures and dehydration at high temperatures or in dry conditions, making it difficult for them to maintain long-term stable performance in complex and changing external environments. To overcome this bottleneck, ionic gels have come into focus due to their excellent thermal stability and anti-volatility. However, traditional ionic gels often rely on organic ionic liquids as solvents, which inevitably leads to drawbacks such as potential liquid leakage, biotoxicity, and high raw material costs, severely restricting their practical application in wearable devices.

[0003] In contrast, deep eutectic solvents (DES) exhibit significant advantages as a substitute. They are formed by the spontaneous association of hydrogen bond acceptors (HBA) and donors (HBD) via hydrogen bond networks, Lewis acid-base coordination, and ion-dipole interactions. This solvent not only has a significantly lower melting point than either component but also possesses excellent properties such as being environmentally friendly, having a simple preparation process, being cost-effective, and exhibiting good thermal stability. Currently, deep eutectic ionogels constructed using deep eutectic solvents as a substrate have become a research hotspot in this field. However, one problem urgently needs to be addressed: most monomers in existing systems have a hydrophilic tendency, and once exposed to moisture or water, they will absorb water and swell, leading to a significant decrease in the material's mechanical properties and severely shortening the device's lifespan. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a deep eutectic ionic gel with anti-swelling properties, its preparation method, and its applications. This invention prepares a deep eutectic solvent through specific terpene alcohols and phenolic compounds, and constructs a hydrophobic polymer network by crosslinking lauryl methacrylate and glycidyl methacrylate. The prepared gel exhibits excellent anti-swelling properties, improving its service life in humid or aquatic environments, while also possessing superior mechanical properties.

[0005] The technical solution of the present invention is as follows: The first aspect of this invention provides a method for preparing a deep eutectic ionogel with anti-swelling properties, comprising the following steps: S1: Solvent for preparing deep eutectic crystals; S2: Mix the hydrophobic monomer, comonomer, deep eutectic solvent prepared in step S1, crosslinking agent and photoinitiator to obtain a mixture, stir, and obtain deep eutectic ion gel prepolymer solution; S3: Pour the deep eutectic ion gel prepolymer from step S2 into a mold, solidify, and demold to obtain the deep eutectic ion gel; In S2, the hydrophobic monomer includes lauryl methacrylate, and the comonomer includes glycidyl methacrylate.

[0006] Preferably, in S1, the method for preparing the deep eutectic solvent includes: mixing a cyclic terpene compound with a phenolic compound, and then repeatedly heating and stirring until a transparent and homogeneous solution is obtained.

[0007] Preferably, the cyclic terpene compounds include at least one of menthol, isomenthol, borneol, and isoborneol; and the phenolic compounds include at least one of thymol, carvacrol, and eugenol.

[0008] Preferably, the molar ratio of the cyclic terpene compound to the phenolic compound is 0.8~1.2:1; When heating and stirring repeatedly, the temperature for each heating is 50~70℃, and / or the heating time for each heating is 20min; and / or the stirring time for each stirring is 10min.

[0009] Preferably, in S2, the mass ratio of the hydrophobic monomer to the comonomer is 1:4 to 3:2, more preferably 2:3.

[0010] Preferably, in step S2, the mass percentage of the deep eutectic solvent prepared in step S1 in the mixture is 3-20%. The total mass ratio of the hydrophobic monomer and the comonomer to the crosslinking agent is 2:0.1~0.3; The total mass ratio of the hydrophobic monomer and the comonomer to the crosslinking agent is 2:0.05~0.25; The crosslinking agent includes at least one of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,6-hexanediol diacrylate. The initiator includes at least one of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, and ethyl 2,4,6-trimethylbenzoylphosphonate; The stirring time is 5 to 30 minutes.

[0011] Preferably, in S3, the curing is ultraviolet curing, and the curing time is 5~30 minutes.

[0012] A second aspect of the present invention provides a deep eutectic ionogel with anti-swelling properties prepared by the preparation method described in the first aspect above.

[0013] A third aspect of the present invention provides a method for preparing fibers with an anti-swelling deep eutectic ionogel coating, comprising the following steps: (1) Fiber surface pretreatment; (2) A deep eutectic ionogel prepolymer solution is prepared according to the preparation method described in the first aspect above; (3) Immerse the fiber surface-treated in step (1) into the gel prepolymer solution in step (2). After 0.5~5 min, pull it out at a speed of 0.5~5 cm / min and perform cross-linking polymerization to obtain fiber with anti-swelling deep eutectic ion gel coating. In step (1), the fiber includes zirconium oxide fiber; The cross-linking polymerization is carried out under ultraviolet light; The thickness of the anti-swelling deep eutectic ionogel coating is 0.05~2mm.

[0014] The fourth aspect of the present invention provides a fiber with an anti-swelling deep eutectic ionogel coating prepared by the preparation method described in the third aspect above.

[0015] The beneficial technical effects of this invention are as follows: This invention synthesizes hydrophobic deep eutectic solvents from natural monoterpenes and phenols. Through optimization of hydrophobic and polymeric monomers, using lauryl methacrylate with a long carbon chain as the hydrophobic monomer and glycidyl methacrylate as the comonomer, a hydrophobic deep eutectic ionic gel with high mechanical strength and excellent anti-swelling properties was successfully prepared. Furthermore, the gel prepared by this invention also exhibits excellent self-healing, antibacterial, and fatigue-resistant properties, providing a new direction and candidate material for the development of flexible electronic devices in harsh environments such as high humidity / underwater environments. Attached Figure Description

[0016] Figure 1 This is a schematic diagram illustrating the synthesis reaction principle of the deep eutectic solvent of this invention.

[0017] Figure 2 Infrared spectra of the deep eutectic solvent, thymol, and menthol raw materials prepared in Example 3 of this invention; In the figure, (a) is thymol, (b) is menthol, and (c) is a deep eutectic solvent.

[0018] Figure 3 The infrared spectrum (a) of the DES prepared in Example 3 of this invention, the raw materials GMA and LMA, and the deep eutectic ion gel MTLG prepared in Examples 3, 6 and 7, and the SEM (b) of the eutectic ion gel MTLG prepared in Example 3.

[0019] Figure 4The XRD patterns are of deep eutectic ionogels MTLG prepared with different DES contents in Examples 3 and 6-9 of this invention.

[0020] Figure 5 The MTLG stress-strain curves of deep eutectic ionogels prepared with different monomer ratios in Examples 1-5 and Comparative Example 1 of this invention.

[0021] Figure 6 Stress-strain curves of deep eutectic ionogels (MTLG) prepared with different crosslinking agent contents in Examples 3 and 10-13 of this invention.

[0022] Figure 7 Stress-strain curves of deep eutectic ionogels MTLG prepared with different DES contents in Examples 3 and 6-9 of this invention.

[0023] Figure 8 Stress-strain curves of deep eutectic ionogels MTLG prepared with different photoinitiators in Examples 3 and 14-17 of this invention.

[0024] Figure 9 Stress-strain curves of deep eutectic ionogels (MTLG) prepared at different curing times in Examples 3 and 18-21 of this invention.

[0025] Figure 10 The deep eutectic ionogel MTLG prepared in Example 3 of this invention was subjected to continuous tensile-unloading cycle tests under different strains (50% to 250%).

[0026] Figure 11 The continuous stretching-unloading cycle curve of the deep eutectic ionogel MTLG prepared in Example 3 of the present invention after soaking in water for 24 hours.

[0027] Figure 12 The continuous stretching-unloading cycle curve of the deep eutectic ionogel MTLG prepared in Example 3 of the present invention after soaking in water for 48 hours.

[0028] Figure 13 The stretch-unloading curves of the deep eutectic ionogel MTLG prepared in Example 3 of the present invention at different recovery times under 100% strain.

[0029] Figure 14 The loading-unloading curve of the deep eutectic ionogel MTLG prepared in Example 3 of the present invention after 20 cycles at 100% strain.

[0030] Figure 15 The adhesion performance test results are for the deep eutectic ionogel MTLG prepared in Example 3 of this invention. Where: a) are the test results of adhesion strength on different material surfaces; b) are the adhesion retention rate diagrams after multiple attach-remove cycles on different material surfaces.

[0031] Figure 16 Test of the self-healing properties of the deep eutectic ionogel MTLG prepared in Example 3 of this invention; In the figure: (a) is a comparison of the length of the sample before and after stretching; (b) is a microscopic observation of the self-healing process of the sample; (c) is the tensile stress-strain curve of the sample after different self-healing times.

[0032] Figure 17 The antibacterial properties of the deep eutectic ionogel MTLG prepared in Example 3 of this invention.

[0033] Figure 18 The antioxidant properties of the deep eutectic ionogel MTLG prepared in Example 3 of this invention.

[0034] In the figure: ad represents the surface condition of the sample at different times.

[0035] Figure 19 The changes in the surface of the deep eutectic ionogel MTLG prepared in Example 3 of this invention after standing for 7 days at 20 °C and 65% RH are shown in (a) and (b).

[0036] In the figure: (a) From left to right, the changes in gel surface after standing for 0 days, 1 day, 2 days, 3 days, 5 days, and 7 days; (b) The changes in gel weight over the number of days.

[0037] Figure 20 The effects of monomer ratio, crosslinking agent, DES, photoinitiator, and curing time on the swelling resistance of deep eutectic ionogel MTLG. Detailed Implementation

[0038] The present invention will now be described in detail with reference to the embodiments.

[0039] To address the problems of existing gels, this invention first provides a deep eutectic ionogel, the preparation method of which includes the following steps: S1: Solvent for preparing deep eutectic crystals; S2: Mix the hydrophobic monomer, comonomer, deep eutectic solvent prepared in step S1, crosslinking agent and photoinitiator to obtain a mixture, stir, and obtain deep eutectic ion gel prepolymer solution; S3: Pour the deep eutectic ion gel prepolymer from step S2 into a mold, solidify, and demold to obtain the deep eutectic ion gel; In S2, the hydrophobic monomer includes lauryl methacrylate, and the comonomer includes glycidyl methacrylate.

[0040] In some embodiments, in S1, the method for preparing the deep eutectic solvent includes: mixing a cyclic terpene compound with a phenolic compound, and then repeatedly heating and stirring until a transparent and homogeneous solution is obtained.

[0041] In some embodiments, the cyclic terpene compounds include at least one of menthol, isomenthol, borneol, and isoborneol; the phenolic compounds include at least one of thymol, carvacrol, and eugenol.

[0042] Figure 1 A schematic diagram illustrating the synthesis reaction principle of the deep eutectic solvent described in one embodiment of the present invention is provided.

[0043] The present invention further prepares continuous zirconia fibers with an anti-swelling deep eutectic ionogel coating by applying the deep eutectic ionogel to the fiber surface.

[0044] In some embodiments of the present invention, the method for preparing the fiber with the anti-swelling deep eutectic ionogel coating includes the following steps: (1) Fiber surface pretreatment; (2) A deep eutectic ionogel prepolymer solution is prepared according to the preparation method described in the first aspect above; (3) Immerse the fiber surface-treated in step (1) into the gel prepolymer solution in step (2). After 0.5~5 min, pull it out at a speed of 0.5~5 cm / min and perform cross-linking polymerization to obtain fiber with anti-swelling deep eutectic ion gel coating. In some embodiments, in step (1), the fiber comprises zirconium oxide fiber; In some embodiments, in step (1), the fiber surface pretreatment method is as follows: the continuous zirconia fiber is washed sequentially with anhydrous ethanol and deionized water, dried, and then placed in an alcohol-water mixed solution containing silane coupling agent for surface coupling treatment. After being taken out, it is washed and dried to obtain surface-activated continuous zirconia fiber.

[0045] In some embodiments, the silane coupling agent-containing alcohol-water mixed solution is obtained by mixing 1.0-3.0 wt% silane coupling agent, 2-5 wt% deionized water, and 92-97 wt% anhydrous ethanol, adjusting the pH to 3.5-5.5, and coupling for 0.5-2 h.

[0046] In some embodiments, the silane coupling agent includes one or more of KH-570, KH-550, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.

[0047] In some embodiments, the crosslinking polymerization is carried out under ultraviolet light.

[0048] The ultraviolet light conditions are: ultraviolet light wavelength of 365 nm, irradiation intensity of 50~150 W, and irradiation time of 2~20 min; preferably, the irradiation intensity is 80 W and the irradiation time is 6~10 min.

[0049] In some embodiments, the thickness of the anti-swelling deep eutectic ionogel coating is 0.05~2 mm.

[0050] The continuous zirconia fiber with anti-swelling deep eutectic ion gel coating prepared by the present invention can be used in the preparation of three-dimensional weaving, lay-up, winding, high-temperature resistant thermal insulation fabrics or ceramic fiber reinforced composite preforms.

[0051] Unless otherwise specified, the reagents and detection methods used in this invention are all conventional methods in the field.

[0052] The present invention will be further described below with reference to embodiments and other examples.

[0053] Example 1 The preparation method of deep eutectic ionogel includes the following steps: (1) Preparation of deep eutectic solvent (DES) Weigh 10.2 g of menthol and 9.8 g of thymol into the original reagent bottle, place them in a 60 ℃ oven and heat for 20 min, then remove and stir for 10 min; place them in a 60 ℃ oven again and heat for 10 min, then remove and continue stirring for 10 min, until a homogeneous and transparent DES solution is formed.

[0054] (2) Preparation of deep eutectic ionogel MTLG Accurately weigh each component according to the formula: 0.4 g lauryl methacrylate (LMA), 1.6 g glycidyl methacrylate (GMA), 0.15 g deep eutectic solvent, 0.2 g polyethylene glycol diacrylate (PEGDA), and 0.15 g 1-hydroxycyclohexyl benzophenone (P-184). Add the above materials to a small beaker in sequence, then place the weighed mixture on a magnetic stirrer and stir at room temperature for 10 min until all components are completely dissolved and a homogeneous and transparent prepolymer solution is formed.

[0055] (3) Pour the prepolymer liquid into the mold to a thickness of about 1.5 mm, and place it in a UV curing oven for 20 min to allow the monomers to fully crosslink and polymerize. After curing, a deep eutectic ionogel is obtained. Carefully peel the gel off the mold, place it in a sealed bag, and store it at room temperature for later use. The UV curing is performed under 365 nm, 80 W UV light.

[0056] Irradiation under ultraviolet light source.

[0057] Example 2 The preparation method of deep eutectic ionogel includes the following steps: (1) Preparation of deep eutectic solvent (DES) The preparation method and conditions are the same as in Example 1.

[0058] (2) Preparation of deep eutectic ionogel MTLG Accurately weigh each component according to the formula: 0.6 g lauryl methacrylate (LMA), 1.4 g glycidyl methacrylate (GMA), 0.15 g deep eutectic solvent, 0.2 g polyethylene glycol diacrylate (PEGDA), and 0.15 g 1-hydroxycyclohexyl benzophenone (P-184). Add the above materials to a small beaker in sequence, then place the weighed mixture on a magnetic stirrer and stir at room temperature for 10 min until all components are completely dissolved and a homogeneous and transparent prepolymer solution is formed.

[0059] (3) Pour the solution into the mold to a thickness of about 1.5 mm, and place it in a UV curing oven for 20 min to cure, so that the monomers can be fully crosslinked and polymerized. After curing, a deep eutectic ionogel is obtained. Carefully peel the gel off the mold, put it in a sealed bag and store it at room temperature for later use. The UV curing is performed under 365 nm, 80 W UV light.

[0060] Example 3 The preparation method of deep eutectic ionogel includes the following steps: (1) Preparation of deep eutectic solvent (DES) The preparation method and conditions are the same as in Example 1.

[0061] (2) Preparation of deep eutectic ionogel MTLG Accurately weigh each component according to the formula: 0.8 g lauryl methacrylate (LMA), 1.2 g glycidyl methacrylate (GMA), 0.15 g deep eutectic solvent, 0.2 g polyethylene glycol diacrylate (PEGDA), and 0.15 g 1-hydroxycyclohexyl benzophenone (P-184). Add the above materials sequentially to a small beaker. Then place the weighed mixture on a magnetic stirrer and stir at room temperature for 10 min until all components are completely dissolved and a homogeneous and transparent prepolymer solution is formed.

[0062] (3) Pour the prepolymer liquid into the mold to a thickness of about 1.5 mm, and place it in a UV curing oven for 20 min to allow the monomers to fully crosslink and polymerize. After curing, carefully peel the gel off the mold to obtain a deep eutectic ionogel, and store it in a sealed bag at room temperature for later use. The UV curing was performed under 365 nm, 80 W UV light.

[0063] Figure 2 Infrared spectra of the deep eutectic solvent, thymol, and menthol raw materials prepared in Example 3 are given. As can be seen from the figures, both thymol and menthol exhibit characteristic absorption peaks of the hydroxyl group, with peaks appearing in the 3200–3500 cm⁻¹ region after the formation of the deep eutectic solvent. -1 The OH stretching vibration peaks within the range broadened significantly and shifted, indicating that a stable hydrogen bond was formed between thymol and menthol. Meanwhile, no new impurity peaks appeared in the obtained deep eutectic solvent, indicating that the system mainly forms a uniform and stable deep eutectic structure through intermolecular interactions.

[0064] Example 4 The preparation method of deep eutectic ionogel includes the following steps: (1) Preparation of deep eutectic solvent (DES) The preparation method and conditions are the same as in Example 1.

[0065] (2) Preparation of deep eutectic ionogel MTLG Accurately weigh each component according to the formula: 1g lauryl methacrylate (LMA), 1g glycidyl methacrylate (GMA), 0.15g deep eutectic solvent, 0.2g polyethylene glycol diacrylate (PEGDA), and 0.15g 1-hydroxycyclohexyl benzophenone (P-184). Add the above materials sequentially to a small beaker. Then place the weighed mixture on a magnetic stirrer and stir at room temperature for 10 minutes until all components are completely dissolved and a homogeneous and transparent prepolymer solution is formed.

[0066] (3) Pour the prepolymer liquid into the mold to a thickness of about 1.5 mm, and place it in a UV curing oven for 20 min to allow the monomers to fully crosslink and polymerize. After curing, a deep eutectic ionogel is obtained. Carefully peel the gel off the mold, place it in a sealed bag, and store it at room temperature for later use. The UV curing is performed under 365 nm, 80 W UV light.

[0067] Example 5 The preparation method of deep eutectic ionogel includes the following steps: (1) Preparation of deep eutectic solvent (DES) The process is the same as in Example 1.

[0068] (2) Preparation of deep eutectic ionogel MTLG Accurately weigh each component according to the formula: 1.2 g lauryl methacrylate, 0.8 g glycidyl methacrylate (GMA), 0.15 g deep eutectic solvent, 0.2 g polyethylene glycol diacrylate (PEGDA), and 0.15 g 1-hydroxycyclohexyl benzophenone (P-184). Add the above materials sequentially to a small beaker. Then place the weighed mixture on a magnetic stirrer and stir at room temperature for 10 min until all components are completely dissolved and a homogeneous and transparent prepolymer solution is formed.

[0069] (3) Pour the prepolymer liquid into the mold to a thickness of about 1.5 mm, and place it in a UV curing oven for 20 min to allow the monomers to fully crosslink and polymerize. After curing, a deep eutectic ionogel is obtained. Carefully peel the gel off the mold, place it in a sealed bag, and store it at room temperature for later use. The UV curing is performed under 365 nm, 80 W UV light.

[0070] Comparative Example 1 It is basically the same as Example 3, except that in step (2), the total mass of LMA and GMA is 2.0g, and the mass ratio of LMA to GMA is 1:9.

[0071] Example 6 It is basically the same as Example 3, except that in step (2), the amount of deep eutectic solvent DES added is 3% of the total amount of the mixture.

[0072] Example 7 It is basically the same as Example 3, except that in step (2), the amount of deep eutectic solvent DES added is 9% of the total amount of the mixture.

[0073] Example 8 It is basically the same as Example 3, except that in step (2), the amount of deep eutectic solvent DES added is 12% of the total amount of the mixture.

[0074] Example 9 It is basically the same as Example 3, except that in step (2), the amount of deep eutectic solvent DES added is 15% of the total amount of the mixture.

[0075] Comparative Example 2 It is basically the same as Example 3, except that DES is not added.

[0076] Figure 3 Figure a shows the infrared spectra of the DES prepared in Example 3 of this invention, the raw materials GMA and LMA, and the deep eutectic ion gel MTLG prepared in Examples 3, 6 and 7. Figure 3Figure b shows the SEM image of the deep eutectic ionogel MTLG prepared in Example 3 of this invention. As can be seen from Figure a, the carbon-carbon double bond-related absorption peaks in GMA and LMA significantly weaken or disappear after gel formation, while characteristic peaks such as the C=O peaks of the ester group are still retained, indicating that the monomers undergo cross-linking polymerization under UV initiation to form a gel network. Figure b shows that the deep eutectic ionogel prepared in Example 3 exhibits a relatively continuous, dense, and uniform microstructure, which is beneficial for improving the mechanical strength and anti-swelling stability of the gel.

[0077] Figure 4 XRD patterns of deep eutectic gels prepared with different DES contents are presented. As shown in the figures, the gel prepared in this invention exhibits good stability. Furthermore, the thermal stability of the gel was also investigated, and the results indicate that the gel prepared in this invention also possesses excellent thermal stability.

[0078] Example 10 It is basically the same as Example 3, except that in step (2), the amount of crosslinking agent is 0.1g.

[0079] Example 11 It is basically the same as Example 3, except that in step (2), the amount of crosslinking agent is 0.15g.

[0080] Example 12 It is basically the same as Example 3, except that in step (2), the amount of crosslinking agent is 0.25g.

[0081] Example 13 It is basically the same as Example 3, except that in step (2), the amount of crosslinking agent is 0.3g.

[0082] Example 14 It is basically the same as Example 3, except that in step (2), the amount of photoinitiator is 0.05g.

[0083] Example 15 It is basically the same as Example 3, except that in step (2), the amount of photoinitiator is 0.1g.

[0084] Example 16 It is basically the same as Example 3, except that in step (2), the amount of photoinitiator is 0.2g.

[0085] Example 17 It is basically the same as Example 3, except that in step (2), the amount of photoinitiator is 0.25g.

[0086] Example 18 It is basically the same as Example 3, except for the curing time in step (3). In this example, the curing time is 30 min.

[0087] Example 19 It is basically the same as Example 3, except for the curing time in step (3). In this example, the curing time is 25 min.

[0088] Example 20 It is basically the same as Example 3, except for the curing time in step (3). In this example, the curing time is 15 min.

[0089] Example 21 It is basically the same as Example 3, except for the curing time in step (3). In this example, the curing time is 10 min.

[0090] Example 22 It is basically the same as Example 3, except that in step (2), the amount of deep eutectic solvent DES added is 5% of the total amount of the mixture.

[0091] Example 23 It is basically the same as Example 3, except that in step (2), the amount of deep eutectic solvent DES added is 10% of the total amount of the mixture.

[0092] Comparative Example 3 A hydrophobic gel, the preparation method of which is as follows: (1) Preparation of hydrophobic deep eutectic solvent TOMAC-EG DES Methyltrioctylammonium chloride (TOMAC, hydrogen bond acceptor HBA) and ethylene glycol (EG, hydrogen bond donor HBD) were mixed in a molar ratio of 1:2 and stirred continuously at 60 °C until a homogeneous and transparent liquid was formed.

[0093] (2) Preparation of gel precursor solution The precursor solution was composed of 30 wt% MAA monomer and 70 wt% TOMAC-EG DES, with 1 wt% PEGDA crosslinking agent relative to the mass of MAA monomer and 1 mol% photoinitiator P-184 relative to the amount of MAA monomer added. The mixture was stirred at 60 °C for 1 h to fully dissolve and form a homogeneous precursor solution.

[0094] (3) Degas the precursor liquid for 20 min, pour it into a polytetrafluoroethylene mold, and irradiate it under 365 nm, 100 W ultraviolet light for 30 min to allow MAA to undergo in-situ free radical polymerization in hydrophobic DES and form a PMAA network, finally obtaining PMAA / TOMAC-EG hydrophobic eutectic gel.

[0095] Testing revealed that the gel prepared in this comparative example had a contact angle of only 66°, a fracture strain of 815%, a fracture stress of 0.89 MPa, and a toughness of 3.54 MJ / m. 3 The Young's modulus is 0.11 MPa, and the swelling rate after soaking in water for 10 days is 180%.

[0096] Gel performance test The mechanical properties, swelling properties, and antibacterial properties of the gels prepared in the embodiments and comparative examples of this invention were tested. Details are as follows: (1) Stress-strain performance test: The mechanical tensile properties of the gel samples prepared in the examples and comparative examples were tested using a universal testing machine. The prepared gels were cut into rectangular shapes of 50 mm × 5 mm × 2 mm, and the tensile rate was 100 mm / min. Load-displacement data were recorded simultaneously, and stress-strain curves were plotted by calculating stress (load / original cross-sectional area) and strain (deformation / original gauge length). Each sample was tested three times, and the average value was taken.

[0097] The results are as follows Figure 5-9 As shown, by Figure 5 It can be seen that Examples 1-5 and Comparative Example 1 changed the monomer ratio. With increasing LMA content, the hydrophobicity of the gel gradually increased, but an excessively high LMA ratio would reduce the flexibility and load-bearing capacity of the polymer network. When the LMA / GMA mass ratio was 2:3, Example 3 exhibited a combination of high elongation at break, high fracture stress, and high toughness. Figure 7 It is known that an appropriate amount of DES can improve the flexibility and energy dissipation capacity of the gel network, but excessive DES content will weaken the network strength. Examples 3 and 10-13 investigated the effect of crosslinking agent dosage. Figure 6 It can be seen that when the crosslinking agent content is too low, the network crosslinking is insufficient, and when the crosslinking agent content is too high, the chain segment movement is restricted. A moderate amount of crosslinking agent is beneficial to obtaining better mechanical properties. Figure 8 The figures show the stress-strain diagrams of the gels in Examples 3 and 14-17. As can be seen from the figures, too low a dosage of photoinitiator will lead to insufficient polymerization, while too high a dosage may lead to excessively short chain segments or increased network defects. A moderate dosage is more beneficial to the overall mechanical properties of the gel. Figure 9Comparing the effects of different curing times in Examples 3 and 18-21, the figure shows that when the curing time is too short, the cross-linking is insufficient, and when the curing time is too long, the material flexibility decreases. An appropriate curing time can balance strength and elongation properties.

[0098] (2) Other mechanical property tests (2-1) Continuous loading-unloading and cyclic loading-unloading test The gel prepared in Example 3 was cut into rectangular pieces of 50 mm × 5 mm × 2 mm and subjected to continuous loading-unloading and cyclic loading-unloading tests using a tensile testing machine. Tensioning was performed at a rate of 30 mm / min at room temperature, and the load-displacement curves were recorded. The continuous tensile-unloading cyclic tests of the deep eutectic ionogel MTLG prepared in Example 3 under different strains (50% to 250%) were obtained through calculation. The results are as follows: Figure 10 As shown in the figure, the hysteresis loop area of ​​the loading-unloading curve gradually increases with increasing strain, indicating that the gel has good energy dissipation capacity during stretching. The continuous and stable cycle curves indicate that the gel still has good elastic recovery capacity and structural integrity under large deformation.

[0099] This invention also conducted continuous tensile-unloading cycle tests on the deep eutectic ionogel MTLG prepared in Example 3 after soaking in water for 24 h and 48 h, and the results are as follows: Figure 11-12 As shown in the figure, the gel can still maintain a relatively complete loading-unloading curve and obvious hysteresis loop after soaking in water, indicating that it is not prone to significant swelling and damage in the water environment and has good anti-swelling stability and cyclic tensile reliability.

[0100] In addition, the tensile-unloading curves of the deep eutectic ionogel MTLG prepared in Example 3 at different recovery times under 100% strain were determined. Specifically, the gel prepared in Example 3 was stretched to 100% strain and then unloaded, and allowed to recover at room temperature for different times. Then, the loading-unloading test was performed again, and the stress-strain curves at different recovery times were recorded. Figure 13 As shown in the figure, the stress response and hysteresis loop of the gel gradually recover with the extension of the recovery time, indicating that the reversible interactions inside the gel can be gradually reconstructed during the resting process, and the material has good self-healing properties. Figure 14 The loading-unloading curves of the deep eutectic ionogel MTLG prepared in Example 3 under 20 cycles at 100% strain are given. As can be seen from the figure, the curve morphology remains relatively stable during the 20 consecutive cycles, with only limited stress decay, indicating that the gel has good fatigue resistance and cyclic stability.

[0101] (2-2) Fracture properties, elasticity, and toughness tests The gels prepared in each embodiment or comparative example were cut into rectangular shapes of 50 mm × 5 mm × 2 mm. Overlap shear tests were performed using a universal testing machine. A sample measuring 30 mm × 15 mm × 2 mm was placed between two substrates (50 mm × 20 mm × 1 mm), and the sample was stretched to failure using the universal testing machine at a speed of 10 mm / min. The maximum displacement and maximum load at fracture were measured. The elongation at fracture was obtained by the ratio of the elongation at fracture to the initial gauge length; the fracture stress was obtained by the ratio of the fracture load to the initial cross-sectional area of ​​the sample. The Young's modulus was obtained from the slope of the initial linear segment of the stress-strain curve; the toughness was obtained by integrating the stress-strain curve. All of the above methods are conventional methods in the art and will not be described in detail here. The test results are shown in Table 1.

[0102] (3) Contact angle test The water contact angle was measured using the seated drop method. Smooth, defect-free gel sheets prepared in the examples and comparative examples were fixed on a horizontal sample stage. 8 μL of ultrapure water was added dropwise under constant temperature, humidity, and windless conditions. Images were captured 3–8 seconds after the droplet contacted the sample. The contact angle was calculated using the Young-Laplace model, with multiple parallel samples taken and the average value calculated. The results are shown in Table 1.

[0103] Table 1 Mechanical properties of gels prepared in the embodiments and comparative examples of the present invention

[0104] Table 1 shows that Examples 1-5 and Comparative Example 1 changed the monomer ratio. As the LMA ratio increased from 1:4 to 3:2, the gel contact angle increased from 81.2° to 107.0°, indicating enhanced hydrophobicity; however, the fracture stress decreased from 1.58 MPa in Example 2 to 0.21 MPa in Example 5, and the toughness decreased from 4.67 MJ / m in Example 3. 3 The concentration decreased to 0.35 MJ / m³ in Example 5. 3 Compared to Comparative Example 1, the elongation at break in Example 3 increased from 176.8% to 444.5%, the fracture stress increased from 0.92 MPa to 1.39 MPa, and the toughness increased from 1.08 MJ / m. 3 Increased to 4.67 MJ / m 3 The contact angle was increased from 72.4° to 98.1°, thus Example 3 achieved the best overall balance between hydrophobicity and mechanical properties.

[0105] Comparing Examples 3, 6-9, and Comparative Example 2, it is evident that the DES content affects the flexibility, ionic interactions, and swelling stability of the gel network. Comparative Example 2, without added DES, exhibited an elongation at break of 265.7% and a toughness of 2.02 MJ / m. 3When the DES content is about 6%, the elongation at break and toughness of Example 3 are increased to 444.5% and 4.67 MJ / m3, respectively; when the DES content is increased to 15%, the fracture stress of Example 9 is reduced to 0.83 MPa, indicating that excessive DES will weaken the load-bearing capacity of the polymer network.

[0106] Comparing Examples 3 and 10-13, it is evident that different amounts of crosslinking agent alter the gel crosslinking density. When the amount of PEGDA was 0.10 g, the fracture stress in Example 10 was 0.82 MPa, indicating insufficient crosslinking. When the amount of PEGDA was 0.30 g, the elongation at break in Example 13 decreased to 302.4%, indicating restricted chain segment movement. Example 3, with an amount of 0.20 g of PEGDA, exhibited both an elongation at break of 444.5% and 4.67 MJ / m². 3 The toughness of this formula makes it the preferred formulation under these conditions.

[0107] Comparing Examples 3 and 14-17, it is evident that different initiator dosages affect the degree of polymerization and network uniformity. When the P-184 dosage is 0.05 g, Example 14 exhibits a fracture stress of 0.86 MPa and a toughness of 2.15 MJ / m. 3 The results indicate that polymerization was incomplete. When the amount of P-184 was increased to 0.25 g, the elongation at break in Example 17 decreased to 365.2%, indicating that excessive initiator reduces the effective length of chain segments. Example 3, with a P-184 content of 0.15 g, showed the best overall performance.

[0108] Comparing Examples 3 and 18-21, it can be seen that different curing times affect the degree of gel crosslinking. After curing for 10 min, Example 21 showed a fracture stress of 0.74 MPa and a toughness of 1.84 MJ / m. 3 This indicates incomplete cross-linking; after curing for 30 minutes, the elongation at break of Example 18 decreased to 338.6%, indicating that over-curing reduced flexibility. Example 3, cured for 20 minutes, exhibited the highest toughness of 4.67 MJ / m. 3 With a high contact angle of 98.1°, this was determined to be the preferred curing time.

[0109] (4) Adhesion and self-healing performance test Adhesion of the prepared gel to different material surfaces was tested: The deep eutectic ionogel prepared in Example 3 was coated onto the surfaces of PET, wood, copper plate, fabric, and paper, respectively. The adhesion strength between the gel and different substrates was determined using an overlap shear test. The results are as follows: Figure 15 As shown in Figure (a). Simultaneously, after applying the gel to the surfaces of the aforementioned different materials, five application-repeat cycles were performed, and the adhesion after multiple removals and reapplications was measured. The results are as follows. Figure 15As shown in Figure (b), the adhesion strength of the gel prepared in Example 3 of this invention on the surfaces of PET, wood, copper plate, fabric, and paper was 63.2 kPa, 58.6 kPa, 51.4 kPa, 46.8 kPa, and 41.5 kPa, respectively. After 5 cycles, the adhesion retention rate on the PET surface was 87.6%, and the adhesion retention rates on the surfaces of wood, copper plate, fabric, and paper were 82.4%, 79.1%, 76.8%, and 72.5%, respectively. This indicates that the gel has repeatable adhesion ability on various substrate surfaces, with the highest repeatable adhesion stability on the PET surface.

[0110] Figure 16 The self-healing properties of the gel prepared in Example 3 are presented. (a) Figure shows the two colored gels prepared in Example 3 cut in the middle and left to stand at 70 °C for 30 min. After standing, the two gels bonded together, and the interface did not break again when stretched to about 2.5 times the original length. (b) Figure shows the microscopic images of the gel interfaces gradually bonding together during the process of cutting and re-contacting the gel prepared in Example 3 and allowing it to stand for recovery. The upper image shows the contact after cutting, and the lower image shows the bonding of the gel interfaces after standing for recovery. (c) Figure shows the stress-strain curves of the gel prepared in Example 3 after different self-healing times. As can be seen from the figure, the fracture stress recovery after self-healing for 10 min, 20 min, 30 min, 40 min, 5 min, and 60 min is as follows. From the stress-strain curves in the figure, it can be seen that the gel of the present invention has a quantitatively characterizable self-healing ability.

[0111] (5) Antibacterial and antioxidant tests The gels prepared in Comparative Example 1, Examples 22-23, and Examples 24 were placed in culture dishes containing *Escherichia coli* and *Staphylococcus aureus*, respectively, and incubated at 37 °C for 24 h for photographic recording. Culture dishes without gel samples were considered blanks. Results are as follows: Figure 17 As shown in the figure, after 24 hours, the growth of surrounding bacterial colonies in the gels prepared in Examples 22-23 of the present invention was significantly inhibited, indicating that the gels prepared in the present invention have antibacterial properties compared with the control and blank.

[0112] The antioxidant test involved applying the gel prepared in Example 3 to the surface of a polished copper sheet, placing it in an environment of 20 °C and 65% RH, and observing the changes on the surface of the copper sheet after standing for different periods of time. Figure 18 The graphs show different standing times. As can be seen from the graphs, no obvious oxidation discoloration was observed on the surface of the copper sheet after the gel was applied during the observation period, indicating that the gel prepared by the present invention has a certain antioxidant protective effect.

[0113] (6) Anti-swelling performance test The gel samples from the examples and comparative examples were cut into squares, 10 mm in length and 1 mm in height. Each hydrogel was immersed in deionized water at room temperature for 10 days, and the sample mass was recorded at different times. The anti-swelling performance was calculated by measuring the mass change before and after swelling. The weight of the hydrogel was measured using an electronic balance.

[0114] Anti-swelling rate (%) = (mass of swollen sample m2 / mass of sample before swelling m1) * 100% The results are as follows Figure 20 As shown in the figure, all examples exhibit good anti-swelling properties. The gels prepared with a photoinitiator dosage of 0.05% or a monomer mass ratio of 2:8 show slightly lower anti-swelling properties, but both still meet the requirements.

[0115] Figure 19 The changes in the surface of the deep eutectic ionogel MTLG prepared in Example 3 after standing for 7 days at 20 °C and 65% RH (Figures show images from day 2 to day 7) are presented (a) and (b) respectively. Figure a shows that the surface morphology of the gel remained largely intact during the standing process, with no obvious cracking, seepage, or shrinkage. Figure b shows that the gel mass changed little with standing time, indicating that the gel has good environmental stability and resistance to water loss.

[0116] Application Example 1 This application example provides a continuous zirconia fiber with an anti-swelling deep eutectic ionogel coating, the preparation method of which specifically includes the following steps.

[0117] (1) Surface treatment of continuous zirconia fibers: Continuous zirconia fibers were ultrasonically cleaned sequentially with anhydrous ethanol and deionized water for 10 min each, and then dried at 60 °C for 1 h. A mixed solution containing 2.5 wt% KH-570, 3.0 wt% deionized water, and 94.5 wt% anhydrous ethanol was prepared, and the pH was adjusted to 4.5 with acetic acid. The dried continuous zirconia fibers were immersed in the above mixed solution for 1 h, then removed, cleaned with anhydrous ethanol, and dried at 60 °C for 1 h to obtain surface-activated continuous zirconia fibers.

[0118] (2) Prepare the deep eutectic ion gel prepolymer solution prepared in Example 3 (the prepolymer solution in step (2)).

[0119] (3) Coating and curing: The surface-activated continuous zirconia fiber obtained in step (1) was immersed in the deep eutectic ion gel prepolymer solution in step (2) for 3 min, pulled out at a speed of 1 cm / min, and after scraping off the excess prepolymer solution, it was placed under a 365 nm, 80 W ultraviolet light source for 20 min to allow the prepolymer solution to crosslink and solidify on the fiber surface. Then, it was post-treated at 45 °C for 30 min to obtain continuous zirconia fiber with an anti-swelling deep eutectic ion gel coating.

[0120] Tests showed that the coating thickness obtained in this embodiment was approximately 0.10 mm; no significant damage was observed after repeated rubbing under a 1 N load for 460 cycles; the water contact angle was 98.5°; and the swelling rate after soaking in deionized water for 10 days was 104.8%.

[0121] Application Example 2 The difference between this application example and application example 1 is that in step (2), the amount of deep eutectic solvent added during the preparation of the deep eutectic ion gel prepolymer is adjusted to 0.10 g; in step (3), the ultraviolet irradiation time is adjusted to 25 min, and the coating thickness is about 0.08 mm. The remaining steps are the same as in application example 1.

[0122] The obtained fibers showed no obvious damage after being repeatedly rubbed 405 times under a 1 N load; the water contact angle was 94.6°; and the swelling rate after soaking in deionized water for 10 days was 106.2%.

[0123] Application Example 3 The difference between this application example and application example 1 is that in step (2), the amount of hydrophobic deep eutectic solvent added during the preparation of the deep eutectic ion gel prepolymer is adjusted to 0.20 g; in step (3), the ultraviolet irradiation time is adjusted to 30 min, and the resulting coating thickness is about 0.12 mm. The remaining steps are the same as in application example 1.

[0124] The prepared coated zirconia fiber did not show obvious damage after repeated rubbing under a 1 N load for 485 cycles; the water contact angle was 98.1°; and the swelling rate after soaking in deionized water for 10 days was 103.9%.

[0125] Application Example 4 The difference between this application example and application example 1 is that in step (2), when preparing the deep eutectic ion gel prepolymer, the amount of lauryl methacrylate and glycidyl methacrylate used is 1.0 g, and the thickness of the resulting coating is about 0.11 mm. The remaining steps are the same as in application example 1.

[0126] The prepared coated zirconia fiber did not show obvious damage after repeated rubbing under a 1 N load for 420 cycles; the water contact angle was 99.3°; and the swelling rate after soaking in deionized water for 10 days was 103.6%.

[0127] Comparative Application Example 1 This comparative application example uses uncoated, raw continuous zirconia fibers.

[0128] Comparative Application Example 2 In this comparative application example, a deep eutectic ionogel system of choline chloride / acrylic acid / hydroxyethyl acrylate was used to coat continuous zirconia fibers. The coating thickness was approximately 0.12 mm. The remaining test methods were the same as in Application Example 1.

[0129] The preparation method of the choline chloride / acrylic acid / hydroxyethyl acrylate deep eutectic ionogel system is as follows: 1.00 g of choline chloride, 1.03 g of acrylic acid and 1.66 g of hydroxyethyl acrylate are mixed and stirred at 60 °C until a homogeneous and transparent solution is formed; then 1 wt% of PEGDA and 1 wt% of 1-hydroxycyclohexylphenyl ketone relative to the total mass of monomers are added, and the mixture is stirred evenly and poured into a mold. The mixture is then cured under 365 nm ultraviolet light for 2 min to obtain the choline chloride / acrylic acid / hydroxyethyl acrylate deep eutectic ionogel system.

[0130] Performance testing of coated fibers The mechanical properties, abrasion resistance, and swelling properties of the gel-coated fibers prepared in various application examples of this invention were determined. The specific methods are as follows: The tensile breaking strength test shall be conducted in accordance with GB / T 3362-2005.

[0131] The stiffness test was conducted in accordance with GB / T 7690.4-2013.

[0132] Wear rate testing was conducted in accordance with FZ / T 01058-1999.

[0133] The coefficient of friction was obtained by testing a reciprocating friction and wear tester under a 1 N load.

[0134] The coating thickness was determined using the microsection method.

[0135] The water contact angle was measured using a contact angle tester.

[0136] The anti-swelling performance was evaluated by measuring the mass change and surface condition of the coated fibers after immersing them in deionized water for 10 days.

[0137] The performance test results of each embodiment and comparative example are shown in Table 2.

[0138] Table 2 Comparison of the performance of continuous zirconia fibers with different coatings

[0139] As shown in Table 1, compared with the original continuous zirconia fiber, the coefficient of friction of the coated fiber obtained in Examples 1-4 of this invention decreased from 0.176 to 0.123-0.138, the wear rate decreased from 2.83% to 2.28%-2.43%, and the tensile breaking strength increased to 6.75-6.93 N. This indicates that the anti-swelling deep eutectic ionogel coating can improve wear resistance and damage resistance while maintaining fiber flexibility.

[0140] Compared to Comparative Application Example 2, which uses a choline chloride / acrylic acid / hydroxyethyl acrylate deep eutectic gel system, Application Examples 1-4 of the present invention are superior in terms of water contact stability, low coefficient of friction, and repeated friction durability. This is because the hydrophobic deep eutectic solvent of menthol / thymol and the long carbon chain structure of lauryl methacrylate together reduce the hydrophilicity of the coating, and the interaction between glycidyl methacrylate and the coupling layer on the fiber surface improves the interfacial adhesion stability of the coating, thus enabling the coating to maintain good integrity and lubricity even in water contact or high humidity environments.

[0141] Considering coating thickness, tensile strength, stiffness, wear rate, coefficient of friction, and anti-swelling performance, Examples 1 and 3 are the preferred solutions. Example 1 has a moderate coating thickness, a low coefficient of friction, and good prepolymer viscosity and traction coating stability during preparation. Example 3 has a higher wear resistance and a lower swelling rate, making it suitable for scenarios with higher requirements for water resistance stability.

[0142] The above description is merely a preferred embodiment of the present invention, and the present invention is not limited to the above embodiments. It is understood that other improvements and variations that are directly derived or conceived by those skilled in the art without departing from the spirit and concept of the present invention should be considered to be included within the protection scope of the present invention.

Claims

1. A method for preparing a swelling-resistant deep eutectic ionogel, characterized in that, Includes the following steps: S1: Solvent for preparing deep eutectic crystals; S2: Mix the hydrophobic monomer, comonomer, deep eutectic solvent prepared in step S1, crosslinking agent and photoinitiator to obtain a mixture, stir, and obtain deep eutectic ion gel prepolymer solution; S3: Pour the deep eutectic ion gel prepolymer from step S2 into a mold, solidify, and demold to obtain the deep eutectic ion gel; In S2, the hydrophobic monomer includes lauryl methacrylate, and the comonomer includes glycidyl methacrylate.

2. The preparation method according to claim 1, characterized in that, In S1, the method for preparing the deep eutectic solvent includes: mixing cyclic terpene alcohols and phenolic compounds, and then repeatedly heating and stirring until a transparent and homogeneous solution is obtained.

3. The preparation method according to claim 2, characterized in that, The cyclic terpene compounds include at least one of menthol, isomenthol, borneol, and isoborneol; The phenolic compounds include at least one of thymol, carvacrol, and eugenol.

4. The preparation method according to any one of claims 2-3, characterized in that, The molar ratio of the cyclic terpene compound to the phenolic compound is 0.8~1.2:1; When heating and stirring repeatedly, the temperature for each heating is 50~70℃, and / or the heating time for each heating is 20min; and / or the stirring time for each stirring is 10min.

5. The preparation method according to claim 1, characterized in that, In S2, the mass ratio of the hydrophobic monomer to the comonomer is 1:4 to 3:2, preferably 2:

3.

6. The preparation method according to claim 1, characterized in that, In S2, the mass percentage of the deep eutectic solvent prepared in step S1 in the mixture is 3-20%. The total mass ratio of the hydrophobic monomer and the comonomer to the crosslinking agent is 2:0.1~0.3; The total mass ratio of the hydrophobic monomer and the comonomer to the photoinitiator is 2:0.05~0.25; The crosslinking agent includes at least one of polyethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,6-hexanediol diacrylate. The initiator includes at least one of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, and ethyl 2,4,6-trimethylbenzoylphosphonate; The stirring time is 5 to 30 minutes.

7. The preparation method according to claim 1, characterized in that, In S3, the curing is ultraviolet curing, and the curing time is 5~30 minutes.

8. A deep eutectic ionogel with anti-swelling properties prepared by the preparation method according to any one of claims 1-7.

9. A method for preparing a fiber with an anti-swelling deep eutectic ionogel coating, characterized in that, Includes the following steps: (1) Fiber surface pretreatment; (2) The deep eutectic ionogel prepolymer solution is prepared according to any one of claims 1-7; (3) Immerse the fiber surface-treated in step (1) into the gel prepolymer solution in step (2). After 0.5~5 min, pull it out at a speed of 0.5~5 cm / min and perform cross-linking polymerization to obtain fiber with anti-swelling deep eutectic ion gel coating. In step (1), the fiber includes zirconium oxide fiber; The cross-linking polymerization is carried out under ultraviolet light; The thickness of the anti-swelling deep eutectic ionogel coating is 0.05~2mm.

10. A fiber with an anti-swelling deep eutectic ionogel coating prepared by the preparation method of claim 9.

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