Mechanically interlocked polymer toughened and reinforced titanium carbide thin film material, method of making and use thereof

Abstract

This invention discloses a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material, its preparation method, and its applications, relating to the fields of synthetic chemistry and nanocomposite material preparation. By reacting mechanically interlocked molecules with a copolymer and further bridging them onto the surface of a titanium carbide thin film, the titanium carbide thin film is reinforced and toughened by utilizing the controllable intramolecular motion mechanism of the mechanically interlocked molecules, such as sliding, rotation, and translation. In particular, the prepared titanium carbide thin film exhibits excellent stretchability, especially maintaining stable conductivity even during repeated stretching, making it suitable for applications in stretchable electronics, such as flexible electronic products, wearable smart devices, and wearable rehabilitation devices.

Description

Technical Field

[0001] This invention relates to the fields of synthetic chemistry and nanocomposite material preparation, specifically to a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material, its preparation method, and its applications. Background Technology

[0002] Titanium carbide (Ti3C2T) X Titanium carbide (TiCarbide) is a two-dimensional material with broad application prospects. Its excellent electrical conductivity and mechanical properties make it popular in various fields, such as flexible electronics, supercapacitors, batteries, sensors, and electromagnetic interference shielding. However, the preparation of high-performance macroscopic thin films from titanium carbide nanosheets is hindered by the inherent brittleness and non-ductility of the films, which limits the further development of applications of titanium carbide materials. The abundant hydroxyl functional groups on the surface of titanium carbide nanosheets can be used to modulate the interactions between the layers. Current research focuses on enhancing the tensile strength of titanium carbide thin films by introducing covalent / non-covalent bonds, but achieving significant elongation remains a challenge. Summary of the Invention

[0003] In order to solve the problems of the prior art, the purpose of this invention is to overcome the shortcomings of the existing technology and provide a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material, its preparation method and its application.

[0004] One objective of this invention is to provide a method for preparing a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material, comprising the following steps:

[0005] S1. Determine the raw materials, including: mechanically interlocking molecules and copolymers, wherein the mechanically interlocking molecules contain one or more hydroxyl functional groups;

[0006] S2. React the mechanically interlocking molecules and the copolymer to extract the mechanically interlocking polymer;

[0007] S3. Dissolve the mechanically interlocking polymer in an organic solvent to prepare an immersion solution, and immerse the titanium carbide film in the immersion solution to obtain the mechanically interlocking polymer-bridged titanium carbide film.

[0008] Preferably, the molar ratio of the mechanically interlocking molecule to the copolymer is 1:(10-20).

[0009] In some preferred embodiments of the present invention, the mechanically interlocking molecule contains two hydroxyl functional groups.

[0010] More preferably, the mechanically interlocking molecule is one or more of rotaxane, sesquicarbon, and daisy chain.

[0011] In some preferred embodiments of the present invention, the mechanically interlocking molecule is a hydroxyl-containing [2] rotaxane with the following structural formula:

[0012]

[0013] In some preferred embodiments of the present invention, the mechanically interlocking molecule is a hydroxyl-containing hydroxyl hydrocarbon with the following structural formula:

[0014]

[0015] In some preferred embodiments of the present invention, the mechanically interlocking molecule is a hydroxyl-containing daisy chain with the following structural formula:

[0016]

[0017] Preferably, the copolymer is N,N'-carbonyldiimidazole.

[0018] Preferably, in S2, the mechanically interlocked molecules and the copolymer react in a reaction solvent under the following conditions: stirring at room temperature, stirring speed of 400-600 rpm, and reaction time of 12-24 h.

[0019] More preferably, the ratio of the mechanically interlocking molecule to the reaction solvent is (100-500) mg: (10-20) mL.

[0020] In some preferred embodiments of the present invention, the ratio of the mechanically interlocking molecule to the reaction solvent is 20 mg / mL.

[0021] More preferably, the reaction solvent is selected from dichloromethane, trichloromethane, toluene, tetrahydrofuran, acetonitrile, or N,N-dimethylformamide.

[0022] In some preferred embodiments of the present invention, the reaction solvent is dichloromethane.

[0023] Preferably, the extraction method of the mechanically interlocked polymer is as follows: after the reaction system of S2 is washed with water multiple times, water is removed with anhydrous magnesium sulfate, and then dichloromethane is removed.

[0024] Preferably, in step S3, the concentration of the mechanically interlocking polymer in the immersion solution is 3–10 mg / mL.

[0025] In some preferred embodiments of the present invention, the ratio of the mechanically interlocking polymer to the organic solvent is 5 mg / mL.

[0026] Preferably, the organic solvent is selected from one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane, chloroform, and dimethyl sulfoxide.

[0027] In some preferred embodiments of the present invention, the organic solvent is selected from N,N-dimethylformamide, tetrahydrofuran, and N,N-dimethylacetamide.

[0028] Preferably, the titanium carbide thin film is a self-supporting membrane prepared by vacuum filtration of an aqueous titanium carbide solution.

[0029] More preferably, the thickness of the titanium carbide film is 3 to 10 μm.

[0030] More preferably, the ratio of the amount of titanium carbide film to the amount of immersion solution is (15-20) mg: (4-6) mL.

[0031] In some preferred embodiments of the present invention, the ratio of the titanium carbide film to the immersion solution is 4 mg / mL.

[0032] Preferably, the soaking treatment is performed by soaking at 20–40°C for 6–12 hours.

[0033] More preferably, the soaking treatment is: soaking at 25-40°C for 8-10 hours.

[0034] In some preferred embodiments of the present invention, the soaking treatment is: soaking at 25°C for 10 hours.

[0035] In some preferred embodiments of the present invention, the soaking treatment is: soaking at 35°C for 10 hours.

[0036] In some preferred embodiments of the present invention, the soaking treatment is: soaking at 40°C for 8 hours.

[0037] Preferably, the extraction of the mechanically interlocked polymer-bridged titanium carbide film is performed by washing with anhydrous ethanol followed by drying.

[0038] More preferably, the drying process is carried out at a temperature of 40–60°C and under vacuum for 2–4 hours.

[0039] In some preferred embodiments of the present invention, the drying process is performed at a temperature of 45°C, a vacuum degree of -0.1 MPa, and a time of 2 to 4 hours.

[0040] The second objective of this invention is to provide a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material, which is prepared using the above-mentioned method for preparing mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material.

[0041] Preferably, the surface of the thin film material is bridged with a mechanically interlocking polymer, the mechanically interlocking polymer containing an ester functional group with an imidazole group.

[0042] The third objective of this invention is to provide an application of a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material in electronic products, wearable smart devices, and wearable rehabilitation devices.

[0043] Preferably, the thin film material is used to prepare a stretchable electroluminescent device.

[0044] More preferably, the thin film material is used to prepare the electrode layer of a stretchable electroluminescent device.

[0045] In some preferred embodiments of the present invention, the device includes the thin film material, a polydioxyethylthiophene layer, and a zinc sulfide / copper / polydimethylsiloxane composite material layer located between the two layers.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] This invention provides a method for preparing a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material. The method involves forming a mechanically interlocked polymer through a reaction between mechanically interlocked molecules and a copolymer, which is then bridged onto the titanium carbide thin film material. The intramolecular movement of the mechanically interlocked molecules is used to enhance and toughen the titanium carbide thin film material, and the elongation is also significantly improved while increasing the strength and toughness.

[0048] The mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material prepared in this invention involves bridging mechanically interlocked molecules onto the surface of a titanium carbide thin film in the form of copolymers. Mechanically interlocked molecules are a type of molecule with a unique topological structure formed based on host-guest recognition, utilizing a spatially entangled molecular structure. Compared to traditional covalent / non-covalent bonds, mechanically interlocked molecules can achieve controllable intramolecular movements, such as sliding, rotation, and translation. This unique intramolecular movement mechanism endows mechanically interlocked molecules with dynamic stability and mechanical adaptability, resulting in titanium carbide thin films with excellent stretchability, especially maintaining stable conductivity even during repeated stretching. This makes them suitable for applications in stretchable electronics, such as flexible electronic products, wearable smart devices, and wearable rehabilitation devices. Attached Figure Description

[0049] Figure 1 The 1H NMR spectrum of mechanically interlocked polymers based on [2] rotaxane at 7.0–8.2 ppm;

[0050] Figure 2 This is a schematic diagram of the reaction for preparing mechanically interlocked polymers using hydroxyl groups in Example 2 of the present invention;

[0051] Figure 3 The 1H NMR spectra of the mechanically interlocked polymers based on hydroxyl groups in the range of 7.0–8.2 ppm.

[0052] Figure 4 The 1H NMR spectrum of the hydroxyl-containing daisy chain monomer prepared in Example 3 of this invention;

[0053] Figure 5 This is a high-resolution mass spectrum of the hydroxyl-containing daisy chain monomer prepared in Example 3 of the present invention;

[0054] Figure 6 The 1H NMR spectra of daisy chain-based mechanically interlocked polymers in the range of 7.0–8.3 ppm.

[0055] Figure 7 This is a schematic diagram of the device structure of the stretchable electroluminescent device prepared in Example 4 of the present invention;

[0056] Figure 8 This is a macroscopic bending photograph of the RBM film prepared in Example 1 of the present invention;

[0057] Figure 9 The images shown are scanning electron microscope (SEM) images (Figure a) and energy dispersive spectroscopy (EDS) images of the RBM thin film prepared in Example 1 of this invention. Figure (b) corresponds to Ti, Figure (c) corresponds to C, and Figure (d) corresponds to N.

[0058] Figure 10 Figure (a) shows the tensile stress-strain curves of titanium carbide thin film samples corresponding to Example 1, Comparative Example 1, and Comparative Example 3 of the present invention, and a comparison diagram of the mechanical properties of the three samples (Figure (b)) including three performance directions: tensile strength, toughness, and fracture strain.

[0059] Figure 11 Figure a shows the tensile stress-strain curves of the titanium carbide thin film samples corresponding to Example 1 and Comparative Example 2 of the present invention, and Figure b shows the mechanical properties of the three samples, including tensile strength, toughness and fracture strain.

[0060] Figure 12 The tensile stress-strain curves of the mechanically interlocked polymer-bridged titanium carbide films prepared in Examples 2 (Figure a) and 3 (Figure b) of the present invention are shown.

[0061] Figure 13 The relative resistance change of the RBM film prepared in Example 1 of the present invention is shown when it is cyclically stretched 500 times within the strain range of 0-15%. R0 and R represent the resistance of the RBM film before and after stretching, respectively.

[0062] Figure 14 The images show the light emission of the stretchable electroluminescent device prepared in Example 4 of this invention under tensile strains of 0%, 5%, 10%, 15%, and 20%. Detailed Implementation

[0063] The present invention will be described in detail below with reference to embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several adjustments and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0064] Example 1

[0065] This embodiment provides a mechanically interlocked polymer-reinforced toughened titanium carbide thin film material, including the following steps:

[0066] S1. Determine the mechanical interlocking molecule.

[0067] The mechanically interlocking molecule used in this embodiment is a hydroxyl-containing [2] rotaxane, the synthesis method of which is described in Angew.Chem.Int.Ed.2024,63,e202404481, and its structural formula is shown below:

[0068]

[0069] S2, Preparation of mechanically interlocked polymers

[0070] 200 mg of the mechanically interlocking molecule was dissolved in 10 mL of dichloromethane, and 250 mg of N,N'-carbonyldiimidazole was added. The mixture was stirred at 25 °C and 500 rpm for 20 hours. After the reaction was completed, the reaction system was washed with water 3-5 times, dried with anhydrous magnesium sulfate, and finally the dichloromethane was removed to obtain the mechanically interlocking polymer. The reaction is as follows:

[0071]

[0072] like Figure 1 The image shows the 1H NMR spectrum of the mechanically interlocked polymer based on [2] rotaxane at 7.0-8.2 ppm, with three characteristic signal peaks H of the imidazole group. 1 H 2 H 3 The concentrations were found at 8.14 ppm, 7.43 ppm and 7.07 ppm, respectively, thus demonstrating that the mechanically interlocked polymer based on [2] rotaxane contains an ester functional group with an imidazole group.

[0073] S3. Dissolve 25 mg of the mechanically interlocked polymer prepared in S2 in 5 mL of N,N-dimethylformamide, take 5 mL to soak the titanium carbide film, soak in 40℃ environment for 8 h, and extract to obtain [2] rotaxane polymer-bridged titanium carbide film, wherein the titanium carbide film is a self-supporting film prepared by vacuum filtration of titanium carbide aqueous solution, with a thickness of 5 μm.

[0074] The extraction method is as follows: the polymer-bridged titanium carbide film obtained in S3 is washed with anhydrous ethanol and then dried in a vacuum oven at 45°C for 3 hours. The vacuum degree of the vacuum oven is -0.1 MPa. The titanium carbide film bridged by rotaxane [2] is obtained and labeled as RBM.

[0075] Example 2

[0076] This embodiment provides a mechanically interlocked polymer-reinforced toughened titanium carbide thin film material, including the following steps:

[0077] S1. Determine the mechanical interlocking molecule.

[0078] The mechanically interlocking molecule used in this embodiment is a hydroxyl-containing hydroxyl group, synthesized as described in J. Am. Chem. Soc. 2023, 145, 9011-9020, with the following structural formula:

[0079]

[0080] S2, Preparation of mechanically interlocked polymers

[0081] 100 mg of the mechanically interlocking molecule was dissolved in 5 mL of dichloromethane, and 200 mg of N,N'-carbonyldiimidazole was added. The mixture was stirred at 25 °C and 500 rpm for 20 hours. After the reaction was complete, the reaction system was washed repeatedly with water 3-5 times, dried with anhydrous magnesium sulfate, and finally the dichloromethane was removed to obtain the mechanically interlocking polymer. The reaction is as follows: Figure 2 As shown;

[0082] like Figure 3 As shown, the 1H NMR spectrum of the mechanically interlocked polymer based on hydroxyl groups in the range of 7.0–8.2 ppm shows three characteristic signal peaks H of the imidazole group. 1 H 2 H 3 The concentrations were found at 8.15 ppm, 7.44 ppm, and 7.08 ppm, respectively, thus demonstrating that the mechanically interlocked polymer based on hydroxyl groups contains an ester functional group with an imidazole group.

[0083] S3. Dissolve 30 mg of the mechanically interlocked polymer prepared in S2 in 6 mL of tetrahydrofuran, take 5 mL to soak the titanium carbide film, soak in 25°C for 10 h, and extract the hydroxyl polymer-bridged titanium carbide film. The titanium carbide film used is the same as that in Example 1.

[0084] The extraction method is as follows: the polymer-bridged titanium carbide film obtained in S3 is washed with anhydrous ethanol and then dried in a vacuum oven at 45°C for 2 hours. The vacuum degree of the vacuum oven is -0.1 MPa. The resulting polymer-bridged titanium carbide film is labeled as CBM.

[0085] Example 3

[0086] This embodiment provides a mechanically interlocked polymer-reinforced toughened titanium carbide thin film material, including the following steps:

[0087] S1. Determine the mechanical interlocking molecule.

[0088] The mechanically interlocking molecule used in this embodiment is a hydroxyl-containing daisy chain, with the following structural formula:

[0089]

[0090] The method for synthesizing daisy chains is as follows:

[0091] S1-1: 5.5 mmol of 8-bromo-1-octanol, 5 mmol of p-hydroxybenzaldehyde, 7.5 mmol of potassium carbonate, and 50 mL of N,N-dimethylformamide (DMF) were mixed and stirred at 100 °C and 500 rpm for 12 h. After the reaction was completed, DMF was removed by rotary evaporation. The crude product was dissolved in dichloromethane (DCM), followed by water washing and extraction. Finally, the DCM organic phase was dried with anhydrous magnesium sulfate (MgSO4), filtered, and DCM was removed by rotary evaporation to obtain product 3.1.

[0092]

[0093] S1-2: 27.4 mmol of 10-bromo-1-decene, 43.2 mmol of potassium benzoyl imide, 50 mL of tetrahydrofuran (THF), and 50 mL of DMF were mixed and refluxed at 80 °C for 12 h. Then, 250 mL of ethanol (EtOH) and 2.5 g of hydrazine hydrate (N2H4·H2O) were added, and the mixture was refluxed at 80 °C for another 5 h. After the reaction was completed, 10 mL of hydrochloric acid solution (6 M) was added. After the solid dissolved, sodium hydroxide solution (NaOH, 3 M) was added to adjust the pH until alkaline. The reaction system was then extracted with ethyl acetate. Finally, the ethyl acetate organic phase was dried over anhydrous MgSO4, filtered, and the ethyl acetate was removed by rotary evaporation to obtain product 3.2.

[0094]

[0095] S1-3. Mix 30 mmol of 3.1, 30 mmol of 3.2 and 250 mL of methanol (MeOH) and react at 75 °C for 24 h. Then add 50 mmol of sodium borohydride (NaBH4) and stir at 500 rpm for 24 h at room temperature. Then add 50 mmol of di-tert-butyl dicarbonate ((Boc)2O) and 100 mL of DCM and stir at 500 rpm for 24 h at room temperature. After the reaction is complete, add water to the system for extraction. Then dry the DCM organic phase with anhydrous MgSO4, filter, remove DCM by rotary evaporation to obtain crude product, and finally purify by column chromatography (eluent: polar petroleum ether: ethyl acetate = 10:1 v / v) to obtain product 3.3.

[0096]

[0097] S1-4: 4.6 mmol of crown ether benzoic acid, 5.97 mmol of 3.3, 2.07 mmol of 4-dimethylaminopyridine (DMAP), 9.25 mmol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl) and 20 mL of DCM were mixed and stirred at 500 rpm for 6 h at room temperature. After the reaction was completed, DCM was removed by rotary evaporation and the solid was washed with diethyl ether to obtain product 3.4.

[0098]

[0099] S1-5. 9.2 mmol of 3.4, 15 mmol of 9-boronbicyclo[3.3.1]nonane (9-BBN), and 18 mL of THF were mixed and refluxed at 65 °C for 6 h under nitrogen protection. Then, 4 mL of EtOH, 6 mL of 4 M NaOH aqueous solution, and 6 mL of hydrogen peroxide (H2O2) were added and mixed. The mixture was stirred at 500 rpm at room temperature for 12 h under nitrogen protection. After the reaction was completed, THF was removed by rotary evaporation, and DCM and water were added for extraction. Finally, the DCM organic phase was dried with anhydrous MgSO4, filtered, and DCM was removed by rotary evaporation to obtain product 3.5.

[0100]

[0101] S1-6. Mix 10 mmol of 3.5 and 4 mL of 6M hydrochloric acid (HCl) aqueous solution and stir at room temperature for 12 h. Then add 20 mL of saturated ammonium hexafluorophosphonate (NH4PF6) aqueous solution and 60 mL of acetone. Stir at room temperature and 500 rpm for 6 h. Filter the resulting precipitate and perform column purification (eluent DCM:MeOH = 100:1 v / v) to obtain hydroxyl-containing daisy chain. The product is named 3.6.

[0102]

[0103] The prepared product 3.6 1 H NMR spectrum ((CD3)2S=O, 298K, 400MHz) as shown Figure 4 As shown, HRMS mass spectrometry Figure 5 As shown.

[0104] 1 H NMR ((CD3)2S=O, 298K, 400MHz) δ (ppm): 7.57 (dd, J=8.5, 1.9Hz, 1H), 7.46 (d, J=1.9Hz, 1H), 7.37 (d, J=8.4Hz, 2H), 7. 09(d,J=8.6Hz,1H),6.97(d,J=8.5Hz,2H),4.23(t,J=6.5Hz,2H),4.17(t,J=3.8Hz,2H),4.13(t,J=4.0Hz,2H),4.01( s,2H),3.96(t,J=6.4Hz,2H),3.80-3.77(m,4H),3.64-3.61(m,4H),3.58-3.55(m,4H),3.84-3.48(m,12H),3.37(t,J =6.4Hz,2H),2.81(t,J=7.7Hz,2H),1.73-1.66(m,4H),1.56(t,J=5.9Hz,2H),1.41-1.37(m,6H),1.33-1.23(m,20H).

[0105] HRMS:m / z calcd for C 48 H 80 NO 12 862.5675[M-PF6] + Found 862.5672[M-PF6] + .

[0106] S2, Preparation of mechanically interlocked polymers

[0107] 400 mg of the mechanically interlocking molecule was dissolved in 20 mL of dichloromethane, and 200 mg of N,N'-carbonyldiimidazole was added. The mixture was stirred at 25 °C and 500 rpm for 20 hours. After the reaction was completed, the reaction system was washed with water 3-5 times, dried with anhydrous magnesium sulfate, and finally the dichloromethane was removed to obtain the mechanically interlocking polymer. The reaction is as follows:

[0108]

[0109] like Figure 6As shown, the 1H NMR spectrum of the daisy chain-based mechanically interlocked polymer at 7.0-8.3 ppm shows three characteristic signal peaks H of the imidazole group. 1 H 2 H 3 The concentrations were found at 8.23 ​​ppm, 7.56 ppm, and 7.06 ppm, respectively, thus demonstrating that the mechanically interlocked polymer based on the daisy chain contains an ester functional group with an imidazole group.

[0110] S3. Dissolve 25 mg of the mechanically interlocked polymer prepared in S2 in 5 mL of N,N-dimethylacetamide, take 5 mL to soak the titanium carbide film, soak in 35°C for 10 h, and extract to obtain the daisy chain polymer-bridged titanium carbide film. The titanium carbide film used is the same as that in Example 1.

[0111] The extraction method is as follows: the polymer-bridged titanium carbide film obtained in S3 is washed with anhydrous ethanol and then dried in a vacuum oven at 45°C for 4 hours. The vacuum degree of the vacuum oven is -0.1 MPa. Daisy chain polymer-bridged titanium carbide film is obtained and labeled as DBM.

[0112] Example 4

[0113] This embodiment provides a method for fabricating stretchable electroluminescent devices using RBM thin films, such as... Figure 7 As shown, it includes:

[0114] The bottom layer is an RBM thin film layer, the middle layer is a zinc sulfide / copper / polydimethylsiloxane (ZnS:Cu / PDMS) composite material layer, and the top layer is a polydioxyethylthiophene (PEDOT) layer. The layers are bonded together by a spin-coating followed by thermosetting curing. The specific steps are as follows: First, the RBM film is flattened on glass. Then, the ZnS:Cu / PDMS composite material is spin-coated onto the RBM film at 3000 rpm for 30 seconds. Next, the ZnS:Cu / PDMS is thermoset at 80°C for 1 hour. Then, the top electrode of the PEDOT layer is spin-coated at 2000 rpm for 30 seconds and dried at 100°C for 15 minutes. Finally, the upper and lower electrode layers are connected with copper foil and then connected to an AC power supply. The light-emitting principle is as follows: when the AC power is turned on, an electric field is formed between the upper and lower electrodes. ZnS:Cu is an electroluminescent phosphor that emits bright blue light when excited by the electric field. Therefore, the device will emit light when the AC power is turned on.

[0115] Comparative Example 1

[0116] The steps in this comparative example are basically the same as those in Example 1, with the following differences:

[0117] [2] Rotaxane was replaced with heptaethylene glycol, and other conditions remained unchanged, resulting in a heptaethylene glycol-bridged titanium carbide film, labeled as: HBM.

[0118] Comparative Example 2

[0119] The steps in this comparative example are basically the same as those in Example 1, with the following differences:

[0120] Step S2 is omitted, and the mechanically interlocked molecule [2]rotaxane from step S1 is directly used in step S3 to replace the mechanically interlocked polymer in S3, resulting in a titanium carbide film containing [2]rotaxane without the participation of N,N'-carbonyldiimidazole, labeled as: RBM-NOCDI.

[0121] Comparative Example 3

[0122] This comparative example is a pure titanium carbide thin film, i.e., the titanium carbide thin film used in the above examples and comparative examples, a self-supporting titanium carbide thin film material (Ti3C2T) prepared by vacuum filtration of an aqueous titanium carbide solution. x ), where T x Representing the surface hydroxyl (-OH) functional group, with a thickness of 5 μm, it is labeled as: MXene.

[0123] Detection and Analysis

[0124] The performance testing and analysis of the above embodiments and comparative examples are described below.

[0125] I. Flexible Testing

[0126] The RBM film is bent, such as Figure 8 As shown, the film is not damaged after bending, indicating that the film is flexible.

[0127] II. SEM and EDS Detection

[0128] The cross-sectional morphology of the RBM film was observed using SEM (test voltage 5kV), such as... Figure 9 As shown in (a), the cross-section is stacked in layers. Elemental analysis of the RBM film surface using EDS is shown in Figures (b) to (d). It can be seen that nitrogen, titanium, and carbon are uniformly dispersed, indicating that [2] rotaxane is uniformly dispersed in the film. The EDS energy dispersive spectroscopy was performed using a field emission scanning electron microscope (Apreo 2S) from FEI at an accelerating voltage of 5 kV. The scanning electron microscope (SEM) image was obtained first, and the EDS spectrum was recorded simultaneously to detect the elemental distribution.

[0129] III. Mechanical Property Testing

[0130] Tensile stress-strain tests were performed on the samples prepared in Examples 1 to 3 and Comparative Examples 1 to 3 (tensile rate of 1 mm / min). Figure 10 and Figure 11 As shown, it can be seen that, Figure 10 As shown, the mechanical properties of RBM films are superior to those of HBM and MXene films, indicating that the presence of [2] rotaxane improves the performance of titanium carbide films, thus further demonstrating that mechanically interlocked molecules can prepare reinforced and toughened titanium carbide film materials; such as Figure 11 As shown, the mechanical properties of the RBM film are significantly better than those of the RBM-NOCDI film, indicating that the participation of N,N'-carbonyldiimidazole is crucial. It can react with the hydroxyl groups of [2] rotaxane and the hydroxyl groups on the surface of the titanium carbide film, thereby crosslinking [2] rotaxane with the titanium carbide film.

[0131] The tensile stress-strain curves of the mechanically interlocked polymer-bridged titanium carbide films prepared in Examples 2 and 3 are shown below. Figure 12 As shown, the films prepared in these two embodiments also exhibit excellent mechanical properties.

[0132] Cyclic tensile testing was performed on the RBM film prepared in Example 1, such as... Figure 13 As shown, the RBM film can be cycled at least 500 times within a strain range of 0% to 15%, and the film exhibits a constant and reversible resistance change, confirming that the RBM film has excellent fatigue tensile properties and can still maintain stable conductivity while being repeatedly stretched.

[0133] V. Combined Tensile-Luminescence Properties Test

[0134] The stretchable electroluminescent device prepared in Example 4 was tested, such as... Figure 14 As shown, the brightness of the light emitted remains basically unchanged from 0% to 20% elongation, further confirming the high elongation of the RBM film.

[0135] In summary, this invention utilizes the unique intramolecular motion of mechanically interlocked molecules to prepare titanium carbide films with high elongation (approximately 20%) and cyclic stretchability (elongation within 15%), which is beneficial for the application of titanium carbide films in the field of flexible electronics. Furthermore, the required mechanically interlocked molecules can be designed as needed, thus this method has universality.

[0136] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A method of making a mechanically interlocking polymer toughened and reinforced titanium carbide thin film material, characterized in that, The preparation method comprises the following steps: S1, determining raw materials, including: mechanical interlocking molecules and N,N'-carbonyl diimidazole, the mechanical interlocking molecules contain one or more hydroxyl functional groups; The mechanical interlocking molecules are one or more of rotaxane, catenane and daisy chain; S2, reacting the mechanical interlocking molecules and N,N'-carbonyl diimidazole to extract a mechanical interlocking polymer; The ratio of the mechanical interlocking molecules to N,N'-carbonyl diimidazole is 1 mol :(10-20) mol; S3, dissolving the mechanical interlocking polymer in an organic solvent to configure an immersion solution, and placing a titanium carbide film in the immersion solution for immersion treatment to extract a mechanical interlocking polymer bridged titanium carbide film; The concentration of the mechanical interlocking polymer in the immersion solution is 3-10 mg / mL; The ratio of the use amount of the titanium carbide film to the immersion solution is (15-20) mg :(4-6) mL; The immersion treatment is immersion at 20-40 ℃ for 6-12 h; The titanium carbide film is a self-supporting film prepared by vacuum suction filtration of a titanium carbide aqueous solution.

2. The method of making a mechanically interlocking polymer toughened titanium carbide reinforced thin film material according to claim 1, wherein, Further comprising one or more of the following technical features: A, in S2, the mechanical interlocking molecules and N,N'-carbonyl diimidazole are reacted in a reaction solvent, and the reaction solvent is selected from dichloromethane, trichloromethane, toluene, tetrahydrofuran, acetonitrile and N,N-dimethylformamide; B, in S3, the organic solvent is selected from one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane, trichloromethane and dimethyl sulfoxide.

3. The method of making a mechanically interlocking polymer toughened titanium carbide reinforced thin film material of claim 2, wherein, Further comprising one or more of the following technical features: The ratio of the mechanical interlocking molecules to the reaction solvent is (100-500) mg :(10-20) mL; The thickness of the titanium carbide film is 3 to 10 μ m.

4. The method of making a mechanically interlocking polymer toughened titanium carbide reinforced thin film material of claim 2, wherein, The mechanical interlocking molecules and N,N'-carbonyl diimidazole are reacted in a reaction solvent, and the reaction conditions are: room temperature stirring, stirring speed 400-600 rpm, and reaction time 12-24 h.

5. The method of making a mechanically interlocking polymer toughened titanium carbide reinforced thin film material of claim 1, wherein, Further comprising one or more of the following technical features: A, in S2, the extraction method of the mechanical interlocking polymer is: after the reaction system of S2 is washed with water for multiple times, anhydrous magnesium sulfate is used to remove water, and then dichloromethane is removed; B, in S3, the extraction method of the mechanical interlocking polymer bridged titanium carbide film is: after washing with anhydrous ethanol, drying treatment is performed, and the drying treatment is performed at a temperature of 40-60 ℃ and vacuum drying for 2-4 h.

6. A mechanically interlocking polymer toughened, reinforced titanium carbide thin film material, characterized in that, The thin film material is prepared according to the method in any one of claims 1-5, the surface of the thin film material is bridged with a mechanical interlocking polymer, and the mechanical interlocking polymer contains an ester group functional group with an imidazole group.

7. Use of a mechanically interlocked polymer-reinforced and toughened titanium carbide thin film material according to claim 6, characterized in that The thin film material is applied to electronic products, wearable smart devices and wearable rehabilitation appliances.

8. Use of a mechanically interlocking polymer toughened, reinforced titanium carbide thin film material according to claim 7, characterized in that The thin film material is applied to a stretchable electroluminescent device.

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