A bisindole crown ether diamine, its preparation method and application

Abstract

The present invention discloses a bis(indolyl) crown ether diamine, its preparation method and application, belonging to the technical field of organic synthesis. The present invention provides a bis(indolyl) crown ether diamine with a novel structure, and provides a synthesis method for the bis(indolyl) crown ether diamine. When synthesizing, 4-trimethylsilyl-3-butyn-1-ol is used as a raw material, and the bis(indolyl) crown ether diamine can be obtained through six steps. The preparation process is simple and suitable for large-scale batch synthesis. The synthesized bis(indolyl) crown ether diamine has a special structure, and can significantly improve the mechanical properties of polymers after being introduced into the polymerization, and is an effective polymer modification reagent.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a bis(indolyl)crown ether diamine, a preparation method thereof and an application thereof. Background Art

[0002] Crown ethers are generally cyclic compounds containing heteroatoms such as oxygen atoms and nitrogen atoms. Common crown ethers include 15-crown-5 and 18-crown-6, both of which contain the structural unit of -O-CH2-. The molecular structure of crown ethers is similar to that of a crown, so they are called crown ethers. Some properties of crown ethers and their derivatives have also been developed and applied in actual production and life by many researchers and play an important role. For example: (1) nanofibers; (2) biomimetic materials; (3) ion channels; (4) catalysts; (5) ion recognition; (6) drug complexation; (7) ion sensors, etc. One of the important properties of crown ethers is that they can form complexation with metal cations. And with the different sizes of the crown ether rings, the crown ether rings can form complexation with different metal cations. For example, 12-crown-4 can accurately recognize lithium ions, 15-crown-5 can accurately recognize sodium ions, 18-crown-6 can accurately recognize potassium ions, etc. At present, supramolecular polymer networks based on the complexation of crown ethers with various metal ions and secondary ammonium salts have received extensive attention and research due to their rich multifunctionality. Especially great progress has been made in improving the mechanical properties of polymer materials.

[0003] Supramolecular polymer networks (SPNs) are macromolecules connected by reversible supramolecular interactions such as hydrogen bonds, metal coordination, hydrophobic interactions or ionic attractions. Due to their excellent properties, SPNs have gradually become candidate materials for the development of tough materials. Host-guest recognition is a kind of supramolecular interaction, generally formed by the complexation of macrocyclic hosts such as crown ethers, cyclodextrins, pillararenes, cucurbiturils, calixarenes, etc. with charged or neutral guest molecules. In recent years, host-guest interactions based on crown ethers and secondary ammonium salts have been widely studied because of their performance advantages.

[0004] One of the most promising applications of SPNs is the preparation of tough hydrogels and elastomers. In the network, a large number of non-covalent bonds acting as sacrificial bonds can dissociate before the main-chain covalent bonds break, and the dissociated dynamic bonds can recombine reversibly. This process increases the energy required for material fracture, representing an efficient toughening mechanism. However, the research on SPNs is still in the exploratory stage, and it is crucial to develop SPNs with novel structures and enhanced properties. Currently, many achievements have been made in the construction of crown ether-based SPNs materials, but these cases mainly focus on SPNs in the elastomeric, gel or solution states. There are few reports on the research of tough thin-film materials based on crown ethers, especially those with in-depth studies on their mechanical properties. Similarly, there are relatively few studies on introducing crown ethers into the polymer main chain in the form of covalent bonds to explore their effects on the mechanical properties of polymers. Summary of the Invention

[0005] In view of the above-mentioned prior art, the present invention provides a bis(indolyl)crown ether diamine, its preparation method and application, so as to provide new ideas for improving the mechanical properties of polymers.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is to provide a bis(indolyl)crown ether diamine, and the structural formula of the bis(indolyl)crown ether diamine is shown in Formula I;

[0007]

[0008] The present invention also discloses a preparation method of the above-mentioned bis(indolyl)crown ether diamine, which includes the following steps:

[0009] S1: Dissolve 4-trimethylsilyl-3-butyn-1-ol, imidazole and tert-butyldimethylsilyl chloride in a first solvent, stir and react at room temperature for 15 h to obtain a compound shown in Formula II;

[0010]

[0011] S2: Dissolve 2-iodo-4-nitroaniline, the compound shown in Formula II, anhydrous lithium chloride, potassium acetate and palladium acetate in a second solvent, react at 70-80 °C for 2-3 h, and then separate and purify to obtain a compound shown in Formula III;

[0012]

[0013] S3: Dissolve the compound shown in Formula III in a third solvent, then dropwise add an aqueous hydrofluoric acid solution to the obtained solution, and then stir and react at room temperature under sealed conditions for 48 h, and then separate and purify to obtain a compound shown in Formula IV;

[0014]

[0015] S4: Dissolve carbon tetrabromide in a fourth solvent, then drop the resulting solution into a mixture formed by mixing the compound shown in Formula IV and triphenylphosphine, and then stir and react at room temperature for 2 - 3 h in the dark. Separate and purify to obtain the compound shown in Formula V;

[0016]

[0017] S5: Co - dissolve diaza - 18 - crown - 6 - ether, sodium iodide and sodium carbonate in a fifth solvent to obtain a mixed solution; dissolve the compound shown in Formula V in the fifth solvent, and drop the resulting solution into the mixed solution under a protective gas atmosphere; then react at 80 - 90 °C for 20 - 25 h, and then separate and purify to obtain the compound shown in Formula VI;

[0018]

[0019] S6: Co - dissolve the compound shown in Formula VI and a palladium catalyst in a sixth solvent, then drop hydrazine hydrate into the resulting solution, and then reflux and react at a reflux temperature of 80 - 90 °C for 12 - 16 h under a protective gas atmosphere, and then separate and purify to obtain the product.

[0020] Further, the first solvent in S1 is anhydrous DMF; the mass ratio of 4 - trimethylsilyl - 3 - butyn - 1 - ol, imidazole and tert - butyldimethylsilyl chloride is 0.85 - 0.86:0.8 - 0.82:1 - 1.1.

[0021] Further, the second solvent in S2 is anhydrous DMF; the mass ratio of 2 - iodo - 4 - nitroaniline, the compound shown in Formula II, anhydrous lithium chloride, potassium acetate and palladium acetate is 2 - 3:0.7 - 0.8:0.2 - 0.3:2.5 - 3:0.1 - 0.15.

[0022] Further, the third solvent in S3 is anhydrous acetonitrile, and the volume concentration of the aqueous solution of hydrofluoric acid is 48%; the feed ratio of the compound shown in Formula III to the aqueous solution of hydrofluoric acid is 0.2 - 0.3 g:2 ml.

[0023] Further, the fourth solvent in S4 is anhydrous acetonitrile; the mass ratio of the compound shown in Formula IV, triphenylphosphine and carbon tetrabromide is 0.9 - 1:1.7 - 1.8:2 - 2.3.

[0024] Further, the fifth solvent in S5 is anhydrous acetonitrile; the mass ratio of diaza - 18 - crown - 6 - ether, sodium iodide, sodium carbonate and the compound shown in Formula V is 0.9 - 1:0.05 - 0.06:1.5 - 2.5:2 - 2.1.

[0025] Further, in S6, the sixth solvent is absolute ethanol, and the palladium catalyst is 10% palladium on carbon; the feed ratio of the compound shown in Formula VI, the palladium catalyst, and hydrazine hydrate is 0.2 g: 0.02 g: 1 ml.

[0026] The present invention also discloses the application of the above-mentioned bis(indole crown ether diamine) in improving the mechanical properties of polymers.

[0027] The beneficial effects of the present invention are as follows: The present invention provides a bis(indole crown ether diamine) with a novel structure and provides a synthesis method for the bis(indole crown ether diamine). When synthesizing, 4-trimethylsilyl-3-butyn-1-ol is used as the raw material, and the bis(indole crown ether diamine) can be obtained through six steps. The preparation process is simple and suitable for large-scale batch synthesis. The synthesized bis(indole crown ether diamine) has a special structure and can significantly improve the mechanical properties of polymers after being introduced into the polymerization, and it is an effective polymer modification reagent. Description of the Drawings

[0028] Figure 1 It is the infrared spectrum characterization result of 3-tert-butyldimethylsilyloxy-trimethylsilyl-butyne;

[0029] Figure 2 It is the 1H NMR spectrum characterization result of 3-tert-butyldimethylsilyloxy-trimethylsilyl-butyne;

[0030] Figure 3 It is the 13C NMR spectrum characterization result of 3-tert-butyldimethylsilyloxy-trimethylsilyl-butyne;

[0031] Figure 4 It is the infrared spectrum characterization result of 3-[2-(tert-butyldimethylsilyloxy)ethyl]-5-nitro-2-trimethylsilylindole;

[0032] Figure 5 It is the 1H NMR spectrum characterization result of 3-[2-(tert-butyldimethylsilyloxy)ethyl]-5-nitro-2-trimethylsilylindole;

[0033] Figure 6 It is the 13C NMR spectrum characterization result of 3-[2-(tert-butyldimethylsilyloxy)ethyl]-5-nitro-2-trimethylsilylindole;

[0034] Figure 7 It is the infrared spectrum characterization result of 3-hydroxyethyl-5-nitroindole;

[0035] Figure 8 It is the 1H NMR spectrum characterization result of 3-hydroxyethyl-5-nitroindole;

[0036] Figure 9 It is the 13C NMR spectrum characterization result of 3-hydroxyethyl-5-nitroindole;

[0037] Figure 10 Infrared spectrum characterization results of 3-bromoethyl-5-nitroindole;

[0038] Figure 11 1H NMR characterization results of 3-bromoethyl-5-nitroindole;

[0039] Figure 12 13C NMR characterization results of 3-bromoethyl-5-nitroindole;

[0040] Figure 13 Infrared spectrum characterization results of bis(indolyl)nitro crown ether;

[0041] Figure 14 1H NMR characterization results of bis(indolyl)nitro crown ether;

[0042] Figure 15 13C NMR characterization results of bis(indolyl)nitro crown ether;

[0043] Figure 16 Infrared spectrum characterization results of bis(indolyl)crown ether diamine;

[0044] Figure 17 1H NMR characterization results of bis(indolyl)crown ether diamine;

[0045] Figure 18 13C NMR characterization results of bis(indolyl)crown ether diamine;

[0046] Figure 19 Structural formula of bis(indolyl)crown ether diamine;

[0047] Figure 20 For INCEAM-DG and INCEAM-DG-K + Tensile stress-strain curves of polymer films;

[0048] Figure 21 For INCEAM-DG and INCEAM-DG-K + Tensile strength and elongation at break of polymer films;

[0049] Figure 22 For INCEAM-DG and INCEAM-DG-K + Fracture energy of polymer films;

[0050] Figure 23 For INCEAM-DG and INCEAM-DG-K + Young's modulus of polymer films. Specific embodiments

[0051] The following examples are used to illustrate the specific embodiments of the present invention in detail.

[0052] Example 1: Preparation of Bis(indole)crown Ether Diamine

[0053] 1. Weigh 854 mg of 4-trimethylsilyl-3-butyn-1-ol, 816 mg of imidazole, and 1.05 g of tert-butyldimethylsilyl chloride. After fully dissolving them in 15 ml of anhydrous DMF, add them to a two-necked flask under a nitrogen atmosphere, and then stir the reaction at room temperature for 15 hours. After the reaction is completed, prepare 15 ml of 10 wt% sodium bicarbonate aqueous solution and slowly add it to the two-necked flask to quench the reaction for 10 min; extract the resulting solution with n-hexane three times, and wash the organic phase with distilled water and saturated sodium chloride aqueous solution three times each; then add anhydrous sodium sulfate to the obtained organic phase to remove the residual water; after drying for 1 h, filter the stirred mixture to remove the sodium sulfate after absorbing water, and then pour the obtained organic phase into a round-bottom flask, concentrate it under reduced pressure at 40 °C on a rotary evaporator to remove n-hexane, and finally dry it in a vacuum oven at 45 °C for 8 h to finally obtain a colorless oily liquid with a yield of 85%.

[0054] The infrared spectrum characterization results, 1H NMR characterization results, and 13C NMR characterization results of the obtained product are shown in Figure 1 , Figure 2 and Figure 3 respectively. The characterization results indicate that the synthesized compound is 3-tert-butyldimethylsilyloxy-trimethylsilyl-butyne (TMS-OTBDMS).

[0055] Example 2: Synthesis of 3-[(2-tert-butyldimethylsilyloxy)ethyl]-5-nitro-2-trimethylsilylindole (IN-TMS-OTBDMS)

[0056] The synthesis reaction formula of IN-TMS-OTBDMS is as follows:

[0057]

[0058] The specific method is as follows:

[0059] Weigh 792 mg of TMS-OTBDMS, 2.60 g of 2-iodo-4-nitroaniline, 254 mg of anhydrous lithium chloride, 2.94 g of potassium acetate, and 110 mg of palladium acetate; perform an anhydrous and anaerobic treatment on the two-necked flask, and then add the above reaction raw materials into the two-necked flask under a nitrogen protection atmosphere. When adding the materials, first add 2-iodo-4-nitroaniline, then add TMS-OTBDMS, and then successively add anhydrous lithium chloride, potassium acetate, and palladium acetate. Finally, add 20 ml of anhydrous DMF. After the raw materials are fully dissolved, place the two-necked flask in an oil bath and heat it to 75 °C, and keep the temperature for reaction for 2.5 h; monitor the progress of the reaction by TLC. After the raw materials have fully reacted, stop heating. After the reaction solution has cooled to room temperature, add 20 ml of ice water and 20 ml of ether to dilute the reaction solution; then pour the mixture into a separatory funnel to separate the aqueous phase and the organic phase. Extract the aqueous phase three times with ethyl acetate. Mix the two obtained organic phases, wash the organic phase three times each with distilled water and saturated sodium chloride aqueous solution. Dry the organic phase with anhydrous sodium sulfate for 2 h, then filter off the sodium sulfate under reduced pressure, and then concentrate under reduced pressure to remove the solvent; use a mixture of petroleum ether:ethyl acetate = 10:1 as the eluent, select silica gel powder with a mesh size of 100-200 as the stationary phase of the chromatographic column, and finally obtain a pale yellow solid after column chromatography purification, with a yield of 68%.

[0060] The infrared spectrum characterization results, 1H NMR characterization results, and 13C NMR characterization results of the obtained product are respectively as Figure 4 , Figure 5 and Figure 6 shown. The characterization results indicate that the synthesized compound is 3-[(2-tert-butyldimethylsilyloxy)ethyl]-5-nitro-2-trimethylsilylindole (IN-TMS-OTBDMS).

[0061] Example 3: Synthesis of 3-hydroxyethyl-5-nitroindole

[0062] The synthesis reaction formula of 3-hydroxyethyl-5-nitroindole is as follows:

[0063]

[0064] The specific method is as follows:

[0065] Dissolve 220 mg of IN-TMS-OTBDMS in acetonitrile, then pour the solution into a PTFE reactor, and dropwise add 2 ml of an aqueous solution of hydrofluoric acid with a concentration of 48% (v / v) to the PTFE reactor under stirring conditions; after the addition is complete, seal the PTFE reactor to prevent the volatilization of HF and acetonitrile, and stir the reaction at room temperature for 48 h, during which monitor the reaction progress by TLC; after the raw materials have fully reacted, prepare a saturated sodium carbonate solution, and dropwise add the saturated sodium carbonate solution to the PTFE reactor under stirring conditions to adjust the pH of the reaction solution to 8; then transfer the reaction solution to a separatory funnel, add 50 ml of ethyl acetate to ensure the complete separation of the aqueous phase and the organic phase; extract the aqueous phase multiple times, then mix the organic phases, wash the organic phase three times with distilled water, and then wash it three times with saturated brine; subsequently, add anhydrous sodium sulfate to dry the organic phase, after drying for 2 h, filter off the anhydrous sodium sulfate under reduced pressure; pour the organic phase separated by filtration into a round-bottom flask, and concentrate it under reduced pressure at 45 °C to remove ethyl acetate; use a mixture of petroleum ether:ethyl acetate = 1:1 - 1:3 as the eluent, select silica gel powder with a mesh size of 100 - 200 as the stationary phase of the chromatographic column, and perform wet loading for separation and purification to obtain a bright yellow solid with a yield of 86%.

[0066] The infrared spectrum characterization results, 1H NMR characterization results, and 13C NMR characterization results of the obtained product are shown in Figure 7 , Figure 8 and Figure 9 respectively. The characterization results indicate that the synthesized compound is 3-hydroxyethyl-5-nitroindole.

[0067] Example 4: Synthesis of 3-bromoethyl-5-nitroindole

[0068] The synthesis reaction formula of 3-bromoethyl-5-nitroindole is as follows:

[0069]

[0070] The specific method is as follows:

[0071] Weigh 175 mg of triphenylphosphine, 221 mg of carbon tetrabromide, and 91.5 mg of 3-hydroxyethyl-5-nitroindole; first, evacuate the reaction apparatus under anhydrous and anaerobic conditions and introduce nitrogen for a certain period of time, then add triphenylphosphine and 3-hydroxyethyl-5-nitroindole into the reaction apparatus under a nitrogen atmosphere; subsequently, dissolve carbon tetrabromide in 6 ml of anhydrous acetonitrile and add the acetonitrile solution of carbon tetrabromide dropwise to the reaction apparatus under an ice-water bath condition; after the dropwise addition, stir the reaction at room temperature for 2.5 h under light-shielded conditions; monitor the progress of the reaction by TLC, and after the raw materials have fully reacted, add ethyl acetate for dilution and transfer the diluted reaction solution to a separatory funnel, and wash the organic phase three times with water and brine respectively; after the washing is completed, add anhydrous sodium sulfate for drying, and after drying for 2 h, filter off the sodium sulfate under reduced pressure; concentrate under reduced pressure at 45 °C to remove ethyl acetate; use a mixture of petroleum ether:ethyl acetate = 4:1 - 1:1 as the eluent, use silica gel powder with a mesh size of 100 - 200 as the stationary phase of the chromatographic column, load the sample by the wet method, and obtain a bright yellow solid after column chromatography purification, with a yield of 85%.

[0072] The infrared spectrum characterization results, 1H NMR characterization results, and 13C NMR characterization results of the obtained product are respectively as Figure 10 , Figure 11 and Figure 12 shown, and the characterization results indicate that the synthesized compound is 3-bromoethyl-5-nitroindole.

[0073] Example 5: Synthesis of bis(indolyl)nitro crown ether

[0074] The synthesis reaction formula of bis(indolyl)nitro crown ether is as follows:

[0075]

[0076] The specific method is as follows:

[0077] Weigh 0.99 g of diaza-18-crown-6-ether, 0.0566 g of sodium iodide, 2.00 g of sodium carbonate and 2.03 g of 3-bromoethyl-5-nitroindole; under a nitrogen atmosphere, add diaza-18-crown-6-ether to a round-bottom flask that has been treated by evacuation under anhydrous and anaerobic conditions, dissolve it with 20 ml of anhydrous acetonitrile, and then add sodium iodide and sodium carbonate to the round-bottom flask; dissolve 3-bromoethyl-5-nitroindole in 20 ml of anhydrous acetonitrile, and under a nitrogen atmosphere, dropwise add the resulting solution to the round-bottom flask, then react at 85 °C for 24 h, and monitor the progress of the reaction by TLC; after the reaction is completed, filter, concentrate the filtrate under reduced pressure at 45 °C to remove acetonitrile, then dissolve it with dichloromethane, wash the resulting solution three times with distilled water, and dry it with anhydrous magnesium sulfate for 1 h after washing; after drying, filter and concentrate under reduced pressure to remove the solvent; use a mixture of acetone:ammonia = 13.5:1 as the eluent, select silica gel powder with a mesh size of 100-200 as the stationary phase of the chromatographic column, and perform separation and purification by wet loading to obtain a yellow solid. Wash the solid particles with anhydrous ethanol at the reflux temperature for 12 h, and perform vacuum filtration under reduced pressure to obtain a bright yellow solid with a yield of 35%.

[0078] The characterization results of the infrared spectrum, 1H NMR spectrum and 13C NMR spectrum of the obtained product are respectively as Figure 13 , Figure 14 and Figure 15 shown, and the characterization results indicate that the synthesized compound is bis(indolyl)nitro crown ether.

[0079] Example 6: Synthesis of bis(indolyl)crown ether diamine

[0080] The synthesis reaction formula of bis(indolyl)crown ether diamine is as follows:

[0081]

[0082] The specific method is as follows:

[0083] Add 0.2 g of bis(indolyl)nitro crown ether and 0.02 g of 10% palladium on carbon to the reaction device, and then add 5 ml of anhydrous ethanol; at the reflux temperature, dropwise add 1 ml of hydrazine hydrate to the reaction device within one hour; then under a nitrogen atmosphere, react at a reflux temperature of 85 °C for 14 h, monitor the progress of the reaction by TLC, after the reaction is completed, filter the reaction solution at atmospheric pressure, and then concentrate the filtrate under reduced pressure to remove the solvent; obtain a grayish-white crude product; then wash the crude product with tetrahydrofuran and anhydrous ethanol for 6 h each to obtain the final product, and the product is a grayish-white solid with a yield of 40%.

[0084] The characterization results of the infrared spectrum, 1H NMR spectrum and 13C NMR spectrum of the obtained product are respectively as Figure 16 , Figure 17 and Figure 18As shown, the characterization results indicate that the synthesized compound is bis(indolyl)crown ether diamine (INCEAM), and the structural formula of bis(indolyl)crown ether diamine is as Figure 19 shown.

[0085] Example 7: Preparation of bis(indolyl)crown ether-based epoxy resin film

[0086] 1. Preparation of INCEAM-DG polymer film

[0087] Mix bis(indolyl)crown ether diamine (INCEAM, 0.17 mmol, 0.098 g) with 2 mL of dimethyl sulfoxide (DMSO), and stir on a magnetic stirrer for 15 min to fully dissolve bis(indolyl)crown ether diamine to obtain a bis(indolyl)crown ether diamine solution; then mix bisphenol A diglycidyl ether (DGEBA, 0.34 mmol, 0.115 g) with the bis(indolyl)crown ether diamine solution, stir on a magnetic stirrer for 30 min to fully mix, dissolve and disperse, and then filter to obtain a slightly light yellow transparent solution.

[0088] Place a clean glass plate steadily and orderly in a levelled vacuum oven, then use a glass dropper to drop the above-obtained transparent solution onto the glass plate, heat the vacuum oven to 120 °C, turn off the vacuum oven after the temperature rise is completed, and cure at this temperature for 12 hours; then turn off the heating and insulation function, and after the polymer film cools to room temperature, immerse the glass plate and the film together in deionized water. After 10 minutes, gently lift the polymer film from the glass plate with a knife to obtain an INCEAM-DG polymer film, and the film is reddish-brown and transparent.

[0089] 2. Preparation of INCEAM-DG-K + polymer film

[0090] Prepare 5 portions of bis(indolyl)crown ether diamine solutions according to the above method, and then add 0.017 mmol (0.0028 g), 0.034 mmol (0.0056 g), 0.085 mmol (0.014 g), 0.17 mmol (0.028 g) and 0.21 mmol (0.035 g) of potassium iodide to the 5 portions of bis(indolyl)crown ether diamine solutions respectively, stir at room temperature for 1 h; then add bisphenol A diglycidyl ether (DGEBA, 0.34 mmol, 0.115 g) to the obtained solutions respectively, stir on a magnetic stirrer for 30 min to fully mix, dissolve and disperse, and then filter to obtain transparent solutions.

[0091] Place the clean glass plate steadily and orderly in the leveled vacuum oven. Then, use a glass dropper to drip the above-obtained transparent solution onto the glass plate. Heat the vacuum oven to 120 °C. After the temperature rise is completed, close the vacuum oven and cure it at this temperature for 12 hours. Then, turn off the heating and insulation function. After the polymer film has cooled to room temperature, immerse the glass plate and the film together in deionized water. After 10 minutes, gently use a knife to peel the polymer film from the glass plate to obtain INCEAM-DG-10%K + , INCEAM-DG-20%K + , INCEAM-DG-50%K + , INCEAM-DG-100%K + and INCEAM-DG-125%K + polymer films.

[0092] 3. Mechanical property analysis of INCEAM-DG polymer films and INCEAM-DG-K + polymer films

[0093] Use an E44.104 type electronic universal testing machine from MEST Industrial Systems (China) Co., Ltd. to test the mechanical properties of the prepared polymer films. When testing, cut the film into specimens with a length of 50 mm, a width of 5 mm, and a thickness of 0.05 mm. The test template is plastic tension, the gauge length is 30 mm, the tensile rate is 2 mm / min, and the sensor used is 50 N.

[0094] INCEAM-DG and INCEAM-DG-K + The tensile stress-strain curves of the polymer films are as Figure 20 shown, and the tensile strength and elongation at break are as Figure 21As shown; it can be seen from the figure that the tensile strength of the film without potassium ions is 75 MPa, and the elongation at break is 7.9%. When no potassium ions are added, the film shows obvious brittle fracture. After adding potassium ions, a yield appears in the stress-strain curve of the film. As the content of potassium ions increases from 0% to 100%, the mechanical strength of the film gradually increases. When the addition amount of potassium ions is 10% (molar ratio of potassium ions to crown ether ring), the tensile strength of the film increases from 75 MPa to 82 MPa, an increase of 7.9%, and the elongation at break increases from 7.9% to 9.7%, an increase of 22.7%. When the addition amount of potassium ions increases to 20%, the tensile strength of the film is 82 MPa, and the elongation at break increases from 7.9% to 12.7%, an increase of 60.8%. When the addition amount of potassium ions is 50%, the tensile strength of the film increases from 75 MPa to 90 MPa, an increase of 18.4%; the elongation at break increases from 7.9% to 13.9%, an increase of 75.9%. When the addition amount of potassium ions is 100%, the tensile strength of the film increases from 75 MPa to 92 MPa, an increase of 21.1%, and the elongation at break increases from 7.9% to 15.9%, an increase of 101.2%. When the addition amount of potassium ions is 125%, the mechanical properties of the film decline.

[0095] INCEAM-DG and INCEAM-DG-K + The fracture energy of the polymer film is as Figure 22 shown, and the Young's modulus is as Figure 23 shown; it can be seen from the figure that the fracture energy of the film increases with the increase of the potassium ion content, from 4.0 MJ / m 3 to 11.2 MJ / m 3 , an increase of 180.0%. The Young's modulus of the film increases from 1.52 GPa to 1.83 GPa, an increase of 20.4%. Similarly, when the addition amount of potassium ions is 125%, the fracture energy and Young's modulus of the film also decline. The improvement of the mechanical properties of the polymer film is attributed to the presence of a stretchable structure in the polymer network. When the film is stretched, the cation-π interaction is destroyed and the polymer chain order is elongated, effectively dissipating the external energy.

[0096] Although the specific implementation manners of the present invention have been described in detail in combination with the embodiments, it should not be construed as a limitation on the protection scope of this patent. Within the scope described in the claims, various modifications and deformations that can be made by those skilled in the art without creative efforts still fall within the protection scope of this patent.

Claims

1. A bis(indolyl) crown ether diamine, characterized in that, The structural formula of the bis(indole-crown ether) diamine is shown in Formula I; 2. The preparation method of the bis(indolyl)crown ether diamine according to claim 1, characterized in that, It includes the following steps: S1: Dissolve 4-trimethylsilyl-3-butyn-1-ol, imidazole and tert-butyldimethylsilyl chloride in a first solvent, and stir and react at room temperature for 15 h to obtain a compound shown in Formula II; S2: Dissolve 2-iodo-4-nitroaniline, the compound shown in Formula II, anhydrous lithium chloride, potassium acetate and palladium acetate in a second solvent, react at 70 - 80 °C for 2 - 3 h, then separate and purify to obtain a compound shown in Formula III; S3: Dissolve the compound shown in Formula III in a third solvent, then dropwise add an aqueous hydrofluoric acid solution to the obtained solution, and then stir and react at room temperature under sealed conditions for 48 h, then separate and purify to obtain a compound shown in Formula IV; S4: Dissolve carbon tetrabromide in a fourth solvent, then drop the obtained solution into a mixture composed of the compound shown in Formula IV and triphenylphosphine, and then stir and react at room temperature under light-shielded conditions for 2 - 3 h, separate and purify to obtain a compound shown in Formula V; S5: Dissolve diaza-18-crown-6-ether, sodium iodide and sodium carbonate in a fifth solvent to obtain a mixed solution; dissolve the compound shown in Formula V in the fifth solvent, and drop the obtained solution into the mixed solution under the atmosphere of a protective gas; then react at 80 - 90 °C for 20 - 25 h, and then separate and purify to obtain a compound shown in Formula VI; S6: Dissolve the compound shown in Formula VI and a palladium catalyst in a sixth solvent, then dropwise add hydrazine hydrate to the obtained solution, and then reflux and react at a reflux temperature of 80 - 90 °C for 12 - 16 h under the atmosphere of a protective gas, and then separate and purify to obtain the product.

3. The preparation method according to claim 2, characterized in that: The first solvent described in S1 is anhydrous DMF; the mass ratio of 4-trimethylsilyl-3-butyn-1-ol, imidazole and tert-butyldimethylsilyl chloride is 0.85 - 0.86:0.8 - 0.82:1 - 1.

1.

4. The preparation method according to claim 2, wherein: The second solvent described in S2 is anhydrous DMF; the mass ratio of 2-iodo-4-nitroaniline, the compound shown in Formula II, anhydrous lithium chloride, potassium acetate and palladium acetate is 2 - 3:0.7 - 0.8:0.2 - 0.3:2.5 - 3:0.1 - 0.

15.

5. The preparation method according to claim 2, characterized in that: The third solvent described in S3 is anhydrous acetonitrile, and the volume concentration of the aqueous hydrofluoric acid solution is 48%; the feed liquid ratio of the compound shown in Formula III to the aqueous hydrofluoric acid solution is 0.2 - 0.3 g:2 ml.

6. The preparation method according to claim 2, characterized in that: The fourth solvent described in S4 is anhydrous acetonitrile; the mass ratio of the compound shown in Formula IV, triphenylphosphine and carbon tetrabromide is 0.9 - 1:1.7 - 1.8:2 - 2.

3.

7. The preparation method according to claim 2, characterized in that: The fifth solvent described in S5 is anhydrous acetonitrile; the mass ratio of diaza-18-crown-6-ether, sodium iodide, sodium carbonate and the compound shown in Formula V is 0.9 - 1:0.05 - 0.06:1.5 - 2.5:2 - 2.

1.

8. The preparation method according to claim 2, characterized in that: The sixth solvent described in S6 is anhydrous ethanol, and the palladium catalyst is 10% palladium on carbon; the feed liquid ratio of the compound shown in Formula VI, the palladium catalyst and hydrazine hydrate is 0.2 g:0.02 g:1 ml.

9. Use of the bis(indolyl)crown ether diamine according to claim 1 in improving the mechanical properties of polymers.

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