Preparation method of anti-fouling supramolecular material with nano structure

Abstract

The application provides a preparation method of an anti-fouling supramolecular material with nano structure, comprising the following steps: synthesizing a POSS-based dendrimer assembly structure unit; preparing an assembly micelle with a teardrop shape of Rupert; polymerizing the nanomicelle into an anti-fouling material; adding the assembly micelle with the teardrop shape of Rupert into bimimidazole, continuously freezing and thawing and degassing, and then stopping the reaction after in-situ deposition polymerization of the colloid under light, so that a surface-treated micelle with the teardrop shape of Rupert is obtained, which is the anti-fouling supramolecular material with nano structure. The application adopts non-covalent bond driving to form a highly ordered functional self-assembly material, and prepares a supramolecular material with special nano structure characteristics through in-situ polymerization, which has hydrophobic and oleophobic properties and is widely applied, and can be applied to metal surface anti-graffiti, anti-rust and anti-scratch, applied on glass and ceramic, and applied to anti-fouling self-cleaning, so that the substrate surface is long and bright like new.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of anti-fouling supramolecular materials, and in particular to a preparation method of an anti-fouling supramolecular material with nanostructure. BACKGROUND

[0002] Supramolecular materials refer to highly ordered functional self-assembled materials formed under the driving of dynamic reversible non-covalent forces (hydrogen bonds, host-guest interactions, pi-pi stacking, etc.), and the supramolecular structure can be disassembled under certain conditions. The introduction of non-covalent forces can realize the regulation of the structure and function of the material, and endow the material with excellent properties such as stimulus responsiveness and self-healing characteristics. If the micro-nano structure formed by assembly can be prepared into supramolecular materials with special nanostructure characteristics through in-situ polymerization.

[0003] "Louplet tears" are a kind of "glass tear drops" formed by melting glass into ice water by gravity, which have wonderful physical properties: the tear drops are harder than ordinary glass, and under 8 tons of pressure, they are not broken, but under the application of weak pressure on the tail, the whole glass tear will be instantaneously exploded and crushed. There are further requirements for the strength of materials with such structure.

[0004] With the high standard requirements of modern technology on the process and quality of polymer materials, supramolecular polymer materials (SPMs) exhibit many unique stimulus responsiveness and mechanical adaptability due to their dynamic and reversible non-covalent interactions, and have been applied in many fields. For example, an impact protection supramolecular polymer material capable of soft-hard switching is prepared by using alcohol with flexible triblock and dimer containing hard segment. In the field of recognition, the supramolecular polymer framework material capable of realizing continuous response and high sensitivity detection is synthesized in patent CN107936262B. The material can respectively recognize Fe 3+ and H2PO4 - . In addition, Sun et al. (Advanced Functional Materials, 2016, 26(48)) designed a polymer-supramolecular polymer double network (PS-DN gel) formed by self-assembled peptide fibers for cartilage regeneration, which has a compressibility of about 66%–90% and can recover quickly within a few seconds. However, since many supramolecular polymer materials do not have special application value based on special self-assembled morphology, it is of great significance to develop supramolecular polymer materials with special nanostructure. SUMMARY

[0005] The present application provides a preparation method of an anti-fouling supramolecular material with nanostructure.

[0006] The application is to design and synthesize POSS (polyhedral oligomeric silsesquioxane) core dendrimer with 8 R groups (containing polymerizable functional groups), and control the micelle morphology and internal stress of the micelles formed by the assembly of the dendrimer in the solvent to control the diffusion. The -NH…C=O on the peripheral groups of the POSS core dendrimer with symmetrical structure can form strong hydrogen bonding under the influence of the solvent and repel each other, attract each other to self-assemble into micelles with uneven size while destroying the symmetrical structure of the POSS, and combine emulsion in-situ polymerization to prepare anti-fouling supramolecular materials with Rupert's tear structure.

[0007] A preparation method of an anti-fouling supramolecular material with nanostructure, which is carried out according to the following steps:

[0008] I. Synthesis of POSS-based dendrimer assembly structure unit:

[0009] The POSS-based dendrimer assembly structure unit is POSS-Lys-Dod, POSS-Dod, POSS-Oed or POSS-Had;

[0010] POSS-Lys-Dod is:

[0011]

[0012] POSS-Dod is:

[0013]

[0014] POSS-Oed is:

[0015]

[0016] POSS-Had is:

[0017]

[0018] II. Preparation of Rupert micelles:

[0019] 2.1) The POSS-based dendrimer assembly structure unit is added to tetrahydrofuran solvent, and ultrasonic dispersion is used to obtain a dispersion liquid;

[0020] 2.2) After the dispersion liquid is sealed and heated, stirring is carried out, water is added dropwise, the micelles are quickly aggregated and assembled, and the Rupert tear micelles are formed after standing for 3-10 h;

[0021] 90-110℃ sealed heating for 3-8 minutes, and further preferably, 100℃ sealed heating for 5 minutes.

[0022] Water was added dropwise through a microsyringe at a dropwise rate of 80-120 μL / 2 min.

[0023] The assembled micelles of the Ruper's tears morphology are strip-shaped, and the two ends of the strip-shaped micelles are different in size, gradually changing from the large end to the small end of the cross-sectional area of the strip-shaped micelles.

[0024] Further preferably, the method comprises:

[0025] ①Taking 1 mg of white powder of POSS-C11 in a 20 mL glass bottle, 10 mL of tetrahydrofuran solvent was added, and the dispersion liquid of POSS-C11 was obtained by ultrasonic dispersion.

[0026] ②1 mL of the dispersion liquid of POSS-Dod / THF was taken in a small glass bottle, and after being sealed and heated at 100°C for 5 minutes, the solution was slowly stirred on a magnetic stirrer, so that the POSS dendrimers were oriented and differentiated in the solution due to the stirring effect along the stirring direction. 300 μL of ultrapure water was added dropwise through a microsyringe at a dropwise rate of 100 μL / 2 min, and the addition of ultrapure water caused the micelles to quickly assemble in a special aggregation due to the solvation effect in the mixed solvent. The "Ruper's tears" morphology was stably maintained after being placed at room temperature for more than 4 h.

[0027] ③The assembled micelles after standing in the above-mentioned ② were transferred to a dialysis bag with a molecular weight cutoff of 8000-14000 by a syringe, and the dialysis bag was sealed and dialyzed in deionized water for 16 h to remove the organic solvent, so that the Ruper's morphology nanomicelles obtained by assembly could be maintained. However, it is not necessary to dialyze it in the polymerization system, and dialysis treatment is helpful for electron microscope observation of the morphology and long-term storage.

[0028] III. Polymerization of nanomicelles into anti-fouling materials

[0029] The assembled micelles of the Ruper's tears morphology prepared in step 2) were added to bimimidazole, and after continuous freeze-thaw degassing, the colloids were dropped on the substrate, and in-situ deposition polymerization occurred under light, and then the reaction was stopped, obtaining micelles with Ruper's morphology surface treated, which are anti-fouling supramolecular materials with nanostructure.

[0030] The light is UV irradiation for 1-5 h.

[0031] Further preferably, the method comprises:

[0032] The preparation method of step one and two is also used to test the 100 times larger amount, but no need to dialysis, after 4h of standing assembly, the formed lutein micelles in this colloidal assembly system, 1mg of bisimidazole is added, after continuous freeze-thaw degassing, the colloidal is dropped on the glass substrate, and the reaction is stopped after in-situ deposition polymerization under light. After light irradiation, the double bond structure in the lutein micelles is polymerized, and the solvent is volatilized at room temperature for 24h to form a coating film.

[0033] Compared with the prior art, the present application has the following advantages:

[0034] The present application adopts non-covalent bond driven to form highly ordered functional self-assembled materials, and in-situ polymerization is used to prepare supramolecular materials with special nanostructure characteristics. The formed material has a knitted structure, is similar to the surface of a lotus leaf, has hydrophobic and oleophobic properties, and is widely used. It can be applied to metal surfaces (such as range hood, stainless steel sink, etc.) to prevent graffiti, rust, and scratches; applied to glass and ceramics to prevent dirt and self-cleaning, so that the surface of the substrate is always bright and new. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The nanomicelle morphology prepared in step one of the embodiment is shown in the figure, with a magnification of 2000 times;

[0036] Figure 2 The nanomicelle morphology prepared in step one of the embodiment is shown in the figure, with a magnification of 12000 times. DETAILED DESCRIPTION

[0037] The technical solutions of the present application will be further described below through specific embodiments.

[0038] In the present application, unless otherwise specified, the raw materials and equipment used can be purchased from the market or commonly used in the art. The methods in the embodiments, unless otherwise specified, are conventional methods in the art.

[0039] Synthesis of POSS-based dendrimer assembly structure unit: through the synthesis method introduced in step one, different carboxylic acid molecules are used as the outer arm of the POSS-based dendrimer, including 10-undecanoic acid, 7-octenoic acid, 5-hexenoic acid, etc. The double bond structure of the carboxylic acid molecule is introduced into the POSS-based dendrimer to form different assembly units. The use of different assembly units in the micelle to supramolecular material polymerization preparation process found that the special molecular structure of the POSS-based dendrimer combined with double bond is a favorable basis for the preparation of lutein supramolecular material.

[0040] I. POSS-Lys-Dod

[0041]

[0042] Lys-Dod-COOH synthesis: 1.47 g (2.98 mmol) of Lys-Dod-COOMe was dissolved in 10 mL of methanol, 8.94 mL of sodium hydroxide aqueous solution (1 M, 8.94 mmol) was added under ice bath. The reaction was stirred for 24 hours under nitrogen atmosphere. After the reaction, the methanol was removed by rotary evaporator, the pH was adjusted to 3 by sodium bisulfate, and the product was extracted by ethyl acetate to obtain 1.38 g of white solid product. The yield was 96.5%.

[0043] POSS-Lys-Dod synthesis: 1.38 g (2.88 mmol) of Lys-Dod-COOH was dissolved in 20 mL of DMF, 0.6 g of NMM (6 mmol) was added. After stirring for 5 min, 1.09 g of HBTU (2.88 mmol) and 0.43 g of HOBt (3.16 mmol) were added, and then 0.24 g of POSS-NH2.HCl (0.21 mmol) was added. The reaction was stirred for 16 h. The reaction solution was poured into 0.5 M aqueous citric acid solution (150 mL), and the white precipitate was filtered and dried. The filter residue was washed with methanol. The product was obtained by column chromatography using DCM:MeOH=9:1 as the mixed solvent. The yield was 61.0%. 1 ​H NMR (POSS-Lys-Dod, DMSO-d6, 500 MHz, ppm): 11.97 (1H, s, COOH), 6.78 (1H, t, NH-Boc), 2.88 (2H, t, NHCH2CH2), 2.19 (2H, t, CH2CH2COOH), 1.40-1.46 (4H, m, CH2CH2CH2), 1.35 (12H, s, CH3), 1.22-1.24 (4H, m, CH2CH2CH2). ESI-MS (POSS-Lys-Dod): Theoretical value [M+Na]+=258.2, found 258.2, the structure of the product is consistent with the design structure.

[0044] The structural formula is as follows:

[0045]

[0046] II. POSS-Dod

[0047] 3 mmol 10-undecenoic acid was dissolved in 30 mL DMF, 0.6 g NMM (6 mmol) was added. 1.2 g HBTU (and 0.52 g HOBt) was added after stirring for 5 min, 0.28 g POSS-NH2.HCl was added, and the reaction was carried out for 16 h. The reaction solution was poured into 0.5 M aqueous citric acid solution (150 mL), and the white precipitate was filtered and dried, then washed with methanol, and the filter residue was obtained. Column chromatography was performed using a mixed solvent of DCM:MeOH=6:1 to obtain 0.28 g of white solid product. Yield 56.1%. 1H NMR (POSS-Dod, DMSO-d6, 500 MHz, ppm): 11.97 (1H, d, COOH), 6.77 (1H, t, NH-Boc), 2.88 (2H, dd, NHCH2CH2), 2.19 (2H, t, CH2CH2COOH), 1.48 (2H, t, CH2CH2CH2), 1.33-1.35 (12H, s, CH3), 1.24 (14H, m, CH2). ESI-MS (POSS-Dod): Theoretical value [M+Na]+=324.2, found 324.2, the structure of the product is consistent with the design structure.

[0048] The structural formula is as follows:

[0049]

[0050] III. POSS-Oed

[0051] POSS-NH2.HCl (0.45 g, 0.5 mmol) was added into the flask. The reaction was stirred for 16 h. The reaction solution was poured into 0.5 M aqueous citric acid solution (150 mL), and the white precipitate was collected by filtration. The product was washed with methanol and dried. The product was purified by column chromatography using DCM:MeOH = 6:1 as the mixed solvent to obtain 0.37 g of white solid product. The yield was 61.0%. 1 H NMR (POSS-Oed, DMSO-d6, 500 MHz, ppm), 7.79 (8H, s, CH2NHCOCH2), 6.74 (8H, t, NH-Boc), 3.01 (16H, t, CH2CH2NHCO), 2.96 (16H, t, CH2CH2NH-Boc), 2.44 (16H, t, NHCOCH2CH2), 1.54-1.39 (32H, m, CH2CH2CH2), 1.25-1.40 (96H, m, CH3), 0.59 (16H, br, SiCH2). FTIR (KBr) v = 3341, 2985, 2932, 1690, 1517, 1372, 1109 cm-1. m / z (ESI-MS, POSS-Oed): [M+2Na]2+theoretical value was 1147.7, the measured value was 1146.9, which was consistent with the measured value, indicating that the structure of the obtained product was consistent with the designed structure.

[0052] The structural formula is as follows:

[0053]

[0054] Ⅳ. POSS-Had

[0055] POSS-NH2.HCl (0.45 g, 0.5 mmol) was added into the flask. The reaction was stirred for 16 h. The reaction solution was poured into 0.5 M aqueous citric acid solution (150 mL), and the white precipitate was collected by filtration. The product was washed with methanol and dried. The product was purified by column chromatography using DCM:MeOH = 6:1 as the mixed solvent to obtain 0.37 g of white solid product. The yield was 61.0%.

[0056] 1HNMR (POSS-Had, DMSO-d6, 500 MHz, ppm): 7.77 (8H, d, CH2NHCOCH2), 6.76 (8H, t, NH-Boc), 3.01 (16H, d, CH2CH2NHCO), 2.88 (16H, d, CH2CH2NH-Boc), 2.04 (16H, t, NHCOCH2CH2), 1.54-1.39 (32H, m, CH2CH2CH2), 1.27-1.39 (96H, m, CH3), 1.20 (16H, m, CH2CH2CH2), 0.59 (16H, s, SiCH2). FT-IR (KBr): v = 3303, 2925, 2861, 1680, 1533, 1465, 1090. m / z (ESI-MS, POSS-Had): [M+2Na]2+theoretical value is 1315.7, the measured value is 1316.7, the measured value is consistent with the theoretical value, which proves that the structure of the obtained product is consistent with the designed structure.

[0057] The structural formula is as follows:

[0058]

[0059] Example 1:

[0060] ①Preparation of nanomicelles with a rosette-shaped morphology: taking POSS-Dod as an example, 100 mg of white powder of POSS-Dod was taken in a 200 mL glass bottle, 100 mL of tetrahydrofuran solvent was added, and ultrasonic dispersion was used to obtain a dispersion of POSS-Dod / THF. The POSS-Dod / THF dispersion was sealed in a glass bottle, and after 5 minutes of sealed heating at 100°C, the solution was slowly stirred on a magnetic stirrer, so that the POSS dendrimers in the solution were oriented and differentially assembled along the stirring direction. A microsyringe was used to add 30 mL of ultrapure water at a drop rate of 1 mL / 2 min, and the addition of ultrapure water caused the micelles to quickly assemble in a special aggregation due to the solvation effect in the mixed solvent. The "rosette-shaped tear" morphology was stably maintained after standing at room temperature for more than 4 hours.

[0061] As shown in Figure 1 and 2 , the assembled micelles with a rosette-shaped tear morphology are strip-shaped, and the size of the two ends of the strip-shaped micelles gradually changes from the end with a large cross-sectional area to the end with a small cross-sectional area.

[0062] ②After standing for 4 hours, the rosette-shaped tear micelles formed in this colloidal assembly system were added with 1 mg of bis-imidazole, and were subjected to continuous freeze-thaw degassing treatment four times.

[0063] ③The assembled micelles were dropped on the surface of clean polysulfone plastic plate or glass substrate, and in-situ polymerization was carried out on the medium surface after UV irradiation for 2h to obtain micelles with surface treatment of Rupert morphology. The surface hydrophilicity and hydrophobicity was determined by a contact angle measuring instrument to be 160°, indicating that the product has hydrophobic characteristics.

[0064] Example 2:

[0065] ①Preparation of Rupert morphology nanomicelles: taking POSS-Dod as an example, 100mg of white powder of POSS-Dod was taken in a 200ml glass bottle, 100ml of tetrahydrofuran solvent was added, and ultrasonic dispersion was used to obtain a dispersion of POSS-Dod / THF. The POSS-Dod / THF dispersion was sealed in a glass bottle, heated at 100℃ for 5 minutes, then slowly stirred the solution on a magnetic stirrer, so that the POSS dendritic macromolecules in the solution were oriented and differentiated assembly along the stirring direction, 30ml of ultrapure water was added at a drop rate of 1ml / 2min (1ml / min, 2ml / min, 3ml / min, 4ml / min) by using a microsyringe, the addition of ultrapure water made the molecules in the mixed solvent quickly assembled in a special aggregation due to the solvation effect, and the "Rupert tear" morphology could be stably maintained after standing at room temperature for more than 4h.

[0066] ②After standing for 4h, the Rupert tear micelles formed in the colloidal assembly system were added with 1mg of bis-imidazole, and after four times of continuous freeze-thaw degassing, the colloids were dropped on the glass substrate, and in-situ deposition polymerization occurred under light, then the reaction was stopped, and after light irradiation, the double bond structure inside the Rupert tear micelles was polymerized, and after standing at room temperature for 24h, the solvent was volatilized to form a coating film.

[0067] Example 3:

[0068] ①Preparation of Rupert morphology nanomicelles: taking POSS-Dod as an example, 100mg of white powder of POSS-Dod was taken in a 200ml glass bottle, 100ml of tetrahydrofuran solvent was added, and ultrasonic dispersion was used to obtain a dispersion of POSS-Dod / THF. The POSS-Dod / THF dispersion was sealed in a glass bottle, heated at 100℃ for 5 minutes, then slowly stirred the solution on a magnetic stirrer, so that the POSS dendritic macromolecules in the solution were oriented and differentiated assembly along the stirring direction, 30ml of ultrapure water was added at a drop rate of 1ml / 2min (1ml / min, 2ml / min, 3ml / min, 4ml / min) by using a microsyringe, the addition of ultrapure water made the molecules in the mixed solvent quickly assembled in a special aggregation due to the solvation effect, and the "Rupert tear" morphology could be stably maintained after standing at room temperature for more than 4h.

[0069] ②Rupert's tears micelles formed after 4h of static assembly, in this micellar assembly system, 1mg of bis-imidazole was added, after four times of freeze-thaw degassing, the colloid was dropped on the glass substrate under argon protection at 62℃, in-situ deposition polymerization occurred under light, the reaction was stopped after polymerization, after light irradiation, the double bond structure in the interior of Rupert's tears micelles polymerized, the solvent volatilized at room temperature for 24h, forming a coating film.

[0070] Example 4:

[0071] ①Preparation of Rupert's micelles: take 100mg of white powder of POSS-Dod in a 200mL glass bottle, add 100mL of tetrahydrofuran solvent, use ultrasonic dispersion to obtain a dispersion of POSS-Dod / THF. The POSS-Dod / THF dispersion was sealed in a glass bottle, heated at 100℃ for 5 minutes, then slowly stirred the solution on a magnetic stirrer, so that the POSS dendrimers in the solution were oriented and differentiated assembly along the stirring direction, use a micro-syringe to add 30mL (10mL, 20mL, 40mL, 50mL) ultrapure water at a drop rate of 1mL / 2min, the addition of ultrapure water makes the micelles quickly assemble in a special aggregation due to the solvation effect in the mixed solvent, and the "Rupert's tears" morphology can be stably maintained after standing at room temperature for more than 4h.

[0072] ②Rupert's tears micelles formed after 4h of static assembly, in this micellar assembly system, 1mg (2mg, 3mg, 4mg, 5mg) of bis-imidazole was added, after four times of freeze-thaw degassing, the colloid was dropped on the glass substrate under argon protection at 62℃, in-situ deposition polymerization occurred under light, the reaction was stopped after polymerization, after light irradiation, the double bond structure in the interior of Rupert's tears micelles polymerized, the solvent volatilized at room temperature for 24h, forming a coating film.

[0073] ③The assembled micelles were dropped on the surface of clean polysulfone plastic plate or glass substrate, and in-situ polymerization was carried out on the medium surface after UV irradiation for 2h, obtaining micelles with Rupert's morphology for surface treatment. The surface hydrophilicity and hydrophobicity was measured by contact angle tester as 160°, indicating that the product has hydrophobic properties.

[0074] ④The micro-morphology of the material was analyzed, and it was found that the material had a knitted structure similar to lotus leaves. The coated glass and plastic plate were tested for waterproofing, and it was found that when water contacted the material surface, it could freely roll off without invading the interior or adhering to the surface of the material, which could effectively prevent water. It can be applied to mobile phone anti-fingerprint, range hood oil-proof, cable surface smoothness, etc.

Claims

1. A method for preparing an antifouling supramolecular material with a nanostructure, characterized in that, Includes the following steps: 1) Synthesize POSS-based dendritic macromolecular assembly structural units; The POSS-based dendritic macromolecular assembly structural unit is POSS-Lys-Dod, POSS-Dod, POSS-Oed, or POSS-Had; Among them, POSS-Lys-Dod is: ； POSS-Dod is: ； POSS-Oed is: ； POSS-Had is: ； 2) Preparation of assembled micelles with Rupert's Tear morphology: 2.1) POSS-based dendritic macromolecules are assembled into structural units, added to tetrahydrofuran solvent, and dispersed by ultrasonication to obtain a dispersion. 2.2) After sealing and heating the dispersion, stir and add water dropwise to make the micelles quickly aggregate and assemble. Let stand for 3~10 hours to form assembled micelles with the morphology of Rupert's Tears. 3) Nanomicelles polymerize into antifouling materials: The assembled micelles with the Rupert tear morphology prepared in step 2) were added to memidazole. After continuous freeze-thaw degassing, the colloids were subjected to in-situ deposition polymerization under light irradiation, and the reaction was stopped to obtain surface-treated micelles with the Rupert morphology, which are antifouling supramolecular materials with nanostructures.

2. The method for preparing the antifouling supramolecular material with a nanostructure according to claim 1, characterized in that, In step 2.2), heat in a sealed container at 90~110℃ for 3~8 minutes.

3. The method for preparing the antifouling supramolecular material with a nanostructure according to claim 1, characterized in that, In step 2.2), water is added dropwise through a microsyringe at a dropping rate of 80~120μL / 2min.

4. The method for preparing the antifouling supramolecular material with a nanostructure according to claim 1, characterized in that, In step 2.2), the assembled micelles of the Rupert's Tear morphology are strip-shaped with different sizes at both ends, gradually changing from the end with a larger cross-sectional area to the end with a smaller cross-sectional area.

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