Photoresponse molecule modified polyarylether compound and preparation method thereof, photoresponse composite membrane as well as preparation method and application of photoresponse composite membrane

Abstract

The invention belongs to the technical field of porous functional materials, and particularly relates to a photoresponse molecule modified polyarylether compound and a preparation method thereof, a photoresponse composite membrane and a preparation method and application thereof. The invention provides a polyarylether compound which has a structure as shown in a formula I. The polyarylether compound provided by the invention has the advantages of stable structure and chemical corrosion resistance, light response molecules can be modified by a chemical modification method, and then the ultraviolet light response polyarylether porous nano composite membrane is prepared by adopting a self-assembly mode. The porous nano channel can realize response to ultraviolet light, current amplification, ion selectivity and rectification characteristics, and provides a new research thought for development and application of a logic circuit based on an optical sensing ion information processing system and ion conduction. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of porous functional materials, and particularly relates to a polyarylether compound modified with a photo-responsive molecule, a preparation method thereof, a photo-responsive composite membrane, a preparation method thereof and an application thereof. Background Art

[0002] In nature, with "ions" as carriers, many things happen all the time, such as information transmission and processing, energy conversion and storage. At the same time, modern artificial intelligence machines process information and transfer energy with "electrons" as carriers. In fact, these two carriers are not parallel but can be intertwined with each other.

[0003] To achieve the encoding and input of external information into biological intelligence, a sensing system based on ion transport should be developed because they operate in the same way as nature. For example, rhodopsin channels existing in nature are a kind of light-controlled cation channels. In addition to directly using such channels, researchers have begun to develop solid-state nanochannels with controllable physical and chemical properties. For example, photoacid molecules are modified on acrylamide / DNA copolymers, and under ultraviolet light irradiation, photoacid generators release hydrogen ions to realize the construction of a photo-responsive DNA hydrogel based on the photo-induced proton transfer process. However, the hydrogel has the problem of poor mechanical properties. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a polyarylether compound modified with a photo-responsive molecule, a preparation method thereof, a photo-responsive composite membrane, a preparation method thereof and an application thereof. After the polyarylether compound of the present invention is modified with a photo-responsive molecule, the prepared photo-responsive membrane has excellent mechanical strength.

[0005] The present invention provides a polyarylether compound, and the polyarylether compound has a structure shown in Formula I:

[0006]

[0007] In Formula I, A independently selects a structure shown in any one of Formula A-1 to A-11:

[0008]

[0009]

[0010] B independently selects a structure shown in any one of Formula B-1 to B-13:

[0011]

[0012] The range of n / (n + m) is 0.1 to 1.

[0013] The present invention also provides a method for preparing the polyarylether compound described in the above technical solution, which includes the following steps:

[0014] After mixing the first monomer, the second monomer, the third monomer, the first organic solvent, the first catalyst and the water-carrying agent for water removal treatment, a polycondensation reaction is carried out to obtain the polyarylether compound;

[0015] The structural formula of the first monomer is HO-A-OH, the structural formula of the second monomer is HO-B-OH, and the structural formula of the third monomer is shown as follows, where X is a halogen group.

[0016]

[0017] The present invention also provides a polyarylether compound modified with a photo-responsive molecule, which includes the polyarylether compound and a photo-responsive molecule modified on the polyarylether compound;

[0018] The photo-responsive molecule includes a spiropyran compound, an azobenzene compound or a triphenylmethane compound;

[0019] The polyarylether compound is the polyarylether compound described in the above technical solution; the photo-responsive molecule is connected to the carboxyl group of part A of the polyarylether compound.

[0020] The present invention also provides a method for preparing the polyarylether compound modified with a photo-responsive molecule described in the above technical solution, which includes the following steps:

[0021] The photo-responsive molecule, the polyarylether compound, the second catalyst and the second organic solvent are mixed to carry out an esterification reaction, an amidation reaction or a substitution reaction to obtain the polyarylether compound modified with a photo-responsive molecule.

[0022] The present invention also provides a photo-responsive film, and the film-forming substance of the photo-responsive film is the polyarylether compound modified with a photo-responsive molecule described in the above technical solution.

[0023] The present invention also provides a method for preparing the photo-responsive film described in the above technical solution, which includes the following steps:

[0024] The polyarylether compound modified with a photo-responsive molecule described in the above technical solution and a third organic solvent are mixed to obtain a casting solution;

[0025] The casting solution is prepared into a film by a non-solvent phase separation method to obtain the photo-responsive film.

[0026] The present invention also provides a photo-responsive composite film, which includes a laminated photo-responsive film and a sulfonated polyethersulfone film;

[0027] The photo-responsive film is the photo-responsive film described in the above technical solution.

[0028] The present invention also provides a method for preparing the photo-responsive composite film described in the above technical solution, including the following steps:

[0029] Mix the polyarylether compound modified with the photo-responsive molecule described in the above technical solution and a third organic solvent to obtain a casting solution;

[0030] Spin-coat the casting solution on the surface of the sulfonated polyethersulfone membrane to obtain the photo-responsive composite film.

[0031] Preferably, the film-forming substance of the sulfonated polyethersulfone membrane is sulfonated polyethersulfone, and the structural formula of the sulfonated polyethersulfone is shown as follows:

[0032]

[0033] In the formula, x is the molar proportion of the chain segment containing the biphenyl group, and the range is 0.1-1.

[0034] The present invention also provides the application of the photo-responsive film or the photo-responsive composite film described in the above technical solution in a biomimetic ion device.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The present invention provides a polyarylether compound with the structure shown in Formula I:

[0037]

[0038] The structure of the polyarylether compound of the present invention contains a benzene ring and a sulfone-based rigid chain segment, has excellent mechanical strength, high-temperature stability, chemical corrosion resistance, and an efficient and stable microporous structure, and can adjust the modification quantity of the photo-responsive group according to the structure design to construct a photo-responsive biomimetic ion device. After the polyarylether compound of the present invention is modified with a photo-responsive molecule, the obtained photo-responsive film has excellent mechanical strength.

[0039] The present invention also provides a polyarylether compound modified with a photo-responsive molecule. The present invention modifies the photo-responsive molecule onto the polyarylether compound, forms a thin film by the method of phase separation self-assembly, and successfully constructs a nanochannel based on the photo-responsive molecule modification, which can realize the regulation of ionic conductivity, ion selectivity, and ion rectification characteristics.

[0040] Under ultraviolet light illumination, the charge density in the nanochannels increases and the pore structure changes in the polyarylether-based compound film modified with photo-responsive molecules of the present invention, rapidly generating a photo-responsive current. This ionic current characteristic can be restored after the removal of illumination, realizing the response characteristic controlled by ultraviolet-visible light, and changing the ionic current of the channel; enabling the prepared product to regulate the ionic current under the stimulation of external light, conduct signal transmission, and simulate the information transmission mode in the living body, where external stimulation generates an action potential to open the ion channel, promoting the transmission of neurotransmitters. And it has rectifying properties, providing a new research strategy for the development and application of photo-sensing ion information processing systems, ion diodes, and ion logic circuits. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0042] Figure 1 1H NMR spectrum of the polyarylether compound prepared in Example 1;

[0043] Figure 2 1H NMR spectrum of the polyarylether compound modified with spiropyran molecules prepared in Example 2;

[0044] Figure 3 IR spectrum of the polyarylether compound modified with spiropyran molecules prepared in Example 2;

[0045] Figure 4 Cross-sectional scanning electron microscope image of the monolayer photo-responsive film in Example 3;

[0046] Figure 5 Planar transmission electron microscope image of the monolayer photo-responsive film in Example 3;

[0047] Figure 6 Ion selectivity image of the monolayer photo-responsive film in Example 3;

[0048] Figure 7 Current-time (I-t) curve of the monolayer photo-responsive film in Test Example 1;

[0049] Figure 8 Mechanical strength diagram of the photo-responsive film prepared in Example 3;

[0050] Figure 9 1H NMR (a) and IR spectra (b) of the polyarylether and sulfonated polyarylether compounds in Example 4;

[0051] Figure 10 It is the planar transmission electron microscope image of the single-layer sulfonated polyarylether membrane in Example 5;

[0052] Figure 11 It is the ion selectivity image of the single-layer sulfonated polyarylether membrane in Example 5;

[0053] Figure 12 It is the cross-sectional scanning electron microscope image of the double-layer light-responsive heterojunction membrane in Example 5;

[0054] Figure 13 It is the current-time (I-t) curve of the double-layer light-responsive heterojunction membrane in Test Example 2;

[0055] Figure 14 It is the relationship diagram between the concentration and the rectification ratio of the double-layer light-responsive nanochannel in Test Example 2;

[0056] Figure 15 It is the current-voltage (I-V) curve of the double-layer light-responsive nanochannel in Test Example 2;

[0057] Figure 16 It is the schematic diagram of the ion device test apparatus. Detailed implementation manners

[0058] The present invention provides a polyarylether compound, and the polyarylether compound has a structure shown in Formula I:

[0059]

[0060] In Formula I, A independently selects any one of the structures shown in Formula A-1 to A-11:

[0061]

[0062]

[0063] B independently selects any one of the structures shown in Formula B-1 to B-13:

[0064]

[0065] The range of n / (n + m) is 0.1 to 1.

[0066] In the present invention, n / (n + m) represents the molar proportion of the polymerization unit containing A, and is preferably 0.2 to 0.8, and specifically can be 0.2, 0.4, 0.6 or 0.8.

[0067] In the present invention, the degree of polymerization of the polyarylether compound is preferably several thousand to several tens of thousands.

[0068] In the present invention, the inherent viscosity of the polyarylether compound is preferably 0.3 to 1.2, specifically it can be 0.51, the number average molecular weight is preferably 40 to 100 kDa, specifically it can be 65 kDa, and the dispersity index is preferably 0.5 to 2.5, specifically it can be 2.1.

[0069] The present invention also provides a method for preparing the polyarylether compound described in the above technical solution, including the following steps:

[0070] After mixing and dehydrating the first monomer, the second monomer, the third monomer, the first organic solvent, the first catalyst and the water-carrying agent, a polycondensation reaction is carried out to obtain the polyarylether compound;

[0071] The structural formula of the first monomer is HO-A-OH, the structural formula of the second monomer is HO-B-OH, and the structural formula of the third monomer is shown as follows, where X is a halogen group.

[0072]

[0073] In the present invention, unless otherwise specified, the materials and equipment used are commercially available products in the art.

[0074] In the present invention, the first monomer is preferably selected from any one of the structures shown in formulas i-1 to i-11:

[0075]

[0076]

[0077] The second monomer is preferably selected from any one of the structures shown in formulas ii-1 to ii-13:

[0078]

[0079] In the present invention, the third monomer is a para-halogenated diphenyl sulfone monomer, and the halogen group is preferably -F or -Cl.

[0080] The present invention has no special limitation on the molar ratio of the first monomer and the second monomer. The molar ratio of the first monomer and the second monomer is preferably (0.25 to 4):1, more preferably (0.25 to 1):1, specifically it can be 2:3 or 1:4.

[0081] In the present invention, the amount of substance of the third monomer is preferably the sum of the amounts of substance of the first monomer and the second monomer.

[0082] In the present invention, the first organic solvent preferably includes sulfolane, dimethyl sulfoxide or N-methylpyrrolidone. The mass of the first organic solvent is preferably 3 to 5 times the total mass of the first monomer, the second monomer and the third monomer, specifically 3 times, 4 times or 5 times.

[0083] In the present invention, the first catalyst preferably includes any one or a mixture of several of alkali metal carbonates and alkali metal hydroxides. The alkali metal carbonate is preferably any one or a mixture of several of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate and cesium bicarbonate. The alkali metal hydroxide is preferably any one or a mixture of several of potassium hydroxide, sodium hydroxide and cesium hydroxide. The amount of substance of the first catalyst is preferably 1.2 to 2 times the sum of the amounts of substance of the first monomer and the second monomer, specifically 1.4 times.

[0084] In the present invention, the water-carrying agent preferably includes benzene, toluene, xylene or chlorobenzene. The volume of the water-carrying agent is preferably 10 to 20% of the volume of the reactor.

[0085] In the present invention, the processes of mixing and water treatment removal and polycondensation reaction of the first monomer, the second monomer, the third monomer, the first organic solvent, the first catalyst and the water-carrying agent are all preferably carried out under a protective atmosphere and stirring conditions. The gas of the protective atmosphere is preferably argon. The present invention has no special limitation on the stirring rate, and the stirring rate commonly used by those skilled in the art can be adopted.

[0086] In the present invention, the temperature of the water treatment removal is preferably 60 to 150 °C, more preferably 125 to 145 °C; the time is preferably 2 to 6 h, more preferably 3 to 4 h.

[0087] In the present invention, the temperature of the polycondensation reaction is preferably 160 to 220 °C, more preferably 165 to 195 °C, specifically 175 °C; the time is preferably 4 to 24 h, more preferably 6 to 15 h. During the water treatment removal process, the water-carrying agent will carry out the water in the system, and when no water is carried out completely, the water treatment removal is completed, and the system is directly heated to carry out the polycondensation reaction. As the polycondensation reaction proceeds, the viscosity of the system continuously increases until the viscosity no longer changes, and the polycondensation reaction ends. During the polycondensation reaction process, the first monomer, the second monomer and the third monomer carry out polycondensation reaction to obtain a polyarylether compound.

[0088] In the present invention, after the polycondensation reaction, it preferably further includes: pouring the obtained product system into deionized water to precipitate solid materials, crushing the solid materials, and then successively washing and drying to obtain a white solid, which is the polyarylether compound. The washing preferably includes washing with water and then with ethanol in sequence. The water washing preferably uses boiling water, and its function is to remove the catalyst and solvent in the system; the number of times of water washing and ethanol washing is independently preferably 3 to 5 times. The drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 80 to 120 °C; the present invention has no special limitation on the time of the vacuum drying, and it can be dried to a constant weight.

[0089] The present invention also provides a polyarylether compound modified with a photo-responsive molecule, including the polyarylether compound and a photo-responsive molecule modified on the polyarylether compound;

[0090] The photo-responsive molecule includes a spiropyran compound, an azobenzene compound or a triphenylmethane compound;

[0091] The polyarylether compound is the polyarylether compound described in the above technical solution; the photo-responsive molecule is connected to the carboxyl group of part A of the polyarylether compound.

[0092] In the present invention, the spiropyran compound is preferably a spiropyran derivative containing a hydroxyl group and / or an amino group, and the structural formula is shown as follows:

[0093]

[0094] In the formula, R 1 , R 5 , R 6 , R 7 , R 8 is selected from one of -COOH, -OH, -H, -CF 3 , an alkoxy group with 1 to 8 carbon atoms, phenyl, nitro, R 2 , R 3 is -H, R 4 is an alkylamine with 1 to 8 carbon atoms or an alkyl alcohol with 1 to 8 carbon atoms, R 9 , R 10 is selected from one of -H and an alkyl group with 1 to 4 carbon atoms.

[0095] In the present invention, the structural formula of the spiropyran compound is preferably shown as follows:

[0096]

[0097] In the present invention, the azobenzene compound is preferably an azobenzene derivative containing a hydroxyl group and / or an amino group, and the structural formula is shown as follows:

[0098]

[0099] In the formula, R 1 is selected from one of -OH, -NH 2 or -COOH, and R 2 is -OH or -NH 2 .

[0100] In the present invention, the structural formula of the azobenzene compound is preferably as shown in the following formula:

[0101]

[0102] In the present invention, the triphenylmethane compound is preferably a triphenylmethane derivative containing hydroxyl and / or amino groups, and the structural formula is as shown in the following formula:

[0103]

[0104] In the formula, X is -OH, and R is -OH, -NH 2 or any one of -Cl.

[0105] In the present invention, the structural formula of the triphenylmethane compound is preferably as shown in the following formula:

[0106]

[0107] The present invention also provides a preparation method of the polyarylether compound modified with the photo-responsive molecule described in the above technical solution, including the following steps:

[0108] Mix the photo-responsive molecule, polyarylether compound, second catalyst and second organic solvent to carry out an esterification reaction, amidation reaction or substitution reaction to obtain the polyarylether compound modified with the photo-responsive molecule.

[0109] In the present invention, the molar ratio of the total number of polymerization units in the photo-responsive molecule and the polyarylether compound is preferably 0.4 to 10:1, and more preferably 2:5.

[0110] In the present invention, the second organic solvent is preferably one or more of dimethyl sulfoxide, N,N-dimethylformamide, acetone, tetrahydrofuran, ethanol, dichloromethane and chloroform. The mass ratio of the second organic solvent to the total reactants is preferably 4 to 15:1, and more preferably 4 to 5:1. The total reactants include the photo-responsive molecule and the polyarylether compound.

[0111] In the present invention, the second catalyst is preferably one or a mixture of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt (EDCI), N,N'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 4-dimethylaminopyridine (DMAP), N-N-hydroxysuccinimide, more preferably EDCI and DMAP, and the molar ratio of EDCI to DMAP is preferably 10:1; the molar ratio of the second catalyst to the functional group is preferably 2-10:1 ， The functional group is the carboxyl group of part A of the polyarylether compound.

[0112] In the present invention, the esterification reaction, amidation reaction or substitution reaction is preferably carried out independently under the conditions of nitrogen, light avoidance and stirring. The reaction time is independently preferably 24-96 h, more preferably 48-72 h, and the rotation speed of the stirring is preferably 120 r / min.

[0113] In the present invention, after the esterification reaction, amidation reaction or substitution reaction, it preferably further includes: washing the obtained product successively with ethanol and water, and then drying.

[0114] Taking the first monomer as i-1 and the second monomer as ii-1 as examples, the reaction formulas for modifying the photo-responsive molecules with spiropyran compounds, azobenzene compounds and triphenylmethane compounds are respectively exemplified as follows:

[0115]

[0116]

[0117] The present invention also provides a photo-responsive film, and the film-forming substance of the photo-responsive film is the photo-responsive molecule-modified polyarylether compound described in the above technical solution.

[0118] The present invention also provides a preparation method of the photo-responsive film described in the above technical solution, including the following steps:

[0119] Mix the photo-responsive molecule-modified polyarylether compound described in the above technical solution with a third organic solvent to obtain a casting solution;

[0120] Prepare the casting solution into a film by the non-solvent phase separation method to obtain a photo-responsive film.

[0121] In the present invention, when the photo-responsive molecule-modified polyarylether compound is mixed with the third organic solvent, a pore-forming agent is preferably further added, and the pore-forming agent preferably includes polyvinylpyrrolidone-K30 or lithium chloride.

[0122] In the present invention, the third organic solvent preferably includes N-methylpyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide.

[0123] In the present invention, the mass of the pore former preferably does not exceed 40-80% of the total mass of the polyarylether compound modified with a photo-responsive molecule and the pore former, more preferably 50-60%; the total mass fraction of the polyarylether compound modified with a photo-responsive molecule and the pore former in the casting solution is preferably 2-60%, more preferably 30-40%.

[0124] In the present invention, the dosage ratio of the polyarylether compound modified with a photo-responsive molecule, the pore former and the third organic solvent is preferably 12 mg: 12 mg: 1 mL. The mixing preferably includes: stirring at room temperature under closed conditions, followed by filtration and degassing; the stirring time is preferably 10 h, the filtration preferably uses a filter cloth, the degassing is preferably static degassing, and the static degassing time is preferably 12 h.

[0125] In the present invention, the non-solvent phase separation method preferably includes the following steps: in an oven, casting the casting solution onto the upper surface of a substrate to form a liquid film on the upper surface of the substrate. The substrate is preferably a glass plate.

[0126] The present invention also provides a photo-responsive composite membrane, including a stacked photo-responsive membrane and a sulfonated polyethersulfone membrane;

[0127] The photo-responsive membrane is the photo-responsive membrane described in the above technical solution.

[0128] The present invention also provides a preparation method of the photo-responsive composite membrane described in the above technical solution, including the following steps:

[0129] Mix the polyarylether compound modified with a photo-responsive molecule and the third organic solvent described in the above technical solution to obtain a casting solution;

[0130] Spin-coat the casting solution on the surface of the sulfonated polyethersulfone membrane to obtain a photo-responsive composite membrane.

[0131] In the present invention, the film-forming substance of the sulfonated polyethersulfone membrane is preferably sulfonated polyethersulfone, and the structural formula of the sulfonated polyethersulfone is preferably as shown in the following formula:

[0132]

[0133] In the formula, x is the molar ratio of the chain segment containing a biphenyl group, and the range is preferably 0.1-1, more preferably 0.2-0.8, and still more preferably 0.4-0.6.

[0134] In the present invention, the preparation method of the sulfonated polyethersulfone membrane preferably includes the following steps:

[0135] Stir and mix sulfonated polyethersulfone, a pore former, and an organic solvent, and then successively filter and let stand to obtain a first casting solution;

[0136] Form a film from the first casting solution to obtain a sulfonated polyethersulfone membrane.

[0137] The stirring and mixing is preferably carried out at room temperature under closed conditions. The room temperature means no additional heating or cooling is required. In the examples of the present invention, the room temperature specifically refers to 25°C; the stirring and mixing time is preferably 8 - 12 h, more preferably 10 h; the present invention has no special limitation on the rotation speed of the stirring and mixing, and a stirring rate well-known to those skilled in the art can be adopted. The standing is preferably carried out at room temperature, and the standing time is preferably 10 - 15 h, more preferably 12 h; the present invention realizes degassing through standing.

[0138] The film formation is preferably carried out by the nonsolvent phase separation method, and preferably includes the following steps: In an oven, cast the first casting solution on the upper surface of a substrate to form a liquid film on the upper surface of the substrate. The substrate is preferably a glass plate. After forming a liquid film on the upper surface of the substrate, preferably expose the liquid film to the air, the function of which is to cause partial volatilization of the solvent at the liquid film - air interface and promote pore formation on the film surface; the oven temperature can be set according to different solvents to cause phase separation. The present invention forms a film by the phase separation method, and the method has simple operation, low cost, and can be produced on a large scale, avoiding the problem that the filtration film formation process in the prior art is difficult to produce on a large scale.

[0139] After obtaining the sulfonated polyethersulfone membrane, the present invention spin - coats a casting solution containing a polyarylether compound modified with a photo - responsive molecule on the surface of the sulfonated polyethersulfone membrane to obtain a photo - responsive composite membrane. The solvent of the spin - coating solution is preferably dichloromethane to form a composite porous membrane with an asymmetric structure. After drying the substrate with the attached polymer membrane, immerse it in water, preferably change the water every 6 - 12 h, and change the water 3 - 4 times in total to remove the residual solvent; the water is preferably deionized water. The drying temperature is preferably 80 - 120°C, and the time is preferably 30 - 36 h. The drying can specifically be: successively heat up to 80°C, 100°C, and 120°C and vacuum dry for 12 h respectively.

[0140] In the present invention, the thickness of the photo - responsive membrane is preferably 1 - 300 μm, more preferably 1 - 20 μm, and specifically can be 10 μm. The thickness of the sulfonated polyethersulfone membrane is preferably 1 - 300 μm, more preferably 1 - 10 μm, and specifically can be 3 μm.

[0141] In the present invention, the pore diameter of the photo - responsive membrane is preferably 10 - 50 nm, and the pore diameter of the sulfonated polyethersulfone membrane is preferably 5 - 100 nm.

[0142] The light-responsive composite membrane obtained in the present invention is an asymmetric ion exchange membrane, which is a composite membrane based on the adjustable ion conductivity of light response. Taking the polyarylether compound modified with spiropyran molecules as an example, the principle of ion conductivity regulation is shown in the following formula:

[0143]

[0144] Under ultraviolet light conditions, spiropyran ring-opening generates positive charges, which changes the charge density of the pores. The ring-opening structure changes the pore size, thereby regulating the conductivity. Under ultraviolet light irradiation, the ion current can increase by 1.5 microamperes.

[0145] The present invention also provides the application of the light-responsive membrane or light-responsive composite membrane described in the above technical solution in a biomimetic ion device.

[0146] In the present invention, the electrode in the biomimetic ion device is preferably a silver / silver chloride electrode, and the electrolyte is preferably an aqueous solution of potassium chloride, an aqueous solution of sodium chloride, an aqueous solution of potassium iodide or an aqueous solution of sodium iodide, more preferably an aqueous solution of potassium chloride; the concentration of the electrolyte is preferably 1 to 5000 mmol / L, more preferably 10 to 1000 mmol / L.

[0147] The present invention uses ions as signal carriers to simulate biological systems, and constructs a biomimetic ion device with fast response, stable structure and good mechanical properties in a liquid environment.

[0148] The present invention uses spiropyran compounds, azo compounds and triphenylmethane derivative compounds as responsive molecules to modify polyether aromatic polymers. The regulation of the ion conductivity of the present invention is achieved by regulating the surface charge density and pore size of the ion channels through ultraviolet light irradiation, accelerating the passage of ions, so as to encode and input external information into the ion current, thereby simulating the generation of action potentials in the body under external stimuli, and then opening the ion channels to promote the transmission of neurotransmitters to achieve the process of information transmission.

[0149] The present invention provides a preparation method of a polyarylether porous membrane with light-regulated ion conductivity compatible in a liquid environment. On the basis of a single-layer membrane, a polyethersulfone ion polymer with a strongly negatively charged sulfonic acid group is selected as the asymmetric layer to prepare a composite membrane with a controllable heterogeneous structure. The rectification effect of the composite membrane is regulated by regulating the thickness, charge density and pore structure of the composite membrane. In a liquid environment simulating an organism, a biomimetic ion diode device with fast response and stable structure is constructed. It provides new research ideas for the development and application of ion information processing systems and ion logic circuits based on intelligent response materials and intelligent sensing.

[0150] To further illustrate the present invention, the polyarylether compounds, polyarylether compounds modified with photo-responsive molecules, their preparation methods, photo-responsive films, composite films, their preparation methods and applications provided by the present invention will be described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0151] Example 1

[0152] Under anhydrous and argon protection conditions, 40.0 mmol (10.1903 g) of 4,4'-difluorodiphenyl sulfone, 16 mmol (4.5811 g) of 4,4-bis(4-hydroxyphenyl)valeric acid, 24.0 mmol (4.4690 g) of 4,4'-dihydroxybiphenyl, 56 mmol (7.7398 g) of potassium carbonate, 30 mL of toluene and 77 mL of sulfolane were added to a 250 mL three-necked flask. The resulting mixed system was heated to reflux (145 °C) for 4 h under stirring conditions to allow toluene to fully remove the water generated in the system; then the resulting system was heated to 175 °C and reacted for 6 h until the viscosity of the system no longer changed; the resulting product system was poured into deionized water to precipitate solid materials. The solid materials were crushed and washed 3 times with boiling water, and then washed 3 times with ethanol, and vacuum dried at 80 °C to constant weight to obtain a white solid, which was a polyarylether compound (carboxyl polyarylether sulfone).

[0153] The inherent viscosity of the obtained polyarylether compound was 0.51, the number average molecular weight was 65 kDa, and the dispersity index was 2.1; its NMR spectrum was as Figure 1 shown, and the data were as follows: 1H NMR (400 MHz, DMSO) δ 12.06 (s, 0H), 7.91 (dd, J = 14.1, 7.5 Hz, 4H), 7.71 (s, 4H), 7.51–6.78 (m, 11H), 2.34 (s, 1H), 2.00 (s, 1H), 1.57 (s, 1H).

[0154] Example 2

[0155] The spiropyran compound, polymer, catalyst and solvent were stirred and reacted for 48 h at a stirring speed of 120 r / min in the presence of nitrogen and protected from light. After the reaction was completed, the product was discharged into deionized water, filtered, and the filter cake was washed thoroughly with ethanol and water in turn, and vacuum dried (120 °C) to obtain a spiropyran-modified polyarylether compound.

[0156] Among them, the spiropyran compound was a hydroxy spiropyran derivative, and its structural formula was as follows:

[0157]

[0158] The polymer is the carboxyl polyarylethersulfone prepared in Example 1, and the molar ratio of the spiropyran compound to the total number of polymerization units in the carboxyl polyarylethersulfone is 2:5.

[0159] The catalysts are 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt (EDCI) and 4-dimethylaminopyridine (DMAP). The molar ratio of EDCI to DMAP is 10:1, and the molar ratio of the catalysts to the carboxyl groups of part A of the polyarylether compound is 2:1. 。

[0160] The solvent is N,N-dimethylformamide, and the mass ratio of the solvent to the total mass of the reactants is 4:1.

[0161] The prepared spiropyran-modified polyethersulfone has a NMR spectrum as Figure 2 shown. By comparing and differentiating Figure 2 with Figure 1 , the differences between the modified product and the original polymer can be seen, and the spiropyran compound is modified on the polymer through the carboxyl group.

[0162] Using the KBr tablet pressing method, the polymers before and after modification are scanned by Fourier transform infrared spectrometer in the wavelength range from 400 to 4000 cm -1 , with a resolution of 2 cm -1 . Compared with polyethersulfone (such as the black line in Figure 3 , PAES-COOH), the spiropyran-modified polyethersulfone (such as the red line in Figure 3 , PAES-COO-SP) shows a new O-C-N characteristic peak at 955 cm -1 and a C-N characteristic peak at 1383 cm -1 , indicating that the spiropyran has been successfully grafted onto the polyethersulfone.

[0163] Example 3

[0164] 60 mg of the spiropyran-modified polyarylether compound prepared in Example 2, 60 mg of polyvinylpyrrolidone-K30 and 5 mL of N-methylpyrrolidone are mixed, and stirred at room temperature (25 °C) under closed conditions for 10 h to obtain a clear and transparent viscous liquid. After filtering with filter cloth and standing for degassing for 12 h, a casting solution is obtained;

[0165] The casting solution is dropped onto the surface of a 2 cm × 2 cm glass plate which is horizontally placed in a preheated oven at 40 °C and is smooth and flat. The oven is heated to 60 °C. After no liquid droplets evaporate and condense on the window, it is heated to 80 °C, 100 °C, and 120 °C successively and vacuum dried for 12 h each time. It is washed 3 times with deionized water at intervals of 12 h to wash away the solvent, and then dried to obtain a single-layer light-responsive film (9 microns thick).

[0166] The cross-sectional scanning electron microscope image of the single-layer light-responsive film is asFigure 4 As shown, the planar transmission electron microscope image is as Figure 5 shown, and the ion selectivity test image is as Figure 6 shown; it can be seen from the cross-sectional electron microscope that the thickness is 9 μm, and from the planar transmission, the pore size is about 20 nm (10 - 50 nm). Ion selectivity can compare positive and negative ions, and the chloride ion ratio is higher than that of sodium ions, which can be used as an anion-selective membrane.

[0167] Example 1-2

[0168] The difference from Example 1 is that the molar ratio of 4,4-bis(4-hydroxyphenyl)valeric acid and 4,4'-dihydroxybiphenyl in Example 1 is changed to 2:8 (8 mmol and 32 mmol respectively), and the remaining steps are the same.

[0169] Example 2-2

[0170] The difference from Example 2 is that the polyarylether compound prepared in Example 1-2 is used, and the remaining steps are the same.

[0171] Example 3-2

[0172] The difference from Example 3 is that the spiropyran-modified polyarylether compound prepared in Example 2-2 is used, and the remaining steps are the same.

[0173] Test Example 1

[0174] Using a picoammeter as the control circuit, the I-t performance test was carried out on the single-layer light-responsive membrane described in Example 3. Among them, the electrolyte solution was a KCl solution with a concentration of 1 mM and a voltage of 1 V. The ionic current fluctuated with the fluctuation of the applied light (180 w), as Figure 7 shown. PAES-COO-SP in the figure 40％ is the light-responsive membrane prepared in Example 3, and PAES-COO-SP 20％ is the light-responsive membrane prepared in Example 3-2. SP 40％ has a better response effect and a higher current rise.

[0175] Figure 8 is the mechanical strength diagram of the light-responsive membrane prepared in Example 3, and the tensile strength is 36 MPa.

[0176] Example 4

[0177] Under anhydrous conditions and under argon protection, 40.0 mmol (10.1903 g) of 4,4'-difluorodiphenyl sulfone, 24.0 mmol (4.4690 g) of 4,4'-dihydroxybiphenyl, 16.0 mmol (4.0044 g) of 4,4-dihydroxydiphenyl sulfone, 48 mmol (6.6341 g) of potassium carbonate, 30 mL of toluene and 80 mL of sulfolane were added to a 250 mL three-necked flask. The resulting mixed system was heated to reflux (145 °C) for 4 h under stirring to allow toluene to fully remove the water generated in the system. Then, the resulting system was heated to 175 °C and reacted for 6 h until the viscosity of the system no longer changed. The resulting product system was poured into deionized water to precipitate solid materials. The solid materials were crushed and washed 3 times with boiling water, and then washed 3 times with ethanol. After vacuum drying at 80 °C to constant weight, a white solid was obtained, which was the polyarylether compound (PPSU-PES).

[0178] The inherent viscosity of the polyarylether compound was 0.50, the number-average molecular weight was 65 kDa, and the dispersity index was 1.3. Its NMR spectrum was as shown in Figure 9 a in Figure 9 shown, and its IR spectrum was as shown in b in

[0179] 4.5 g of the polyarylether polymer synthesized in the above step was weighed and sulfonated with 75 mL of concentrated sulfuric acid. The resulting product system was poured into deionized water to precipitate solid materials. The solid materials were washed with deionized water until neutral, and then vacuum dried at 80 °C to constant weight to obtain a white solid, which was the sulfonated polyarylether compound (PPSU-PES-SO 3- ), and its NMR spectrum was as shown in Figure 9 a in Figure 9 shown, and its IR spectrum was as shown in -1 b in. After sulfonation, the chemical environment of the hydrogen on the benzene ring changed, and new splitting peaks e, f, and g appeared. A characteristic peak of the sulfonic acid group appeared at 1050 cm

[0180] Example 5

[0181] 60 mg of the sulfonated polyarylether compound prepared in Example 4, 60 mg of polyvinylpyrrolidone-K30, and 5 mL of N-methylpyrrolidone were mixed and stirred at room temperature (25 °C) under airtight conditions for 10 h to obtain a clear and transparent viscous liquid. After filtering with a filter cloth and standing for degassing for 12 h, a casting solution was obtained;

[0182] The casting solution was dropwise added to the surface of a 2 cm × 2 cm glass plate that was horizontally placed in a preheated oven at 40 °C and was smooth and flat. The oven was heated to 60 °C. After no liquid droplets evaporated and condensed on the window, it was sequentially heated to 80 °C, 100 °C, and 120 °C and vacuum dried for 12 h each. It was washed 3 times with deionized water at intervals of 12 h to wash away the solvent, and then dried to obtain a single-layer sulfonated polyarylether membrane (3 μm thick, SPPSU0.6 -PES 0.4 )。

[0183] The planar transmission electron microscopy image of the single-layer sulfonated polyarylether membrane is as Figure 10 shown. It can be seen from the planar transmission that the pore size is about 8 nm. The ion selectivity test image is as Figure 11 shown, showing good sodium ion selectivity, providing guarantee for the subsequent work.

[0184] 50 mg of the spiropyran-modified polyarylether compound prepared in Example 2 was mixed with 1 mL of dichloromethane, and stirred at room temperature (25 °C) under airtight conditions for 10 h to obtain a clear and transparent viscous liquid. After filtering with a filter cloth and standing for degassing for 12 h, a spin-coating solution was obtained; it was spin-coated onto the single-layer sulfonated polyarylether membrane prepared in the above step to obtain a bilayer polyarylether composite membrane with responsive and rectifying properties (the spin-coated layer is 10 microns and the bottom layer is 3 microns). The cross-sectional scanning electron microscopy image is as Figure 12 shown.

[0185] Test Example 2

[0186] Using a picoammeter as the control circuit, the I-t performance test was carried out on the bilayer light-responsive heterojunction membrane described in Example 5; among them, the electrolyte solution was a KCl solution with a concentration of 1 mM and a voltage of 1 V. The ionic current fluctuated with the fluctuation of the applied light, as Figure 13 shown.

[0187] The I-V performance test was carried out on the bilayer light-responsive heterojunction membrane; among them, the electrolyte solution was a KCl solution with a concentration of 1 mM, and the scanning voltage range was from -2 V to 2 V. The rectification ratio performance was the best at a concentration of 10 -3 M. The measured I-V curve was non-linear, and the rectification ratio increased to 25 after illumination, as Figure 14 and Figure 15 shown, Figure 15 where AfterUV in represents the rectification curve after an irradiation duration of 100 s.

[0188] The ion device test device is as Figure 16 shown. The ultraviolet light source is above, and the electrolytic cells are on the left and right sides, filled with potassium chloride solution. The black line represents the external picoammeter circuit, and the black line inserted into the solution is the silver electrode.

[0189] Example 6

[0190] An azobenzene compound, a polymer, a catalyst, and a solvent were stirred and reacted at a stirring speed of 120 r / min for 48 h in the presence of nitrogen and protected from light. After the reaction was completed, the product was discharged into deionized water, filtered, and the filter cake was washed thoroughly with ethanol and water in sequence, and then dried under vacuum to obtain the azobenzene-modified polyarylether compound.

[0191] Among them, the azobenzene compound is a hydroxyazobenzene derivative, and its structural formula is as follows:

[0192]

[0193] The polymer is the carboxyl polyarylether sulfone prepared in Example 1, and the molar ratio of the azobenzene compound to the total number of polymerization units in the carboxyl polyarylether sulfone is 2:5.

[0194] The catalyst is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt (EDCI) and 4-dimethylaminopyridine (DMAP). The molar ratio of EDCI to DMAP is 10:1, and the molar ratio of the catalyst to the carboxyl group of part A of the polyarylether compound is 2:1. 。

[0195] The solvent is N,N-dimethylformamide, and the ratio of the solvent mass to the total mass of the reactants is 4:1.

[0196] Example 7

[0197] Mix 60 mg of the sulfonated polyarylether compound prepared in Example 4, 60 mg of polyvinylpyrrolidone-K30, and 5 mL of N-methylpyrrolidone, and stir at room temperature (25°C) under airtight conditions for 10 h to obtain a clear, transparent and viscous liquid. After filtering with a filter cloth and standing for degassing for 12 h, a casting solution is obtained.

[0198] The casting solution is dropwise added onto the surface of a 2 cm × 2 cm glass plate that is horizontally placed in a preheated oven at 40°C and is smooth and flat. The oven is heated to 60°C. When there is no liquid drop volatilized and condensed on the window, it is heated to 80°C, 100°C, and 120°C in sequence and vacuum dried for 12 h each time. It is washed with deionized water 3 times at intervals of 12 h each time to wash away the solvent, and then dried to obtain a single-layer sulfonated polyarylether membrane.

[0199] Mix 50 mg of the azobenzene-modified polyarylether compound prepared in Example 6 and 1 mL of chloroform, and stir at room temperature (25°C) under airtight conditions for 10 h to obtain a clear, transparent and viscous liquid. After filtering with a filter cloth and standing for degassing for 12 h, a spin-coating solution is obtained; it is spin-coated onto the single-layer sulfonated polyarylether membrane prepared in the above step to obtain a double-layer polyarylether composite membrane with responsiveness and rectification properties.

[0200] Test Example 3

[0201] Using a picoammeter as the control circuit, perform I-t performance testing on the double-layer light-responsive heterogeneous membrane described in Example 7; among them, the electrolyte solution is a KCl solution with a concentration of 1 mM, the voltage is 1 V, and the ionic current fluctuates with the fluctuation of the applied light.

[0202] Perform I-V performance tests on the double-layer light-responsive heterogeneous film; among them, the electrolyte solution is a KCl solution with a concentration of 1 mM, the scanning voltage range is from -2V to 2V, and the measured I-V curve is non-linear, and the rectification ratio is increased to about 20.

[0203] Example 8

[0204] React a triphenylmethane derivative compound, a polymer, a catalyst, and an anhydrous solvent under the presence of nitrogen and in the dark with a stirring speed of 120 r / min for 72 h. After the reaction is completed, discharge the product into deionized water, filter, and wash the filter cake thoroughly with ethanol and water in sequence, and then dry it under vacuum to obtain a polyarylether compound modified with a triphenylmethane derivative.

[0205] The triphenylmethane derivative is a triphenylmethane derivative with R being -NH 2 and its structural formula is as follows:

[0206]

[0207] The polymer is the carboxyl polyarylether sulfone prepared in Example 1, and the molar ratio of the total number of polymerization units in the triphenylmethane derivative compound and the carboxyl polyarylether sulfone is 2:5.

[0208] The catalyst is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt (EDCI) and 4-dimethylaminopyridine (DMAP), the molar ratio of EDCI and DMAP is 10:1, and the molar ratio of the catalyst to the carboxyl group of part A of the polyarylether compound is 2:1 。

[0209] The solvent is N,N-dimethylformamide, and the mass ratio of the solvent to the total mass of the reactants is 4:1.

[0210] Example 9

[0211] Mix 60 mg of the sulfonated polyarylether compound prepared in Example 4, 60 mg of polyvinylpyrrolidone-K30, and 5 mL of N-methylpyrrolidone, and stir at room temperature (25°C) under airtight conditions for 10 h to obtain a clear and transparent viscous liquid. After filtering with a filter cloth and standing for degassing for 12 h, a casting solution is obtained;

[0212] Drop the casting solution onto the surface of a 2 cm × 2 cm glass plate that is horizontally placed in a preheated oven at 40°C and is smooth and flat. Heat the oven to 60°C. Wait until no liquid droplets evaporate and condense on the window, then sequentially heat to 80°C, 100°C, and 120°C and dry under vacuum for 12 h. Soak it in deionized water 3 times at intervals of 12 h each time to wash away the solvent, and then dry it to obtain a single-layer sulfonated polyarylether membrane;

[0213] 50 mg of the polyarylether compound modified with the triphenylmethane derivative prepared in Example 8 was mixed with 1 mL of dichloromethane and stirred at room temperature (25 °C) under a closed condition for 10 h to obtain a clear and transparent viscous liquid. After filtration with a filter cloth and standing for degassing for 12 h, a spin coating solution was obtained; it was spin-coated onto the single-layer sulfonated polyarylether membrane prepared in the above step to obtain a bilayer polyarylether composite membrane with responsive and rectifying properties.

[0214] Test Example 4

[0215] Using a picoammeter as the control circuit, the I-t performance of the bilayer light-responsive heterojunction membrane described in Example 9 was tested; among them, the electrolyte solution was a KCl solution with a concentration of 1 mM, the voltage was 1 V, and the ionic current fluctuated with the fluctuation of the applied light.

[0216] The I-V performance of the bilayer light-responsive heterojunction membrane was tested; among them, the electrolyte solution was a KCl solution with a concentration of 1 mM, the scanning voltage range was from -2 V to 2 V, and the measured I-V curve was non-linear, and the rectification ratio was increased to about 23.

[0217] The current value of the light-responsive membrane prepared by the present invention changes rapidly after illumination, showing fast response; it has a benzene ring rigid group in the main chain, with stable structure and good mechanical properties. Moreover, the aromatic ring structure makes the polymer have high chemical stability.

[0218] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, not all embodiments. People can also obtain other embodiments according to the embodiments of the present invention without creative labor, and these embodiments all belong to the protection scope of the present invention.

Claims

1. A polyarylether compound, characterized in that: The polyarylether compound has a structure shown in Formula I: In Formula I, A is independently selected from any one of the structures shown in Formulas A-1 to A-11: B is independently selected from any one of the structures shown in formula B-1 to B-13: The range of n / (n+m) is 0.1 to 1.

2. The method for preparing the polyarylether compound according to claim 1, characterized in that: The following steps are involved: The first monomer, the second monomer, the third monomer, the first organic solvent, the first catalyst and the water-carrying agent are mixed and dehydrated, and then subjected to polycondensation reaction to obtain the polyarylether compound; The structural formula of the first monomer is HO-A-OH, the structural formula of the second monomer is HO-B-OH, and the structural formula of the third monomer is as shown below, wherein X is a halogen group, 3. A polyarylether compound modified with a photoresponsive molecule, characterized in that: The invention comprises the polyarylether compound and a photoresponsive molecule modified on the polyarylether compound; The photoresponsive molecules include spiropyran compounds, azobenzene compounds or triphenylmethane compounds; The polyarylether compound is the polyarylether compound according to claim 1; the photoresponsive molecule is connected to the carboxyl group of part A of the polyarylether compound.

4. The method for preparing the photoresponsive molecule-modified polyarylether compound according to claim 3, characterized in that: The following steps are involved: The photoresponsive molecule, the polyarylether compound, the second catalyst and the second organic solvent are mixed to carry out esterification reaction, amidation reaction or substitution reaction to obtain the polyarylether compound modified by the photoresponsive molecule.

5. A photoresponsive film, characterized in that: The film-forming material of the photoresponsive film is the polyarylether compound modified with the photoresponsive molecules as described in claim 3.

6. The method for preparing the photoresponsive film according to claim 5, characterized in that: The following steps are involved: Mixing the photoresponsive molecule-modified polyarylether compound according to claim 3 and a third organic solvent to obtain a casting solution; The casting solution is prepared into a film by a non-solvent phase separation method to obtain the light-responsive film.

7. A photoresponsive composite film, characterized in that: including a stacked photoresponsive membrane and a sulfonated polyethersulfone membrane; The photoresponsive film is the photoresponsive film according to claim 5.

8. The method for preparing the light-responsive composite film according to claim 7, characterized in that: The following steps are involved: Mixing the photoresponsive molecule-modified polyarylether compound according to claim 3 and a third organic solvent to obtain a casting solution; The film casting solution is spin-coated on the surface of the sulfonated polyethersulfone membrane to obtain the light-responsive composite membrane.

9. The preparation method according to claim 8, characterized in that: The film-forming material of the sulfonated polyethersulfone membrane is sulfonated polyethersulfone, and the structural formula of the sulfonated polyethersulfone is shown as follows: Wherein, x is the molar ratio of the chain segment containing biphenyl groups, ranging from 0.1 to 1.

10. Use of the photoresponsive film according to claim 5 or the photoresponsive composite film according to claim 7 in a bionic ionic device.

Images