WO2022017518A1 - 制备聚离子薄膜的方法、聚离子薄膜以及检测试剂盒 - Google Patents

制备聚离子薄膜的方法、聚离子薄膜以及检测试剂盒 Download PDF

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WO2022017518A1
WO2022017518A1 PCT/CN2021/108245 CN2021108245W WO2022017518A1 WO 2022017518 A1 WO2022017518 A1 WO 2022017518A1 CN 2021108245 W CN2021108245 W CN 2021108245W WO 2022017518 A1 WO2022017518 A1 WO 2022017518A1
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film
polyion
vinylimidazole
bromobutane
silicon wafer
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PCT/CN2021/108245
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English (en)
French (fr)
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张书鹏
段晓东
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上海安翰医疗技术有限公司
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Priority to US18/017,854 priority Critical patent/US20230295360A1/en
Publication of WO2022017518A1 publication Critical patent/WO2022017518A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/48—Acrylonitrile with nitrogen-containing monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80—Indicating pH value
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/84—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving inorganic compounds or pH
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/18—Homopolymers or copolymers of nitriles
    • C08J2433/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member

Definitions

  • the application belongs to the technical field of materials, and in particular relates to a method for preparing a polyion film (especially a polyion film with surface patterning), a polyion film prepared by the method, and a detection kit comprising the polyion film .
  • Stimuli-sensitive (responsive) materials refer to materials that respond to changes in the external environment, such as changes in pH, temperature, light, etc., which cause changes in the microstructure of the material, thereby showing changes in color, physical, and chemical forms. This property makes stimuli-sensitive materials promising for applications in sensors, drug release, and bioengineering. Such as pH-sensitive films, which are widely used in pH sensors, drug controlled release, in vivo detection and other fields. However, the relationship between the microscopic morphology of thin films and macroscopic changes (such as response rate) is rarely studied.
  • a polymer mask with a predetermined pattern needs to be formed on the substrate by a dispensing process, and then the substrate is subjected to oxygen plasma treatment or ultraviolet light irradiation treatment, and then A conductive film is prepared on the substrate attached with the polymer mask by a solution process, and finally the polymer mask is peeled off from the substrate to obtain a patterned conductive film.
  • this preparation method only some electric thin films with simple patterns can be obtained, and the pattern precision is low. The method prepares the electric thin film through a dispensing process.
  • the glue itself has ductility or fluidity, which is difficult to control precisely, and is affected by the dispensing parameters (such as air pressure, dispensing volume), and the resulting polymer mask itself has low precision (plasma treatment or UV light treatment, Its curing rate is affected by the amount of glue, the accuracy is high or low), and it is easy to form jagged edges, which will affect the final accuracy of the film.
  • the preparation process of the method disclosed in the prior art is difficult to control, and the finished product is difficult to peel off, and it is difficult to ensure the integrity of the film.
  • the preparation of the patterned metal thin film in the prior art also includes: first immersing a clean substrate in a dopamine solution to form a polydopamine film on the surface of the substrate, taking it out, rinsing with water, and then blowing dry with nitrogen to obtain a substrate with the polydopamine film attached ; Then place a photomask on the obtained substrate with the polydopamine film attached, then irradiate it under ultraviolet light for 15 minutes, rinse with water, and dry it with nitrogen to obtain a polydopamine substrate cured by ultraviolet, and finally on the substrate Metal ions are deposited to obtain patterned metal films.
  • the purpose of the present application is to provide a simple, convenient and efficient method for preparing polyion films (especially surface-patterned polyion films).
  • the application provides a method for preparing a polyion film, the method comprising the following steps:
  • the substrate comprises a silicon wafer
  • the silicon wafer is a silicon wafer whose surface has been patterned
  • the surface of the silicon wafer has raised ridges, or the surface of the silicon wafer has recessed grooves, or the surface of the silicon wafer is provided with protruding cylindrical components, or the surface of the silicon wafer is provided with circular holes penetrating the silicon wafer.
  • the first lubricant and the second lubricant are inert to ultraviolet light and do not interfere with ultraviolet light;
  • the first lubricant is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, and lubricating grease.
  • the film-forming liquid includes one or more of imidazole-based ionic liquids, pyridine-based ionic liquids, quaternary ammonium salt-based ionic liquids, quaternary phosphine-based ionic liquids, and pyrrolidine-based ionic liquids kind;
  • the film-forming liquid includes 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium chloride, N-ethylpyridinium bromide, tributylmethyl chloride One or more of ammonium chloride, tributylethylphosphine bromide, N-butyl-N-methylpyrrolidine bromide;
  • the cover plate is a glass plate or a UV-resistant hard plastic plate
  • the second lubricant is selected from white petrolatum, silicone oil, paraffin, mineral oil, grease.
  • step (3) the polymerization reaction is carried out under the irradiation of ultraviolet light;
  • the wavelength of the ultraviolet light is 250nm ⁇ 400nm;
  • the irradiation time is 15min-30min.
  • step (3) the polymerization reaction is carried out at a temperature of 20°C to 60°C;
  • the polymerization reaction is initiated by an initiator; more preferably, the initiator is selected from photoinitiator 907, photoinitiator 184, azobisisobutyronitrile, 2,4,6-(trimethylbenzene) formyl) diphenylphosphine oxide or benzoin and derivatives thereof.
  • the initiator is selected from photoinitiator 907, photoinitiator 184, azobisisobutyronitrile, 2,4,6-(trimethylbenzene) formyl) diphenylphosphine oxide or benzoin and derivatives thereof.
  • the step of separating the polyion membrane comprises: placing the cover plate attached with the polyion membrane into water and standing;
  • the cleaning includes performing ultrasonic cleaning in clean water, absolute ethanol and clean water in sequence.
  • step (1) it also includes wetting the substrate with a solvent before spreading the tin foil on the substrate;
  • the solvent is water, ethanol or a mixed solvent thereof.
  • step (2) the film-forming solution is prepared by the following steps:
  • the method further comprises, after fully mixing the ionic liquid monomers, performing ultrasonic treatment on the obtained mixed solution; more preferably, performing ultrasonic treatment for 10 to 30 minutes;
  • step (b) the ultrasonic treatment is performed for 10 min to 30 min.
  • the ionic liquid monomers include bromobutane, vinylimidazole and acrylonitrile;
  • the crosslinking agent is N,N-methylenebisacrylamide, and the initiator is 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide;
  • the molar ratio of bromobutane and vinylimidazole is 2:1 to 1:1;
  • the mass of acrylonitrile is greater than or equal to the sum of the mass of bromobutane and vinylimidazole;
  • the mass of the crosslinking agent is 8wt% to 12wt% calculated on the total mass of bromobutane, vinylimidazole and acrylonitrile, and the mass of the initiator is bromobutane 0.5wt% to 2wt% calculated on the total mass of alkane, vinylimidazole and acrylonitrile.
  • the film-forming liquid is prepared by the following steps:
  • the method further comprises immersing the polyionic film in a dye solution with a dye;
  • the dyestuff is selected from one of bromocresol green, cresol red and methyl orange;
  • the dye solution is a solution obtained by dissolving the dye in a mixed solvent of water and ethanol, wherein, in the mixed solvent of water and ethanol, the volume ratio of water to ethanol is 4:1 to 1:8, preferably 1 : 4.
  • the concentration of the dye is 0.5-8 mg/ml, more preferably 3.95 mg/ml.
  • a polyion film prepared by the above method A polyion film prepared by the above method.
  • a detection kit comprising the above-mentioned polyion film.
  • the detection kit further includes a colorimetric card.
  • the preparation method of the polyion film provided by the present application reduces the difficulty of separating the polyion film from the substrate by using a lubricant.
  • the use of tin foil not only helps to speed up the film formation speed of the polyion film, but also avoids the direct contact between the film formation liquid and the substrate (for example, silicon wafer) before film formation, and ensures the integrity of the film and the uniformity of film thickness. , and greatly reduces the time required for membrane separation.
  • the present application also uses the patterned silicon wafer as a template to prepare a surface-patterned polyion film.
  • the method of the present application is easy to operate, the polyion film is easy to separate, the film thickness is uniform and adjustable, and the technical threshold is low, so it has great application potential.
  • the surface-patterned polyion film of the present application can be applied to at least the following methods.
  • the polyion membrane can be fixed in the river, and a colorimetric card can be set next to the polyion membrane. By observing the polyion membrane Changes in color to determine the pH value.
  • 1 is a schematic view of a silicon wafer surface with raised ridges
  • FIG. 2 is a schematic diagram of a groove with a recess on the surface of a silicon wafer
  • FIG. 3 is a schematic diagram of a protruding cylindrical part provided on the surface of a silicon wafer
  • FIG. 4 is a schematic diagram showing that the surface of the silicon wafer is provided with a circular hole passing through the silicon wafer;
  • Figure 5 is a photomicrograph of a polyion film with a pinstripe pattern prepared by the method of the present application
  • Figure 7 is a photomicrograph of a polyion film with a complex pattern prepared by the method of the present application.
  • an embodiment of the present application provides a method for preparing a polyion film comprising the following steps:
  • the polyion film is separated and cleaned to obtain a polyion film with a patterned surface.
  • the above method realizes the rapid preparation of the polyion film by forming the polyion film between the two surfaces coated with the lubricant by using the film-forming liquid of the polyion film.
  • the surface of the substrate may be smooth, or the surface may be uneven and patterned.
  • Lubricants should be applied evenly to obtain higher quality polyionic films.
  • the preparation method of the present application can prepare polyion films with different surface morphologies, and is simple in synthesis, low in cost, and easy in large-scale production, and provides a variety of applications for polyion films in sensors, medical detection and other fields. choose.
  • the substrate includes a silicon wafer, that is, a silicon wafer is used as a substrate or a substrate assembly including a silicon wafer is used.
  • silicon wafers are inert, insensitive to environmental factors such as temperature and ultraviolet rays, and have excellent stability; they do not interfere with chemical components such as film-forming liquids, and will not affect curing and film formation. Process; the surface of the silicon wafer is easy to control and can be patterned on the surface, thereby improving the accuracy of the polyion thin film film.
  • the film-forming liquid can be spread evenly, so that the overall thickness of the film (ie, the polyion film) can be controlled, and the phenomenon of film thickness or too low will not occur.
  • the preparation method of polyion films provided in this application can select cover plates of different thicknesses or different qualities, so as to adjust the thickness of the film.
  • the thickness of the plate should be within a range that allows ultraviolet rays to pass through the cover plate, and details are not repeated here.
  • the silicon wafer may be a silicon wafer with a smooth surface or a silicon wafer with a patterned surface.
  • different patterned films have different response speeds during detection, which can be adjusted as needed in practical applications.
  • the ion exchange rate of the films with different patterns prepared according to the patterned silicon wafer substrate is different, and the ion exchange rate will affect the response rate and uniformity of the color development of the film.
  • the films prepared by the method of the present application will show great advantages.
  • the surface of the silicon wafer may be a raised ridge, a recessed groove, a cylinder protruding from the surface of the silicon wafer, or a circular hole penetrating the silicon wafer.
  • the individual features that form the pattern eg, ridges, grooves, cylinders, or holes
  • the surface of the silicon wafer is engraved with fine stripes, and the gap and the size of the stripes can be adjusted.
  • the surface of the silicon wafer has raised ridges.
  • the surface of the silicon wafer has recessed trenches.
  • the surface of the silicon wafer is provided with protruding cylindrical parts.
  • the surface of the silicon wafer is provided with circular holes penetrating the silicon wafer.
  • a first lubricant is applied on the surface of the tin foil.
  • Tinfoil has strong inertness and is not easy to react with lubricant or film-forming liquid of polyion film, and the surface of tinfoil is very smooth, which is conducive to the formation of more uniform polyion film.
  • the tin foil can be easily peeled off from the film (even the tin foil can be peeled off manually), and the side of the resulting polyion film in contact with the cover plate can be separated in a liquid environment, thus shortening the separation time .
  • the method comprises the following steps:
  • the first lubricant is inert to ultraviolet light and does not interfere with ultraviolet light. More preferably, in step (1), the first lubricant can be white petrolatum, silicone oil, paraffin, mineral oil or lubricating grease.
  • the first lubricant needs to be non-toxic, non-corrosive, non-residue and transparent in coating. In the field of medical devices, especially in areas with high safety requirements, such as sensors and controlled drug release, there are higher requirements for the first lubricant, so medical grade lubricants need to be used.
  • the first lubricant is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, and lubricating grease.
  • the second lubricant is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, grease.
  • the film-forming liquid in step (2) of the above method, different film-forming liquids can be selected according to different needs and application scenarios.
  • the film-forming liquid may include one or more of imidazole-based ionic liquids, pyridine-based ionic liquids, quaternary ammonium salt-based ionic liquids, quaternary phosphine-based ionic liquids, or pyrrolidine-based ionic liquids .
  • the film-forming liquid may include functionalized ionic liquids commonly used in the art.
  • Imidazole ionic liquids (1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium chloride), pyridine ionic liquids (N-ethylpyridinium bromide), quaternary Ammonium salt type ionic liquid (tributylmethylammonium chloride), quaternary phosphine type ionic liquid or pyrrolidine type ionic liquid (tributylethylphosphine bromide, N-butyl-N-methylpyrrolidine bromide).
  • the cover plate may be a transparent substrate.
  • the cover plate may be a transparent glass plate or a rigid plastic plate that is resistant to ultraviolet light (does not react with ultraviolet light and can transmit ultraviolet light).
  • the cover plate is a glass plate or a hard transparent plastic plate that is resistant to UV light.
  • the transparent glass plate or the UV-resistant rigid transparent plastic plate can make the polymerization reaction proceed under the irradiation of ultraviolet light, which provides an optional solution for the polymerization reaction.
  • the UV-resistant rigid transparent plastic sheet means that the material in the transparent plastic sheet is not sensitive to ultraviolet rays, and the transparent plastic sheet will not be denatured due to the penetration of ultraviolet rays.
  • the material for preparing the transparent plastic plate is PC (Polycarbonate, polycarbonate), TPU (Thermoplastic polyurethanes, thermoplastic polyurethane elastomer), acrylic and the like.
  • the second lubricant is inert to ultraviolet light and does not interfere with ultraviolet light and is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, and lubricating grease.
  • the polymerization reaction is carried out under the irradiation of ultraviolet light.
  • the wavelength of the ultraviolet light is 250nm ⁇ 400nm.
  • the time of ultraviolet light irradiation is 15min-30min.
  • the polymerization reaction is carried out under the condition of heating, and the polymerization reaction is carried out at a temperature of 20°C to 60°C.
  • the polymerization reaction is initiated by an initiator.
  • the initiator can be an initiator commonly used in the art, such as photoinitiator 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone), photoinitiator 184 (1 -Hydroxycyclohexyl phenyl ketone), azobisisobutyronitrile, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO), benzoin and its derivatives, etc.
  • Those skilled in the art can select appropriate initiators according to the specific components of the film-forming liquid.
  • the separation of the polyion film from the cover plate is achieved by placing the cover plate attached with the polyion film into water and standing.
  • the polyion film can be automatically separated from the cover plate, the operation is simple, and the yield is improved.
  • the cleaning includes performing ultrasonic cleaning in clean water, absolute ethanol, and clean water in sequence.
  • the step (1) of the embodiments of the present application also includes wetting the substrate with a solvent before spreading the tin foil on the substrate.
  • the purpose of wetting the substrate is to remove the air between the substrate and the tin foil, and increase the bonding force between the substrate and the tinfoil through the adhesion of the solvent and the tinfoil, so that the tinfoil is easier to smooth and improve the flatness of the surface of the tinfoil.
  • the solvent is preferably water, ethanol or a mixed solvent thereof.
  • the film-forming liquid can be prepared by the following steps:
  • step (a) it further includes performing ultrasonic treatment on the obtained mixed solution after fully mixing the ionic liquid monomers. More preferably, the ultrasonic treatment is carried out for 10 min to 30 min.
  • step (b) the ultrasonic treatment is performed for 10 min to 30 min.
  • the ionic liquid monomers include bromobutane, vinylimidazole and acrylonitrile.
  • the crosslinking agent is N,N-methylenebisacrylamide (MBA)
  • the initiator is 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO).
  • the molar ratio of bromobutane and vinylimidazole is 2:1 to 1:1; preferably 1:1. Taking into account the reaction ratio of the two, conversion rate, consumption and subsequent cleaning process, the molar ratio of bromobutane and vinylimidazole is 1:1.
  • the mass of acrylonitrile is greater than or equal to the sum of the mass of bromobutane and vinylimidazole.
  • the mass of acrylonitrile is the sum of the mass of bromobutane and vinylimidazole.
  • the mass of the crosslinking agent is 8wt% to 12wt% calculated on the total mass of bromobutane, vinylimidazole and acrylonitrile, for example, it can be 8wt% %, 9wt%, 10wt%, 12wt%, etc.
  • the mass of the initiator is 0.5wt% to 2wt% calculated on the total mass of bromobutane, vinylimidazole and acrylonitrile, such as 0.5wt%, 1wt%, 1.5wt%, 2wt%, etc.
  • the film-forming liquid can be prepared by the following steps:
  • step (a) ultrasonic treatment can increase the energy field for the mixed solution of bromobutane and vinylimidazole, thereby accelerating the reaction.
  • the methods provided in the embodiments of the present application further include immersing the obtained surface-patterned polyionic thin film in a dye solution with a dye to obtain a polyionic thin film that can be used for pH detection.
  • the dyes used above can be commonly used dyes in the art, as long as they can be stably combined with the film substrate, and the safety can be guaranteed.
  • the dye may be selected from one of bromocresol green (BG), cresol red (CR), methyl orange (MO).
  • BG, CR or MO are exchanged with the film, they are responsive to pH value. Under different pH conditions, they show different molecular structures, different microscopic absorption peaks in the ultraviolet spectrum, and different macroscopic colors. .
  • the dye solution is a solution in which the dye is dissolved in a water-ethanol mixed solvent, wherein, in the water-ethanol mixed solvent, the volume ratio of water to ethanol is 4:1 to 1:8.
  • the ratio of water to ethanol is 4:1, 2:1, 1:1, 1:2, 1:4, 1:6 or 1:8.
  • the concentration of the dye is 0.5-8 mg/ml.
  • the concentration of dye is 0.5 mg/ml, 1.0 mg/ml, 1.5 mg/ml, 2.0 mg/ml, 2.5 mg/ml, 3.0 mg/ml, 3.5 mg/ml, 4.0 mg/ml, 4.5 mg/ml , 5.0 mg/ml, 5.5 mg/ml, 6.0 mg/ml, 6.5 mg/ml, 7.0 mg/ml, 7.5 mg/ml or 8.0 mg/ml.
  • the concentration of dye is 3.95 mg/ml.
  • the present application also provides a polyion film obtained by the preparation method in the above embodiment.
  • the present application also provides a detection kit, which includes a polyion film obtained by dipping a dye.
  • the detection kit includes a colorimetric card and the above-mentioned polyion membrane. Through the change of the color of the polyion film, the pH value of the liquid to be detected can be quickly detected by comparing with the pre-made colorimetric card.
  • the formed assembly was placed under the ultraviolet light of 265nm, irradiated from the transparent glass cover for 20min (ambient temperature was 55°C) to initiate the polymerization reaction between bromobutane, vinylimidazole and acrylonitrile to form a transparent film .
  • the assembly was cooled to room temperature and then put into water as a whole. After soaking for 20 minutes, the polyion film was automatically peeled off from the glass cover. Then ultrasonically clean the polyion film with pure water.
  • the polyion film is immersed in the BG dye solution (the concentration of the BG dye is 8 mg/ml, and the solvent is a mixed solvent of water and ethanol, and the volume ratio of water and ethanol is 1:4), placed at a temperature of 30°C for 20 min, and the polyion film was taken out.
  • the polyion film was blue, and the polyion film was ultrasonically cleaned with pure water, absolute ethanol, and pure water in sequence. Under microscope observation, it can be seen that the polyion film presents thin stripes (as shown in Figure 5), and then it is blown dry for use.
  • Polyionic membranes impregnated with BG dyes can be used for pH detection of solutions.
  • bromobutane and vinylimidazole with a molar ratio of 1:1, place them in a glass bottle, ultrasonically treat them for 20 min to fully mix the two, and then add acrylonitrile solution with the same mass as bromobutane and vinylimidazole. , and then add MBA with a mass ratio of 12% calculated from the total mass of bromobutane, vinylimidazole and acrylonitrile, and a mass ratio calculated from the total mass of bromobutane, vinylimidazole and acrylonitrile as 2% TPO, and then ultrasonically treated for 30 min to form a clear and transparent polyion film-forming solution.
  • the formed assembly was irradiated under ultraviolet light of 365 nm for 30 min (the ambient temperature at this time was 55° C.) to initiate a polymerization reaction between bromobutane, vinylimidazole and acrylonitrile to form a transparent film. After the polymerization reaction, the assembly was cooled to room temperature and then placed in water as a whole. After soaking for 25 minutes, the polyion film was automatically peeled off from the glass cover. Then use pure water to ultrasonically clean the polyion film.
  • the polyion film is immersed in a BG dye solution (concentration is 0.5mg/ml, and the solvent is a mixed solvent of water and ethanol, and the volume ratio of water and ethanol is 1: In 1), place at 30°C for 20min, take out the polyion film, at this time the polyion film is sky blue, use pure water, absolute ethanol, pure water to ultrasonically clean the polyion in sequence. Under microscope observation, it can be seen that the polyion film is a flat surface, and then blown dry for use.
  • a BG dye solution concentration is 0.5mg/ml, and the solvent is a mixed solvent of water and ethanol, and the volume ratio of water and ethanol is 1: In 1
  • place at 30°C for 20min take out the polyion film, at this time the polyion film is sky blue, use pure water, absolute ethanol, pure water to ultrasonically clean the polyion in sequence. Under microscope observation, it can be seen that the polyion film is a flat surface, and
  • bromobutane and vinylimidazole with a molar ratio of 1.5:1, put them in a glass bottle, mix them evenly, then ultrasonically treat them for 15 minutes until the two are fully mixed, and then add the same mass as bromobutane and vinylimidazole.
  • the acrylonitrile solution then add MBA with a mass ratio of 8% calculated based on the total mass of bromobutane, vinylimidazole and acrylonitrile and calculated based on the total mass of bromobutane, vinylimidazole and acrylonitrile
  • the mass ratio of TPO is 0.5%, and then ultrasonically treated for 10 min to form a clear and transparent polyion film-forming solution.
  • the formed assembly was placed under the ultraviolet light of 254nm, and irradiated from one side of the hard transparent plastic plate for 15min (ambient temperature was 55°C) to initiate a polymerization reaction between bromobutane, vinylimidazole and acrylonitrile to form Transparent film. After the polymerization reaction is completed, the assembly is cooled to room temperature and then placed in water as a whole. After soaking for 20 minutes, the polyion film is automatically peeled off from the glass cover. Then ultrasonically clean the polyion film with pure water.
  • the polyion film is immersed in a CR dye solution (the concentration of CR dye is 3.95 mg/ml, and the solvent is a mixed solvent of water and ethanol, and the volume ratio of water and ethanol is 4:1), placed at a temperature of 30°C for 20 min, and the polyion film was taken out, and the film was dark blue at this time.
  • the polyion film was ultrasonically cleaned with pure water, anhydrous ethanol, and pure water in turn. Under microscope observation, it could be seen that the polyion film showed a pit shape (as shown in Figure 6), and then dried for use.
  • Polyionic membranes impregnated with CR dyes can be used for pH detection of solutions.
  • the assembly After the polymerization reaction is completed, the assembly is cooled to room temperature and then placed in water as a whole. After soaking for 20 minutes, the polyion film is automatically peeled off from the glass cover plate. Then ultrasonically clean the polyion film with pure water. After the ultrasonic cleaning, the polyion film is immersed in the MO dye solution (the concentration of MO dye is 3.95 mg/ml, and the solvent is a mixed solvent of water and ethanol, and the volume of water and ethanol is 3.95 mg/ml).
  • This application example introduces the application of the polyion film prepared by the method of the present application in the detection of body fluids.
  • a gastric tube was inserted into the subject's stomach, and 20 ml of gastric juice was drawn through a vacuum suction pump.
  • the gastric juice was transferred into a clean beaker, placed in the polyion film (CR-dyed) prepared as in the previous example, and allowed to stand. Then, the polyion film was taken out, the color change of the polyion film was observed, and the pH value of the gastric juice was obtained by comparing the color of the polyion film after the change with the color chart.
  • the pH of gastric juice is a value between 2 and 3. If the measured pH value exceeds the reference range of the normal value, it can be preliminarily inferred that the subject's stomach may have pathological changes.
  • This application example introduces the application of the polyion membrane prepared by the method of the present application in water quality detection.
  • the polyionic film prepared by the method of the present application can be used in the detection of the pH value of water.
  • pH value is an important indicator of water quality. It determines many chemical and biological processes in the water body and is a barometer of water quality. Too high or too low pH value will directly harm fish and shrimp. If the pH value is too low, the pH value of the blood of the fish and shrimp will decrease, which will weaken its oxygen-carrying capacity, which may cause the physiological hypoxia of the fish and shrimp. At this time, although the dissolved oxygen in the water is sufficient, the fish and shrimp will still float their heads due to physiological hypoxia and stop feeding. If the pH value is too high, the gill tissue will be corroded, which may cause a large number of fish and shrimp to die.
  • Too high or too low pH will inhibit the activity of microorganisms in the water, making it difficult for organic substances to decompose.
  • a large amount of ionic ammonia will be converted into toxic NH 3 ;
  • the pH value is lower than 6.0, more than 90% of the sulfide in the water will exist in the form of H 2 S, which increases the toxicity of the sulfide.
  • Fish and shrimp cannot survive when the pH value is lower than 4.0 or higher than 10.6. Therefore, the real-time detection of pH value is very important.
  • the polyion film (with a hole structure) prepared by the application is placed in water, and the pH value of the water quality at this time is judged by the real-time color change of the polyion film.
  • the operation is very simple. Compared with pH test paper, there is no need to sample and test, and there is no need to worry about the pollution of water quality caused by dye overflow; compared with electrochemical sensors, the polyion film of the present application is cheaper.

Abstract

本申请提供一种制备聚离子薄膜(尤其是具有不同表面形貌的聚离子薄膜)的方法以及由该方法制备的聚离子薄膜，所述方法包括步骤：提供基板，在所述基板的表面上或在覆盖于所述基板的表面的锡纸的表面上涂抹第一润滑剂；将聚离子薄膜的成膜液覆盖在涂有所述基板的表面上，涂覆均匀后，将涂有第二润滑剂的盖板覆盖在成膜液上；使成膜液中的离子液体单体发生聚合反应，形成聚离子薄膜；将所述聚离子薄膜分离，清洗后即得聚离子薄膜。本申请的制备方法能够制备出具有不同表面形貌的聚离子薄膜，成本低、易于规模化生产，为聚离子薄膜在传感器、医疗检测等多个领域的应用提供有力保障。本申请还提供一种检测试剂盒。

Description

制备聚离子薄膜的方法、聚离子薄膜以及检测试剂盒
本申请要求于2020年07月24日提交中国专利局，申请号为202010725943.6，申请名称为“制备聚离子薄膜的方法、聚离子薄膜以及检测试剂盒”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于材料技术领域，具体地涉及一种制备聚离子薄膜(尤其是表面图案化的聚离子薄膜)的方法，以及由该方法制备得到的聚离子薄膜和包含该聚离子薄膜的检测试剂盒。
背景技术
刺激敏感型(响应型)材料是指面对外界环境变化时有响应的材料，例如pH值、温度、光等的改变引起材料微观结构的改变，从而呈现出诸如颜色改变、物理、化学形态的改变，这种性质使刺激敏感型材料在传感器、药物释放、生物工程等方面有着巨大的应用前景。如pH敏感型薄膜，其在pH传感器、药物控缓释、体内检测等领域应用广泛。但薄膜微观形貌与宏观变化(如响应速率)间的联系却少有人研究。如何放大响应变化、提高响应速率，对pH型离子薄膜更好的服务于工业生产中，有着巨大意义，但不同微观形貌的响应型离子薄膜的合成是一个难题。因此，人们寻求一种能合成不同表面形貌的pH型离子薄膜制备方法，简单便捷且薄膜能重复使用。
在现有技术中，为了制备带有图案的电薄膜，首先需要在衬底上采用点胶工艺形成预定图形的聚合物掩模，然后对该衬底进行氧等离子处理或紫外光照射处理，再通过溶液工艺在附有所述聚合物掩模的衬底上制备导电薄膜，最后将该聚合物掩模从所述衬底上剥离，从而得到图形化的导电薄膜。但是，根据这种制备方法只能得到一些形成有简单的图案电薄膜，且图案精度低。该方法通过点胶工艺来制备电薄膜。胶水本身具有延展性或流动性，很难精确控制，并且受点胶参数的影响(例如气压大小、点胶量)的影响，形成的聚合物掩模本身精度低(等离子处理或紫外光处理，其固化速率受胶量的影响，精度或高或低)，容易形成锯齿状边缘，影响最终影响薄膜的精度。并且，现有技术中公开的方法制备过程难以控制，且成品难以剥离，薄膜完整性很难保证。
此外，现有技术中的制备图案化金属薄膜还包括：先将洁净的基底浸没在多巴 胺溶液中，至基底表面形成聚多巴胺膜，取出用水冲洗后氮气吹干，得到附有聚多巴胺膜的基底；然后将得到的附有聚多巴胺膜的基底上放置光掩膜，然后在紫外光下照射15分钟，再用水清洗，氮气吹干，得到被紫外固化后的聚多巴胺的基底，最后在基底上沉积金属离子得到图案化的金属薄膜。根据此合成方法虽然能够得到不同图案的薄膜，但步骤多，需要先形成多巴胺膜，又需要光掩模，且需要不断地进行水和氮气的冲洗以保证薄膜的图案化的完整，并且利用紫外光氧化破坏聚多巴胺膜来形成图案薄膜，导致该工艺方法精度低，难以大规模生产高精度的图案化薄膜。
申请内容
本申请的目的在于提供一种简单、便捷、高效的制备聚离子薄膜(尤其是表面图案化的聚离子薄膜)的方法。
本申请提供一种制备聚离子薄膜的方法，所述方法包括以下步骤：
(1)提供基板，在所述基板的表面上或在覆盖于所述基板的表面的锡纸的表面上涂抹第一润滑剂；
(2)将聚离子薄膜的成膜液覆盖在涂有所述基板或所述锡纸的表面上，涂覆均匀后，将涂有第二润滑剂的盖板覆盖在成膜液上；
(3)使成膜液中的离子液体单体发生聚合反应，形成聚离子薄膜；
(4)将所述聚离子薄膜分离，清洗后即得聚离子薄膜。
优选地，所述基板包括硅片；
优选地，所述硅片是表面已被图案化的硅片；
优选地，硅片表面具有凸起的脊部、或硅片表面具有凹陷的沟槽、或硅片表面设置有突出的圆柱状部件、或硅片表面设置有贯穿硅片的圆孔。
优选地，在步骤(1)中，所述第一润滑剂及第二润滑剂对紫外光是惰性的且对紫外光不产生干扰；
优选地，在步骤(1)中，所述第一润滑剂选自白凡士林、硅油、石蜡、矿物油、润滑脂中的一种或多种。
优选地，在步骤(2)中，所述成膜液包括咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季膦类离子液体、吡咯烷类离子液体中的一种或多种；
优选地，所述成膜液包括1-乙基-3-甲基咪唑四氟硼酸盐、1-乙基-3-甲基咪唑氯盐、N-乙基吡啶溴盐、三丁基甲基氯化铵、三丁基乙基溴化膦、N-丁基-N-甲基吡咯 烷溴盐中的一种或多种；
优选地，所述盖板为玻璃板、或耐紫外光的硬质塑料板；
优选地，所述第二润滑剂选自白凡士林、硅油、石蜡、矿物油、润滑脂。
优选地，在步骤(3)中，所述聚合反应在紫外光的照射下进行；
优选地，紫外光的波长为250nm～400nm；
优选地，照射的时间15min～30min。
优选地，在步骤(3)中，所述聚合反应在20℃～60℃的温度下进行；
优选地，所述聚合反应由引发剂引发；更优选地，所述引发剂选自光引发剂907、光引发剂184、偶氮二异丁腈、2,4,6-(三甲基苯甲酰基)二苯基氧化膦或苯偶姻及其衍生物。
优选地，在步骤(4)中，所述聚离子薄膜分离的步骤包括：将附着有聚离子薄膜的盖板放入水中静置；
优选地，所述清洗包括依次在清水、无水乙醇和清水中进行超声清洗。
优选地，在步骤(1)中，还包括将锡纸铺在基板上之前，用溶剂将所述基板润湿；
优选地，所述溶剂为水、乙醇或其混合溶剂。
优选地，在步骤(2)中，所述成膜液通过以下步骤来制备：
(a)将离子液体单体充分混合；
(b)加入交联剂和引发剂，然后进行超声处理，得到所述成膜液；
优选地，在步骤(a)中，还包括在将离子液体单体充分混合后，将得到的混合液进行超声处理；更优选地，超声处理进行10min～30min；
优选地，在步骤(b)中，超声处理进行10min～30min。
优选地，在步骤(a)中，所述离子液体单体包括溴丁烷、乙烯基咪唑和丙烯腈；
优选地，所述交联剂为N,N-亚甲基双丙烯酰胺，所述引发剂为2,4,6-(三甲基苯甲酰基)二苯基氧化膦；
优选地，溴丁烷和乙烯基咪唑的摩尔比为2∶1至1∶1；
优选地，丙烯腈的质量大于或等于溴丁烷与乙烯基咪唑二者的质量之和；
优选地，在步骤(b)中，所述交联剂的质量为以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的8wt％～12wt％，引发剂的质量为以溴丁烷、乙烯基咪唑和丙烯 腈三者的总质量计算的0.5wt％～2wt％。
优选地，所述成膜液通过以下步骤来制备：
(a)将等摩尔比的溴丁烷和乙烯基咪唑混合，将得到的混合液进行超声处理15min，直至两者充分混合；然后加入与溴丁烷和乙烯基咪唑二者的质量之和相等的丙烯腈；
(b)加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为8wt％的N,N-亚甲基双丙烯酰胺以及以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为1.0wt％的2,4,6-(三甲基苯甲酰基)二苯基氧化膦，加完后超声处理15min，得到成膜液。
优选地，所述方法还包括将所述聚离子薄膜浸没在具有染料的染料溶液中；
优选地，所述染料选自溴甲酚绿、甲酚红、甲基橙中的一种；
优选地，所述染料溶液为染料溶解在水与乙醇的混合溶剂中得到的溶液，其中，在水与乙醇的混合溶剂中，水与乙醇的体积比为4∶1～1∶8，优选1∶4。
优选地，在所述染料溶液中，染料的浓度为0.5～8mg/ml，更优选3.95mg/ml。
一种聚离子薄膜，所述聚离子薄膜通过上述的方法制备得到。
一种检测试剂盒，包括上述的所述的聚离子薄膜。
优选地，所述检测试剂盒还包括比色卡。
本申请提供的聚离子薄膜的制备方法通过润滑剂的使用，降低聚离子薄膜与基板分离的难度。另外，锡纸的使用不仅有利于加快聚离子薄膜的成膜速度，而且避免了成膜前成膜液与基板(例如，硅片)的直接接触，保证了薄膜的完整性与薄膜厚度的均一性，并且大大缩减了薄膜分离所需要的时间。本申请还以图案化的硅片作为模板制备表面图案化的聚离子薄膜。
本申请的方法易于操作，聚离子薄膜易于分离，膜厚均一且可调控，技术门槛低，因此具有很大的应用潜力。
本申请的表面图案化的聚离子薄膜至少可以应用于以下几个方法。
(1)体液的酸碱值的体内或体外检测。例如，将聚离子薄膜固定于胃镜上，或将胃液取出至体外，使聚离子薄膜与胃液接触，通过观察薄膜变化来判断体内的酸碱值；
(2)酸碱动态监测，例如用于检测泳池中的水的酸碱度；
(3)环境检测，例如，工业废水的排放会导致河流的污染，在这种情形下，可以将聚离子薄膜固定在河流中，同时在聚离子薄膜旁边设置比色卡，通过观察聚离子薄膜颜色的变化来判断酸碱值。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性的，并不能限制本申请。
附图说明
图1是硅片表面具有凸起的脊部的示意图；
图2是硅片表面具有凹陷的沟槽的示意图；
图3是硅片表面设置有突出的圆柱状部件示意图；
图4是硅片表面设置有贯穿硅片的圆孔示意图；
图5是由本申请的方法制备的具有细条纹图案的聚离子薄膜的显微照片；
图6是由本申请的方法制备的具有凹坑状图案的聚离子薄膜的显微照片；
图7由本申请的方法制备的具有复杂图案的聚离子薄膜的显微照片。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请实施例，对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请提供的技术方案及所给出的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。
需要说明的是，本文中使用的术语“和/或”或者“/”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点 值之间、各个范围的端点值或单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围。
如果没有特别的说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。除非另有定义或说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。
为了解决上述的技术问题，本申请的实施例提供一种制备聚离子薄膜的方法包括以下步骤：
(1)提供基板，在基板的表面上或在覆盖于基板的表面的锡纸的表面上涂抹第一润滑剂；
(2)将聚离子薄膜的成膜液覆盖在涂有第一润滑剂的基板的表面上，涂覆均匀后，将涂有第二润滑剂的盖板覆盖在成膜液上；
(3)使成膜液中的离子液体单体发生聚合反应，形成聚离子薄膜；
(4)将聚离子薄膜分离，清洗后即得表面图案化的聚离子薄膜。
上述方法通过在涂有润滑剂的两个表面之间使用聚离子薄膜的成膜液形成聚离子薄膜，实现聚离子薄膜的快速制备。
在本申请的实施例中，基板的表面可以是光滑的，也可以是表面不平坦且带有图案的。润滑剂应涂抹均匀，以获得更高质量的聚离子薄膜。
本申请的制备方法能够制备出具有不同表面形貌的聚离子薄膜，且合成简便、成本低、易于规模化生产，为聚离子薄膜在传感器、医疗检测等多个领域的应用提供了多样性的选择。
在本申请的一个实施例中，基板包括硅片，即采用硅片作为基板或采用包含有硅片的基板组件等。采用硅片作为基板具有如下优势：硅片具有惰性的性质，对温度、紫外线等环境因素不敏感，具有优良的稳定性；对成膜液等化学成分不起干扰，不会影响固化成膜的过程；硅片的表面易控，可以在表面进行图案化加工，从而提高聚离子薄膜的精度主要原因在于，硅片与本申请的方法结合使用，成膜液在已定的形貌中进行固化成膜。同时，由于盖板的压合，可以使成膜液均匀平铺开，从而可以控制薄膜(即聚离子薄膜)的整体厚度，不会出现薄膜厚度或高过低的现象。根据不同的生产需求，为了满足不同厚度聚离子薄膜的需要，本申请提供的聚离子 薄膜的制备方法可以选择不同厚度或不同质量的盖板，从而对薄膜的厚度进行调节，需要注意的是盖板的厚度应当处于允许紫外线透过盖板的范围内，在此不再赘述。
在本申请的实施例中，硅片可以是表面光滑的硅片，也可以是表面已被图案化的硅片。其中，不同图案化的薄膜在进行检测时其响应速度也是不同的，在实际应用中可以根据需要进行调控。具体来说，根据具有图案的硅片基底制得的具有不同图案的薄膜的离子交换速率不同，而离子交换速率会影响薄膜显色的响应速率以及均一性。特别地，针对一些灵敏度要求更高或更精细的但传统传感器的应用受限制(例如受体积限制)的领域(比如体内检测)，由本申请的方法制备得到的薄膜就会表现出巨大的优势。
硅片表面的图案可以有多种。例如，硅片表面可以是凸起的脊部、凹陷的沟槽、突出于硅片表面的圆柱体，也可以是贯穿硅片的圆孔。形成图案的独立部件(例如脊部、沟槽、圆柱或圆孔)可以具有不同的尺寸或间距。例如，硅片的表面刻有细小的条纹，条纹的间隙和条纹大小可以调整，例如条纹的间隙和大小均调整为微米级别(例如50μm)或调整至毫米级别。
如图1所示，硅片表面具有凸起的脊部。
如图2所示，硅片表面具有凹陷的沟槽。
如图3所示，硅片表面设置有突出的圆柱状部件。
如图4所示，硅片表面设置有贯穿硅片的圆孔。
在本申请方法的一种实施方式中，在锡纸的表面上涂抹第一润滑剂。锡纸具有很强的惰性，不易于润滑剂或聚离子薄膜的成膜液发生反应，且锡纸的表面很光滑，有利于形成更加均匀的聚离子薄膜。在聚离子薄膜的分离过程中，锡纸可以轻易地与薄膜剥离(甚至可以手动将锡纸撕下)，生成的聚离子薄膜与盖板接触的一侧可在液体环境下分离，因此缩短了分离时间。
在一个优选的实施方式中，方法包括以下步骤：
(1)将锡纸铺在图案化的硅片上，将锡纸抚平，在锡纸的远离硅片的表面上涂抹第一润滑剂；
(2)将用于制备聚离子薄膜的成膜液覆盖在锡纸的表面上，涂覆均匀，将预先涂有第二润滑剂的盖板覆盖在载有成膜液的锡纸上；其中，涂有第二润滑剂的盖板的表面与锡纸上的成膜液相接触；
(3)使成膜液中的离子液体单体发生聚合反应，形成聚离子薄膜；
(4)将聚离子薄膜从盖板上分离，清洗后即得表面图案化的聚离子薄膜。
在本方法一个实施例的步骤(1)中，第一润滑剂对紫外光是惰性的且对紫外光不产生干扰。更优选地，在步骤(1)中，第一润滑剂可以为白凡士林、硅油、石蜡、矿物油或润滑脂等。第一润滑剂需要无毒，无腐，无残留且涂覆透明。在医疗器械领域，特别是对安全性要求高的领域，如传感器和药物控缓释等，对第一润滑剂具有更高的要求，因此需要采用医用级别的润滑剂。优选地，在步骤(1)中，第一润滑剂选自白凡士林、硅油、石蜡、矿物油、润滑脂中的一种或多种。类似地，第二润滑剂选自白凡士林、硅油、石蜡、矿物油、润滑脂中的一种或多种。
本申请的一个实施例，在上述方法的步骤(2)中，可以根据不同的需求和应用场景选择不同的成膜液。根据成膜液中离子液体的成分，成膜液可以包括咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季膦类离子液体或吡咯烷类离子液体中的一种或多种。根据成膜液中离子液体所发挥的功能，成膜液可以包括本领域常用的功能化离子液体。咪唑类离子液体(1-乙基-3-甲基咪唑四氟硼酸盐、1-乙基-3-甲基咪唑氯盐)、吡啶类离子液体(N-乙基吡啶溴盐)、季铵盐类离子液体(三丁基甲基氯化铵)、季膦类离子液体或吡咯烷类离子液体(三丁基乙基溴化膦、N-丁基-N-甲基吡咯烷溴盐)。
优选地，在一实施例中，根据上述方法的步骤(2)，盖板可以是透明基板。在基板是透明基板的情况下，盖板可以是透明的玻璃板或耐紫外光(不与紫外光反应且紫外光可以透过)的硬质塑料板。盖板为玻璃板或耐紫外光的硬质透明塑料板。透明的玻璃板或耐紫外光的硬质透明塑料板可以使聚合反应在紫外的照射下进行，为聚合反应的进行提供了一种可选的方案。在本申请中，耐紫外光的硬质透明塑料板是指透明塑料板中的材料对紫外线不敏感，不会因为紫外线的穿过而导致透明塑料板发生变性。例如，制备透明塑料板的材料为PC(Polycarbonate，聚碳酸酯)、TPU(Thermoplastic polyurethanes，热塑性聚氨酯弹性体)、亚克力等。
优选地，在本实施例中，第二润滑剂对紫外光是惰性的且对紫外光不产生干扰且选自白凡士林、硅油、石蜡、矿物油、润滑脂中的一种或多种。
在本申请一实施例的方法的步骤(3)中，聚合反应在紫外光的照射下进行。优选地，紫外光的波长为250nm～400nm。优选地，紫外光照射的时间15min～30min。
在一实施例中，聚合反应在加热的条件下进行，聚合反应在20℃～60℃的温度下进行。
在另一实施例中，为了促进聚合反应的发生，聚合反应由引发剂引发。引发剂可以是本领域常用的引发剂，例如光引发剂907(2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮)、光引发剂184(1-羟基环己基苯基甲酮)、偶氮二异丁腈、2,4,6-(三甲基苯甲酰基)二苯基氧化膦(TPO)、苯偶姻及其衍生物等，本领域技术人员可以根据成膜液的具体成分选择适当的引发剂。
优选地，通过将附着有聚离子薄膜的盖板放入水中静置来实现聚离子薄膜从盖板上的分离。通过上述的方式，可以使聚离子薄膜自动地从盖板上分离，操作简单，同时提高了良品率。
在本实施例的步骤(4)中，清洗包括依次在清水、无水乙醇、清水中进行超声清洗。
值得一提的是，在本申请的实施例的步骤(1)中，还包括将锡纸铺在基板上之前，用溶剂将基板润湿。将基板润湿的目的是为了排除基板与锡纸之间的空气，通过溶剂与锡纸的贴合性来增加基板与锡纸的结合力，从而使锡纸更易于抚平，提高锡纸表面的平整度。将基板润湿的溶剂可以有多种，但是从来源、成本和环保的角度，溶剂优选为水、乙醇或其混合溶剂。
在一实施例的步骤(2)中，成膜液可以通过以下步骤来制备：
(a)将离子液体单体充分混合；
(b)加入交联剂和引发剂，然后进行超声处理，得到成膜液；
优选地，在本申请的实施例中，在步骤(a)中，还包括在将离子液体单体充分混合后，将得到的混合液进行超声处理。更优选地，超声处理进行10min～30min。
优选地，在步骤(b)中，超声处理进行10min～30min。
在上述步骤(a)中，离子液体单体包括溴丁烷、乙烯基咪唑和丙烯腈。优选地，交联剂为N,N-亚甲基双丙烯酰胺(MBA)，引发剂为2,4,6-(三甲基苯甲酰基)二苯基氧化膦(TPO)。
具体来说，在本实施例中，溴丁烷和乙烯基咪唑的摩尔比为2∶1至1∶1；优选1∶1。考虑到二者反应配比、转化率、用量及后续的清洗处理过程，溴丁烷和乙烯基咪唑的摩尔比为1∶1。
优选地，在本实施例中，在步骤(a)中，为确保反应完全，丙烯腈的质量大于或等于溴丁烷与乙烯基咪唑的质量之和。考虑到三者反应配比、转化率、用量及后续的清洗处理过程，丙烯腈的质量为溴丁烷与乙烯基咪唑质量之和。
优选地，在本申请提供的方法的步骤(b)中，交联剂的质量为以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的8wt％～12wt％，例如可以为8wt％、9wt％、10wt％、12wt％等。引发剂的质量为以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的0.5wt％～2wt％，例如可以为0.5wt％、1wt％、1.5wt％、2wt％等。
具体地，在本实施例提供的方法的步骤(2)中，成膜液可以通过以下步骤来制备：
(a)将等摩尔比的溴丁烷和乙烯基咪唑混合，将得到的混合液进行超声处理15min，直至两者充分混合；然后加入与溴丁烷和乙烯基咪唑二者的质量之和相等的丙烯腈；若混合溶液的表面有漂浮的杂质，则可以通过吸管或移液管将杂质去除；
(b)加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为8wt％的N,N-亚甲基双丙烯酰胺(MBA)以及以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为1.0wt％的2,4,6-(三甲基苯甲酰基)二苯基氧化膦(TPO)，加完后超声处理15min，得到成膜液。
在在步骤(a)中，超声处理可以为溴丁烷和乙烯基咪唑的混合液增加能量场，从而加速反应的进行。
本申请实施例提供的方法还包括将得到的表面图案化的聚离子薄膜浸没在具有染料的染料溶液中，以得到一种可用作pH检测的聚离子薄膜。
上述所用的染料可以为本领域常用染料，只要其能够与薄膜基底稳定结合，且安全性得到保证即可。例如，染料可以选自溴甲酚绿(BG)、甲酚红(CR)、甲基橙(MO)中的一种。小分子染料BG、CR或MO与薄膜交换后，对pH值具有响应性，在不同的pH条件下，呈现出不同的分子结构，微观表现为不同的紫外光谱吸收峰，宏观表现出不同的颜色。
优选地，染料溶液为染料溶解在水-乙醇混合溶剂中的溶液，其中，在水-乙醇混合溶剂中，水与乙醇的体积比为4∶1～1∶8。例如水与乙醇的比例为4∶1、2∶1、1∶1、1∶2、1∶4、1∶6或1∶8。
优选地，在染料溶液中，染料的浓度为0.5～8mg/ml。例如，染料的浓度为0.5 mg/ml、1.0mg/ml、1.5mg/ml、2.0mg/ml、2.5mg/ml、3.0mg/ml、3.5mg/ml、4.0mg/ml、4.5mg/ml、5.0mg/ml、5.5mg/ml、6.0mg/ml、6.5mg/ml、7.0mg/ml、7.5mg/ml或8.0mg/ml。优选地，染料的浓度为3.95mg/ml。
因此，本申请还提供一种聚离子薄膜，该聚离子薄膜通过上述实施例中的制备方法得到。
因此，本申请还提供一种检测试剂盒，该检测试剂盒包括浸渍染料后得到的聚离子薄膜。
在本申请优选的检测试剂盒的一种实施方式中，检测试剂盒包括比色卡和上述的聚离子薄膜。通过聚离子薄膜颜色的变化，对照预先制作的比色卡，可以快速检测被检测液体的pH值。
下面以具体的实施例详细描述聚离子薄膜的制备过程以及聚离子薄膜的具体应用。
实施例1
取摩尔比为2∶1的溴丁烷和乙烯基咪唑，置于玻璃瓶中，超声处理10min至两者充分混合。在溶液可见漂浮的类似油状的浮沫杂质，通过吸管去除杂质后加入与溴丁烷和乙烯基咪唑二者的质量相等的丙烯腈溶液，再加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为8％的MBA(交联剂)和以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为1.0％的TPO(聚合反应的光引发剂)，然后超声处理10min，形成澄清透明的聚离子薄膜的成膜液。
取一块透明玻璃板，在玻璃板的一个表面上均匀涂抹白凡士林，吸取成膜液，覆盖在光滑的透明玻璃板上，盖上透明玻璃板(透明玻璃板与成膜液接触的表面涂有硅油)，轻压透明玻璃板。将两玻璃板形成的组合体放在250nm的紫外光下，照射15min，(环境温度为20℃)，以引发溴丁烷、乙烯基咪唑和丙烯腈之间发生聚合反应，形成透明薄膜。聚合反应束后，将组合体冷却至室温。将粘有透明薄膜的组合体与放入水中，浸泡20min后，聚离子薄膜自动从两透明玻璃板之间剥离。随后用纯水超声清洗聚离子薄膜，超声清洗结束后，依次采用纯水、无水乙醇、纯水进行超声清洗聚离子薄膜，然后吹干以备用。
实施例2
取摩尔比为1∶1的溴丁烷和乙烯基咪唑，置于玻璃瓶中，混合均匀，然后超声处理30min至两者充分混合，去除杂质后加入与溴丁烷和乙烯基咪唑二者的质量相等的丙烯腈溶液，再加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为8％的MBA(交联剂)和以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为1％的TPO(光引发剂)，然后超声处理20min，形成澄清透明的聚离子薄膜的成膜液。
取一块图案化(如细纹)并清洗干净的硅片(晶向N<100>)上，将硅片清洁，用水/乙醇(体积比为1∶1)的混合溶剂将硅片表面润湿，用清洁、平整的锡纸将硅片包住，将锡纸抚平，然后在锡纸上均匀涂抹石蜡。吸取成膜液，将成膜液覆盖在硅片上，盖上透明玻璃盖板(玻璃盖板的与锡纸接触的表面涂有白凡士林)。将形成的组合体放在265nm的紫外光下，从透明玻璃盖板侧照射20min，(环境温度为55℃)以引发溴丁烷、乙烯基咪唑和丙烯腈之间发生聚合反应，形成透明薄膜。聚合反应束后，将组合体冷却至室温后整体放入水中，浸泡20min后，聚离子薄膜自动从玻璃盖板上剥离。随后用纯水超声清洗聚离子薄膜，超声清洗结束后，将聚离子薄膜浸没在BG染料溶液中(BG染料的浓度为8mg/ml，溶剂为水与乙醇的混合溶剂，水与乙醇体积比为1∶4)，在30℃的温度下放置20min，取出聚离子薄膜，此时聚离子薄膜呈蓝色，依次采用纯水、无水乙醇、纯水进行超声清洗聚离子薄膜。在显微镜观察下可以看到聚离子薄膜呈现出细条纹状(如图5所示)，然后吹干以备用。浸染了BG染料的聚离子薄膜可以用于溶液pH值的检测。
实施例3
取摩尔比为1∶1的溴丁烷和乙烯基咪唑，置于玻璃瓶中，超声处理20min至两者充分混合，然后加入与溴丁烷和乙烯基咪唑二者的质量相等的丙烯腈溶液，再加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为12％的MBA和以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为2％的TPO，然后超声处理30min，形成澄清透明的聚离子薄膜的成膜液。
取一块表面平整的硅片(晶向N<100>)上，将硅片用清洁，然后用水与乙醇(体积比为1∶1)的混合溶剂将硅片表面润湿，用清洁、平整的锡纸包住硅片，将锡纸 抚平，然后在锡纸上均匀涂抹白凡士林。吸取成膜液，将成膜液覆盖在硅片上，盖上玻璃盖板(玻璃盖板与锡纸接触的表面涂有白凡士林)。将形成的组合体放在365nm的紫外光下照射30min(此时环境温度为55℃)，以引发溴丁烷、乙烯基咪唑和丙烯腈之间发生聚合反应，形成透明薄膜。聚合反应束后，将组合体冷却至室温后整体放入水中，浸泡25min后，聚离子薄膜自动从玻璃盖板上剥离。随后用纯水超声清洗聚离子薄膜，超声清洗结束后，将聚离子薄膜浸没在BG染料溶液(浓度为0.5mg/ml，溶剂为水与乙醇的混合溶剂，水与乙醇的体积比为1∶1)中，在30℃的温度下放置20min，取出聚离子薄膜，此时聚离子薄膜呈天蓝色，依次采用纯水、无水乙醇、纯水进行超声清洗聚离子。在显微镜观察下可以看到聚离子薄膜为平整的表面，然后吹干以备用。
实施例4
取摩尔比为1.5∶1的溴丁烷和乙烯基咪唑，置于玻璃瓶中，混合均匀，然后超声处理15min至两者充分混合，然后加入与溴丁烷和乙烯基咪唑二者的质量相等的丙烯腈溶液，再加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为8％的MBA和以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为0.5％的TPO，然后超声处理10min，形成澄清透明的聚离子薄膜的成膜液。
将溶液吸取，取一块表面具有凹坑的硅片(晶向N<100>，图案自行设计)上，将硅片清洁，然后用水/乙醇(体积比为1∶1)的混合溶剂将硅片表面润湿，用清洁、平整的锡纸包住硅片，将锡纸抚平，然后在锡纸上均匀涂抹白凡士林。吸取成膜液，将成膜液覆盖在硅片上，盖上耐紫外光的硬质透明塑料板(塑料板与锡纸接触的表面涂有白凡士林)。将形成的组合体放在254nm的紫外光下，从硬质透明塑料板一侧照射15min(环境温度为55℃)，以引发溴丁烷、乙烯基咪唑和丙烯腈之间发生聚合反应，形成透明薄膜。聚合反应结束后，将组合体冷却至室温后整体放入水中，浸泡20min后，聚离子薄膜自动从玻璃盖板上剥离。随后用纯水超声清洗聚离子薄膜，超声清洗结束后，将聚离子薄膜浸没在CR染料溶液中(CR染料的浓度为3.95mg/ml，溶剂为水与乙醇的混合溶剂，水与乙醇体积比为4∶1)，在30℃的温度下放置20min，取出聚离子薄膜，此时薄膜呈深蓝色。依次采用纯水、无水乙醇、纯水超声清洗聚离子薄膜，在显微镜观察下可以看到聚离子薄膜呈现出凹坑状(如图6 所示)，然后吹干以备用。浸染了CR染料的聚离子薄膜可以用于溶液pH值的检测。
实施例5
取摩尔比为1∶1的溴丁烷和乙烯基咪唑，置于玻璃瓶中，混合均匀，然后超声处理15min至两者充分混合，然后加入与溴丁烷和乙烯基咪唑二者的质量相等的丙烯腈溶液，再加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为10％的MBA和以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为1.0％的TPO，然后超声处理15min，形成澄清透明的聚离子薄膜的成膜液。
取一块刻有复杂图案的硅片(晶向N<100>，图案自行设计)上，将硅片清洁后，用清洁、平整的锡纸包住硅片，将锡纸抚平，然后在锡纸上均匀涂抹矿物油。吸取成膜液，将成膜液覆盖在硅片上，盖上玻璃盖板(玻璃盖板与锡纸接触的表面涂有润滑脂)。将形成的组合体放在254nm的紫外光下照射15min(此时环境温度为55℃)，以引发溴丁烷、乙烯基咪唑和丙烯腈之间发生聚合反应，形成透明薄膜。聚合反应结束后，将组合体冷却至室温后整体放入水中，浸泡20min后，聚离子薄膜自动从玻璃盖板上剥离。随后用纯水超声清洗聚离子薄膜，超声清洗结束后，将聚离子薄膜浸没在MO染料溶液中(MO染料的浓度为3.95mg/ml，溶剂为水与乙醇的混合溶剂，水与乙醇的体积比为1∶8)，在30℃的温度下放置20min，取出聚离子薄膜，此时聚离子薄膜呈深蓝色，依次采用纯水、无水乙醇、纯水超声清洗聚离子薄膜。在显微镜观察下可以看到聚离子薄膜呈现出与硅片对应的图案(如图7所示)，然后吹干以备用。浸染了MO染料的聚离子薄膜可以用于溶液pH值的检测。
应用例1
本应用例介绍本申请的方法制备的聚离子薄膜在体液检测中的应用。
具体地，将胃管插入受试者的胃内，通过真空抽吸泵抽取20ml胃液。将胃液转移至干净的烧杯内，放入如前述实施例中制备得到的聚离子薄膜(经过CR浸染)并静置。之后取出该聚离子薄膜，观察聚离子薄膜的颜色变化，并根据聚离子薄膜变化后的颜色，与比色卡对比得到胃液的pH值。通常，胃液的pH为2～3之间的数值，若测得pH值超出正常值的参考范围，可初步推测，受试者胃部具有发生病变的可能性。
应用例2
本应用例介绍本申请的方法制备的聚离子薄膜在水质检测中的应用。
具体地，本申请的方法制备的聚离子薄膜可以用在水的pH值的检测中。pH值是水质的重要指标，它决定着水体中的很多化学和生物过程，是水质的晴雨表，pH值过高或过低对鱼虾都有直接的危害。pH值过低可使对鱼虾血液的pH值下降，削弱其载氧能力，可能造成对鱼虾生理缺氧。此时尽管水中溶氧充足但对鱼虾仍会因生理缺氧而浮头，并停止摄食。pH值过高则腐蚀鳃组织，可能引起对鱼虾大量死亡。pH值过高或过低都会使水中微生物活动受到抑制，使有机物质不易分解。pH值高于8.0，大量的离子氨会转化成有毒的NH 3；低于6.0时，水中90％以上的硫化物会以H 2S的形式存在，增大硫化物的毒性。pH值低于4.0或高于10.6时对鱼虾不能存活。因此pH值的实时检测十分重要，在本应用例中，将本申请制备的聚离子薄膜(具有孔洞结构)放置于水中，通过聚离子薄膜的实时显色变化来判断此时水质的pH值，操作十分简单。相对于pH试纸，无需取样测试，也无需担心染料溢出造成对水质的污染；相对于电化学传感器，采用本申请的聚离子薄膜价格更便宜。
以上仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。
需要指出的是，本专利申请文件的一部分包含受著作权保护的内容。除了对专利局的专利文件或记录的专利文档内容制作副本以外，著作权人保留著作权。

Claims (18)

  1. 一种制备聚离子薄膜的方法，其特征在于，所述方法包括以下步骤：
    提供基板，在所述基板的表面上或在覆盖于所述基板的表面的锡纸的表面上涂抹第一润滑剂；
    将聚离子薄膜的成膜液覆盖在涂有所述基板或所述锡纸的表面上，涂覆均匀后，将涂有第二润滑剂的盖板覆盖在成膜液上；
    使成膜液中的离子液体单体发生聚合反应，形成聚离子薄膜；
    将所述聚离子薄膜分离，清洗后即得聚离子薄膜。
  2. 根据权利要求1所述的方法，其特征在于，所述基板包括硅片；所述硅片是表面已被图案化的硅片；
    或者，所述硅片表面具有凸起的脊部、或硅片表面具有凹陷的沟槽、或硅片表面设置有突出的圆柱状部件、或硅片表面设置有贯穿硅片的圆孔。
  3. 根据权利要求1所述的方法，其特征在于，所述第一润滑剂及第二润滑剂对紫外光是惰性的且对紫外光不产生干扰；
    或者，所述第一润滑剂选自白凡士林、硅油、石蜡、矿物油、润滑脂中的一种或多种。
  4. 根据权利要求1所述的方法，其特征在于，所述成膜液包括咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季膦类离子液体、吡咯烷类离子液体中的一种或多种；
    或者，所述成膜液包括1-乙基-3-甲基咪唑四氟硼酸盐、1-乙基-3-甲基咪唑氯盐、N-乙基吡啶溴盐、三丁基甲基氯化铵、三丁基乙基溴化膦、N-丁基-N-甲基吡咯烷溴盐中的一种或多种。
  5. 根据权利要求4所述的方法，其特征在于，所述盖板为玻璃板、或耐紫外光的硬质塑料板；
    或者，所述第二润滑剂选自白凡士林、硅油、石蜡、矿物油、润滑脂。
  6. 根据权利要求1所述的方法，其特征在于，所述聚合反应在紫外光的照射下进行；
    所述紫外光的波长为250nm～400nm；
    照射的时间为15min～30min。
  7. 根据权利要求1所述的方法，其特征在于，所述聚合反应在20℃～60℃的温度下进行；
    或者，所述聚合反应由引发剂引发，所述引发剂选自光引发剂907、光引发剂184、偶氮二异丁腈、2,4,6-(三甲基苯甲酰基)二苯基氧化膦或苯偶姻及其衍生物。
  8. 根据权利要求1所述的方法，其特征在于，所述聚离子薄膜分离的步骤包括：将附着有聚离子薄膜的盖板放入水中静置；
    或者，所述清洗包括依次在清水、无水乙醇和清水中进行超声清洗。
  9. 根据权利要求1所述的方法，其特征在于，还包括将锡纸铺在基板上之前，用溶剂将所述基板润湿；
    所述溶剂为水、乙醇或其混合溶剂。
  10. 根据权利要求1所述的方法，其特征在于，所述成膜液通过以下步骤来制备：
    (a)将离子液体单体充分混合；
    (b)加入交联剂和引发剂，然后进行超声处理，得到所述成膜液。
  11. 根据权利要求10所述的方法，其特征在于，在步骤(a)中，还包括在将离子液体单体充分混合后，将得到的混合液进行超声处理；超声处理进行10min～30min；
    在步骤(b)中，超声处理进行10min～30min。
  12. 根据权利要求10所述的方法，其特征在于，所述离子液体单体包括溴丁烷、乙烯基咪唑和丙烯腈；
    或者，溴丁烷和乙烯基咪唑的摩尔比为2∶1至1∶1；
    或者，丙烯腈的质量大于或等于溴丁烷与乙烯基咪唑二者的质量之和。
  13. 根据权利要求12所述的方法，其特征在于，所述交联剂为N,N-亚甲基双丙烯酰胺，所述引发剂为2,4,6-(三甲基苯甲酰基)二苯基氧化膦；
    或者所述交联剂的质量为以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的8wt％～12wt％，引发剂的质量为以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的0.5wt％～2wt％。
  14. 根据权利要求10所述的方法，其特征在于，所述成膜液通过以下步骤来制 备：
    (a)将等摩尔比的溴丁烷和乙烯基咪唑混合，将得到的混合液进行超声处理15min，直至两者充分混合；然后加入与溴丁烷和乙烯基咪唑二者的质量之和相等的丙烯腈；
    (b)加入以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为8wt％的N,N-亚甲基双丙烯酰胺以及以溴丁烷、乙烯基咪唑和丙烯腈三者的总质量计算的质量比为1.0wt％的2,4,6-(三甲基苯甲酰基)二苯基氧化膦，加完后超声处理15min，得到成膜液。
  15. 根据权利要求1至14任一项所述的方法，其特征在于，所述方法还包括将所述聚离子薄膜浸没在具有染料的染料溶液中；
    所述染料选自溴甲酚绿、甲酚红、甲基橙中的一种；
    或者，所述染料溶液为染料溶解在水与乙醇的混合溶剂中得到的溶液，其中，在水与乙醇的混合溶剂中，水与乙醇的体积比为4∶1～1∶8，或者为1∶4；
    或者，在所述染料溶液中，染料的浓度为0.5～8mg/ml，或者为3.95mg/ml。
  16. 一种聚离子薄膜，其特征在于，所述聚离子薄膜通过权利要求15所述的方法制备得到。
  17. 一种检测试剂盒，其特征在于，包括权利要求16所述的聚离子薄膜。
  18. 根据权利要求17所述的试剂盒，其特征在于，所述检测试剂盒还包括比色卡。
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CN111812338B (zh) * 2020-07-24 2024-02-27 上海安翰医疗技术有限公司 潜血检测薄膜及其制备方法、应用和潜血检测试剂盒
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