阅读说明：本技术 制备聚离子薄膜的方法、聚离子薄膜以及检测试剂盒 (Method for preparing polyion film, polyion film and detection kit ) 是由 张书鹏 段晓东 于 2020-07-24 设计创作，主要内容包括：本发明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：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的表面上,涂覆均匀后,将涂有第二滑润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。本发明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。本发明还提供一种检测试剂盒。(The present invention provides a method of preparing polyion films, especially polyion films having different surface morphologies, and polyion films prepared by the method, the method comprising the steps of: 1) providing a substrate, and smearing a first lubricant on the surface of the substrate or the surface of the tinfoil covering the surface of the substrate; (2) covering the film forming solution of the polyion film on the surface coated with the substrate, and covering the cover plate coated with the second lubricant on the film forming solution after the film forming solution is uniformly coated; (3) polymerizing the ionic liquid monomer in the film-forming solution to form a polyion film; (4) and separating the polyion film, and cleaning to obtain the polyion film. The preparation method can prepare the polyion film with different surface appearances, has low cost, is easy for large-scale production, and provides powerful guarantee for the application of the polyion film in a plurality of fields such as sensors, medical detection and the like. The invention also provides a detection kit.)

1. A method of making a polyionic film, comprising the steps of:

(1) providing a substrate, and smearing a first lubricant on the surface of the substrate or the surface of the tinfoil covering the surface of the substrate;

(2) covering the film forming solution of the polyion film on the surface coated with the substrate or the tinfoil, and covering the cover plate coated with the second lubricant on the film forming solution after uniform coating;

(3) polymerizing the ionic liquid monomer in the film-forming solution to form a polyion film;

(4) and separating the polyion film, and cleaning to obtain the polyion film.

2. The method of claim 1, wherein the substrate comprises a silicon wafer;

preferably, the silicon wafer is a silicon wafer whose surface has been patterned;

preferably, the surface of the silicon wafer is provided with a raised ridge, or the surface of the silicon wafer is provided with a depressed groove, or the surface of the silicon wafer is provided with a protruding cylindrical component, or the surface of the silicon wafer is provided with a round hole penetrating through the silicon wafer.

3. The method of claim 1, wherein in step (1), the first and second lubricants are inert to and do not interfere with ultraviolet light;

preferably, in step (1), the first lubricant is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, and grease.

4. The method according to claim 1, wherein in step (2), the deposition solution comprises one or more of imidazole-based ionic liquid, pyridine-based ionic liquid, quaternary ammonium salt-based ionic liquid, quaternary phosphine-based ionic liquid, pyrrolidine-based ionic liquid;

preferably, the film-forming solution comprises one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium chloride, N-ethylpyridine bromide, tributylmethylammonium chloride, tributylethylphosphine bromide and N-butyl-N-methylpyrrolidine bromide;

preferably, the cover plate is a glass plate or a hard plastic plate resistant to ultraviolet light;

preferably, the second lubricant is selected from white petrolatum, silicone oil, paraffin, mineral oil, grease.

5. The method according to claim 1, wherein in step (3), the polymerization reaction is performed under irradiation of ultraviolet light;

preferably, the wavelength of the ultraviolet light is 250nm to 400 nm;

preferably, the irradiation time is 15min to 30 min.

6. The process according to claim 1, wherein in step (3), the polymerization reaction is carried out at a temperature of 20 ℃ to 60 ℃;

preferably, the polymerization is initiated by an initiator; more preferably, the initiator is selected from the group consisting of photoinitiator 907, photoinitiator 184, azobisisobutyronitrile, 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide or benzoin and derivatives thereof.

7. The method of claim 1, wherein in step (4), the step of polyionic membrane separation comprises: placing the cover plate attached with the polyion film into water for standing;

preferably, the cleaning comprises ultrasonic cleaning in clean water, absolute ethyl alcohol and clean water in sequence.

8. The method of claim 1, wherein in step (1), further comprising wetting the substrate with a solvent prior to laying the tinfoil on the substrate;

preferably, the solvent is water, ethanol or a mixed solvent thereof.

9. The method according to claim 1, wherein, in step (2), the deposition solution is prepared by:

(a) fully mixing the ionic liquid monomer;

(b) adding a cross-linking agent and an initiator, and then carrying out ultrasonic treatment to obtain the film-forming solution;

preferably, in the step (a), after fully mixing the ionic liquid monomer, subjecting the obtained mixed solution to ultrasonic treatment; more preferably, the ultrasonic treatment is carried out for 10min to 30 min;

preferably, in step (b), the sonication is carried out for 10min to 30 min.

10. The process of claim 9, wherein in step (a), the ionic liquid monomers comprise bromobutane, vinylimidazole and acrylonitrile;

preferably, the crosslinking agent is N, N-methylenebisacrylamide, and the initiator is 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide;

preferably, the molar ratio of bromobutane to vinylimidazole is from 2: 1 to 1: 1;

preferably, the mass of acrylonitrile is greater than or equal to the sum of the masses of bromobutane and vinylimidazole;

preferably, in step (b), the mass of the crosslinking agent is 8 to 12 wt% based on the total mass of the bromobutane, the vinylimidazole and the acrylonitrile, and the mass of the initiator is 0.5 to 2 wt% based on the total mass of the bromobutane, the vinylimidazole and the acrylonitrile.

11. The method according to claim 9, wherein the deposition solution is prepared by:

(a) mixing bromobutane and vinyl imidazole in equal molar ratio, and carrying out ultrasonic treatment on the obtained mixed solution for 15min until the bromobutane and the vinyl imidazole are fully mixed; then adding acrylonitrile with the mass sum of the bromobutane and the vinyl imidazole equal to that of the bromobutane and the vinyl imidazole;

(b) adding 8 wt% of N, N-methylene bisacrylamide and 1.0 wt% of 2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide, wherein the mass ratio is calculated by the total mass of bromobutane, vinyl imidazole and acrylonitrile, and carrying out ultrasonic treatment for 15min after the addition is finished to obtain the film forming liquid.

12. The method of any one of claims 1 to 11, further comprising immersing the polyionic film in a dye solution having a dye;

preferably, the dye is selected from one of bromocresol green, cresol red and methyl orange;

preferably, the dye solution is obtained by dissolving a dye in a mixed solvent of water and ethanol, wherein the volume ratio of water to ethanol in the mixed solvent of water and ethanol is 4: 1-1: 8, preferably 1: 4;

preferably, the concentration of the dye in the dye solution is 0.5-8 mg/ml, and more preferably 3.95 mg/ml.

13. A polyionic film prepared by the method of claim 11.

14. A test kit comprising the polyionic film of claim 13.

15. The kit of claim 14, wherein the test kit further comprises a color chart.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a method for preparing a polyion film (especially a surface-patterned polyion film), the polyion film prepared by the method and a detection kit containing the polyion film.

Background

The stimulus-sensitive (responsive) material is a material which responds to the change of the external environment, for example, the change of pH value, temperature, light and the like causes the change of the microstructure of the material, thereby showing the changes of color, physical and chemical forms, and the property makes the stimulus-sensitive material have great application prospect in the aspects of sensors, drug release, biological engineering and the like. Such as pH sensitive film, which is widely applied in the fields of pH sensor, drug controlled release, in vivo detection, etc. However, the correlation between the micro-topography of the film and the macro-changes (such as response rate) has been rarely studied. How to amplify the response change and improve the response rate has great significance on better serving the pH type ion film in industrial production, but the synthesis of the response type ion films with different microscopic appearances is a difficult problem. Therefore, people seek a preparation method of the pH type ionic thin film capable of synthesizing different surface morphologies, which is simple and convenient and the thin film can be repeatedly used.

In the prior art, in order to prepare an electrical thin film with a pattern, a polymer mask with a predetermined pattern is formed on a substrate by a dispensing process, then the substrate is subjected to oxygen plasma treatment or ultraviolet irradiation treatment, a conductive thin 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, so that the patterned conductive thin film is obtained. However, according to this manufacturing method, only a few electric thin films formed with simple patterns can be obtained, and the pattern accuracy is low. The method prepares the electrical thin film by a dispensing process. The glue itself has ductility or fluidity, is difficult to control accurately, and is influenced by the dispensing parameters (such as air pressure and dispensing amount), the formed polymer mask has low precision (plasma treatment or ultraviolet light treatment, the curing rate of which is influenced by the glue amount, and the precision is high or low), and the jagged edges are easy to form, which finally influences the precision of the film. In addition, the preparation process of the method disclosed in the prior art is difficult to control, the finished product is difficult to peel, and the integrity of the film is difficult to ensure.

In addition, the preparation of the patterned metal thin film in the prior art further includes: firstly, immersing a clean substrate in a dopamine solution until a polydopamine film is formed on the surface of the substrate, taking out the substrate, washing the substrate with water, and then drying the substrate with nitrogen to obtain the substrate attached with the polydopamine film; and then placing a photomask on the obtained substrate attached with the polydopamine film, irradiating for 15 minutes under ultraviolet light, cleaning with water, drying with nitrogen to obtain the ultraviolet-cured polydopamine substrate, and finally depositing metal ions on the substrate to obtain the patterned metal film. Although films with different patterns can be obtained according to the synthesis method, the synthesis method has multiple steps, a dopamine film and a photomask need to be formed firstly, water and nitrogen are continuously flushed to ensure the completeness of the patterning of the film, and the poly dopamine film is damaged by ultraviolet light oxidation to form the patterned film, so that the precision of the process method is low, and the high-precision patterned film is difficult to produce on a large scale.

Disclosure of Invention

In view of the problems in the prior art, the invention provides a simple, convenient and efficient method for preparing polyion films (especially polyion films with patterned surfaces).

The invention provides a method for preparing a polyion film, which comprises the following steps:

(1) providing a substrate, and smearing a first lubricant on the surface of the substrate or the surface of the tinfoil covering the surface of the substrate;

(2) covering the film forming solution of the polyion film on the surface coated with the substrate or the tinfoil, and covering the cover plate coated with the second lubricant on the film forming solution after uniform coating;

(3) polymerizing the ionic liquid monomer in the film-forming solution to form a polyion film;

(4) and separating the polyion film, and cleaning to obtain the polyion film.

Preferably, the substrate comprises a silicon wafer;

preferably, the silicon wafer is a silicon wafer whose surface has been patterned;

preferably, the surface of the silicon wafer is provided with a raised ridge, or the surface of the silicon wafer is provided with a depressed groove, or the surface of the silicon wafer is provided with a protruding cylindrical component, or the surface of the silicon wafer is provided with a round hole penetrating through the silicon wafer.

Preferably, in step (1), the first and second lubricants are inert to and do not interfere with ultraviolet light;

preferably, in step (1), the first lubricant is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, and grease.

Preferably, in the step (2), the film-forming solution comprises one or more of imidazole ionic liquid, pyridine ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphine ionic liquid and pyrrolidine ionic liquid;

preferably, the film-forming solution comprises one or more of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium chloride, N-ethylpyridine bromide, tributylmethylammonium chloride, tributylethylphosphine bromide and N-butyl-N-methylpyrrolidine bromide;

preferably, the cover plate is a glass plate or a hard plastic plate resistant to ultraviolet light;

preferably, the second lubricant is selected from white petrolatum, silicone oil, paraffin, mineral oil, grease.

Preferably, in step (3), the polymerization reaction is performed under irradiation of ultraviolet light;

preferably, the wavelength of the ultraviolet light is 250nm to 400 nm;

preferably, the irradiation time is 15min to 30 min.

Preferably, in step (3), the polymerization reaction is carried out at a temperature of 20 ℃ to 60 ℃;

preferably, the polymerization is initiated by an initiator; more preferably, the initiator is selected from the group consisting of photoinitiator 907, photoinitiator 184, azobisisobutyronitrile, 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide or benzoin and derivatives thereof.

Preferably, in the step (4), the step of separating the polyion membrane comprises: placing the cover plate attached with the polyion film into water for standing;

preferably, the cleaning comprises ultrasonic cleaning in clean water, absolute ethyl alcohol and clean water in sequence.

Preferably, in step (1), before the tinfoil is laid on the substrate, the substrate is wetted by a solvent;

preferably, the solvent is water, ethanol or a mixed solvent thereof.

Preferably, in step (2), the deposition solution is prepared by:

(a) fully mixing the ionic liquid monomer;

(b) adding a cross-linking agent and an initiator, and then carrying out ultrasonic treatment to obtain the film-forming solution;

preferably, in the step (a), after fully mixing the ionic liquid monomer, subjecting the obtained mixed solution to ultrasonic treatment; more preferably, the ultrasonic treatment is carried out for 10min to 30 min;

preferably, in step (b), the sonication is carried out for 10min to 30 min.

Preferably, in step (a), the ionic liquid monomers include bromobutane, vinylimidazole and acrylonitrile;

preferably, the crosslinking agent is N, N-methylenebisacrylamide, and the initiator is 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide;

preferably, the molar ratio of bromobutane to vinylimidazole is from 2: 1 to 1: 1;

preferably, the mass of acrylonitrile is greater than or equal to the sum of the masses of bromobutane and vinylimidazole;

preferably, in step (b), the mass of the crosslinking agent is 8 to 12 wt% based on the total mass of the bromobutane, the vinylimidazole and the acrylonitrile, and the mass of the initiator is 0.5 to 2 wt% based on the total mass of the bromobutane, the vinylimidazole and the acrylonitrile.

Preferably, the deposition solution is prepared by the following steps:

(a) mixing bromobutane and vinyl imidazole in equal molar ratio, and carrying out ultrasonic treatment on the obtained mixed solution for 15min until the bromobutane and the vinyl imidazole are fully mixed; then adding acrylonitrile with the mass sum of the bromobutane and the vinyl imidazole equal to that of the bromobutane and the vinyl imidazole;

(b) adding 8 wt% of N, N-methylene bisacrylamide and 1.0 wt% of 2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide, wherein the mass ratio is calculated by the total mass of bromobutane, vinyl imidazole and acrylonitrile, and carrying out ultrasonic treatment for 15min after the addition is finished to obtain the film forming liquid.

Preferably, the method further comprises immersing the polyionic film in a dye solution having a dye;

preferably, the dye is selected from one of bromocresol green, cresol red and methyl orange;

preferably, the dye solution is obtained by dissolving a dye in a mixed solvent of water and ethanol, wherein the volume ratio of water to ethanol in the mixed solvent of water and ethanol is 4: 1-1: 8, preferably 1: 4.

Preferably, the concentration of the dye in the dye solution is 0.5-8 mg/ml, and more preferably 3.95 mg/ml.

A polyion film is prepared by the method.

A detection kit comprises the polyion film.

Preferably, the detection kit further comprises a color comparison card.

According to the preparation method of the polyion film, the difficulty of separating the polyion film from the substrate is reduced by using the lubricant. In addition, the use of the tinfoil is beneficial to accelerating the film forming speed of the polyion film, and the direct contact between the film forming solution and a substrate (such as a silicon wafer) before film forming is avoided, so that the integrity of the film and the uniformity of the thickness of the film are ensured, and the time required by film separation is greatly shortened. The invention also takes the patterned silicon chip as a template to prepare the polyion film with the patterned surface.

The method of the invention is easy to operate, the film is easy to separate, the film thickness is uniform and controllable, and the technical threshold is low, so that the method has great application potential.

The surface-patterned polyion film of the present invention can be applied to at least the following methods.

(1) In vivo or in vitro detection of the pH of body fluids. For example, fixing the polyion film on a gastroscope, or taking the gastric juice out of the body, contacting the polyion film with the gastric juice, and determining the pH value in the body by observing the change of the film;

(2) acid-base dynamic monitoring, such as for detecting the ph of water in a swimming pool;

(3) environmental tests, for example, discharge of industrial wastewater may cause pollution of rivers, and in this case, the polyion film may be fixed in the rivers while a color chart is disposed beside the polyion film, and the pH value may be judged by observing the color change of the polyion film.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Drawings

FIG. 1 is a schematic view of a silicon wafer surface having raised ridges;

FIG. 2 is a schematic view of a silicon wafer having a recessed trench in its surface;

FIG. 3 is a schematic view of a silicon wafer having a surface provided with protruding cylindrical members;

FIG. 4 is a schematic view of a silicon wafer having a circular hole formed through the surface thereof;

FIG. 5 is a photomicrograph of a polyion film having a fine fringe pattern made by the process of the present invention;

FIG. 6 is a photomicrograph of a polyion film having a crater-like pattern produced by the process of the present invention;

FIG. 7 is a photomicrograph of a polyion film having a complex pattern made by the process of the present invention.

Detailed Description

In order to make the purpose, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it should be apparent that the described embodiments are some but not all of the embodiments of the present application. All other embodiments obtained by those skilled in the art without any creative effort based on the technical solutions and the given embodiments provided in the present application belong to the protection scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.

It should be noted that the term "and/or"/"used herein is only one kind of association relationship describing associated objects, and means that there may be three relationships, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, one or more new numerical ranges may be obtained by combining the individual values, or by combining the individual values.

All the technical features mentioned herein, as well as preferred features, may be combined with each other to form new solutions, if not mentioned specifically. Unless defined or indicated otherwise, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art.

In order to solve the above technical problems, embodiments of the present application provide a method for preparing a polyion film, including the steps of:

(1) providing a substrate, and smearing a first lubricant on the surface of the substrate or the surface of the tinfoil covered on the surface of the substrate;

(2) covering the film forming liquid of the polyion film on the surface of the substrate coated with the first lubricant, and covering the cover plate coated with the second lubricant on the film forming liquid after uniform coating;

(3) polymerizing the ionic liquid monomer in the film-forming solution to form a polyion film;

(4) and separating the polyion film, and cleaning to obtain the polyion film with the patterned surface.

The method realizes the rapid preparation of the polyion film by forming the polyion film between two surfaces coated with the lubricant by using the film-forming solution of the polyion film.

In the embodiment of the present invention, the surface of the substrate may be smooth, or the surface may be uneven and patterned. The lubricant should be applied uniformly to obtain a higher quality polyion film.

The preparation method can prepare the polyion film with different surface appearances, has simple and convenient synthesis, low cost and easy large-scale production, and provides a selection according to diversity for the application of the polyion film in a plurality of fields such as sensors, medical detection and the like.

In one embodiment of the present invention, the substrate comprises a silicon wafer, that is, a silicon wafer is used as the substrate or a substrate assembly including a silicon wafer is used. The silicon chip adopted as the substrate has the following advantages: (1) the silicon chip has the inert property, is insensitive to environmental factors such as temperature, ultraviolet rays and the like, and has excellent stability; (2) the chemical components such as film forming liquid and the like are not interfered, and the curing and film forming process is not influenced; (3) the surface of the silicon chip is easy to control, and patterning processing can be carried out on the surface, so that the precision of the polyion film is improved. Meanwhile, the film forming liquid can be evenly spread due to the pressing of the cover plate, so that the whole thickness of the film can be controlled, and the phenomenon of over-low thickness or height of the film can not occur. According to different production requirements, in order to meet the requirements of polyion films with different thicknesses, cover plates with different thicknesses or different qualities can be selected by the polyion film preparation method provided by the application, so that the thickness of the film can be adjusted, and it should be noted that the thickness of the cover plate is within the range of allowing ultraviolet rays to penetrate through the cover plate, and details are not repeated herein.

In the embodiment of the present invention, the silicon wafer may be a silicon wafer with a smooth surface, or a silicon wafer with a patterned surface. The response speeds of different patterned films are different during detection, and the films can be regulated and controlled according to requirements in practical application. Specifically, the ion exchange rates of films with different patterns, which are manufactured according to silicon wafer substrates with patterns, are different, and the ion exchange rates affect the response rate and uniformity of film color development. In particular, for some fields (such as in vivo detection) where higher or finer sensitivity is required but where the application of conventional sensors is limited (e.g. volume-limiting), the films prepared by the method of the present invention would show great advantages.

The pattern on the surface of the silicon wafer can be various. For example, 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 through the silicon wafer. The individual features (e.g., ridges, grooves, cylinders, or circular holes) that form the pattern may have different sizes or pitches. For example, the surface of the silicon wafer is engraved with fine stripes, and the gaps and the sizes of the stripes can be adjusted, for example, the gaps and the sizes of the stripes are adjusted to 50 μm or to millimeter level.

As shown in fig. 1, the silicon wafer surface has raised ridges.

As shown in fig. 2, the silicon wafer surface has a recessed trench.

As shown in FIG. 3, the silicon wafer surface is provided with a protruding columnar member.

As shown in fig. 4, a circular hole penetrating through the silicon wafer is formed on the surface of the silicon wafer.

In one embodiment of the method of the present invention, a first lubricant is applied to the surface of the tinfoil. The tin foil has strong inertia, is not easy to react with a lubricant or a film forming solution of the polyion film, and has smooth surface, thereby being beneficial to forming more uniform polyion films. During the separation of the polyion film, the tin foil can be easily peeled off from the film (even the tin foil can be manually torn off), and only the side of the generated polyion film, which is in contact with the cover plate, needs to be separated in a liquid environment, so that the separation time is shortened.

In a preferred embodiment, the method comprises the steps of:

(1) spreading the tinfoil on the patterned silicon wafer, flattening the tinfoil, and smearing a lubricant on the surface of the tinfoil far away from the silicon wafer;

(2) covering the film forming liquid for preparing the polyion film on the surface of the tin foil, uniformly coating, and covering the cover plate which is coated with the lubricant in advance on the tin foil loaded with the film forming liquid; wherein, the surface of the cover plate coated with the lubricant is contacted with the film-forming solution on the tinfoil;

(3) polymerizing the ionic liquid monomer in the film-forming solution to form a polyion film;

(4) and separating the polyion film from the cover plate, and cleaning to obtain the polyion film with the patterned surface.

In step (1) of one embodiment of the method, the first lubricant is inert to and does not interfere with ultraviolet light. More preferably, in step (1), the lubricant may be white petrolatum, silicone oil, paraffin, mineral oil, grease, or the like. The lubricant needs to be non-toxic, non-corrosive, non-residue and transparent in coating. In the field of medical devices, especially in the fields with high requirements on safety, such as sensors and controlled release of drugs, the first lubricant has higher requirements, and therefore, a medical grade lubricant is required. Preferably, in step (1), the first lubricant is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, and grease.

In step (2) of the above method, different deposition solutions may be selected according to different requirements and application scenarios. The deposition solution may include one or more of an imidazole-based ionic liquid, a pyridine-based ionic liquid, a quaternary ammonium salt-based ionic liquid, a quaternary phosphonium-based ionic liquid, or a pyrrolidine-based ionic liquid, depending on the composition of the ionic liquid in the deposition solution. Depending on the function to be performed by the ionic liquid in the deposition solution, the deposition solution may comprise a functionalized ionic liquid commonly used in the art. Imidazole ionic liquids (1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole chloride), pyridine ionic liquids (N-ethylpyridine bromide), quaternary ammonium salt ionic liquids (tributyl methyl ammonium chloride), quaternary phosphine ionic liquids or pyrrolidine ionic liquids (tributyl ethyl phosphine bromide, N-butyl-N-methylpyrrolidine bromide).

Preferably, in an embodiment, the cover plate may be a transparent substrate according to step (2) of the above method. In the case where the substrate is a transparent substrate, the cover plate may be a transparent glass plate or a rigid plastic plate resistant to ultraviolet light (which does not react with and is transparent to ultraviolet light). The cover plate is a glass plate or a hard transparent plastic plate resistant to ultraviolet light. The transparent glass plate or the ultraviolet light resistant hard transparent plastic plate can enable the polymerization reaction to be carried out under the irradiation of ultraviolet light, and an alternative scheme is provided for the polymerization reaction. In the present invention, the ultraviolet light resistant rigid transparent plastic plate means that the material in the transparent plastic plate is not sensitive to ultraviolet light and does not cause the transparent plastic plate to be denatured by the penetration of ultraviolet light. For example, the materials in the transparent plastic plate are PC, TPU, acryl.

Preferably, in this embodiment, the second lubricant is inert to and does not interfere with ultraviolet light and is selected from one or more of white petrolatum, silicone oil, paraffin, mineral oil, grease.

In step (3) of the method according to an embodiment of the present invention, the polymerization reaction is performed under irradiation of ultraviolet light. Preferably, the wavelength of the ultraviolet light is 250nm to 400 nm. Preferably, the time of ultraviolet irradiation is 15min to 30 min.

In one embodiment, the polymerization is carried out under heating, and the polymerization is carried out at a temperature of 20 ℃ to 60 ℃.

In another embodiment, to facilitate the polymerization reaction, the polymerization reaction is initiated by an initiator. The initiator may be any initiator commonly used in the art, such as photoinitiator 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-one), photoinitiator 184 (1-hydroxycyclohexylphenylketone), azobisisobutyronitrile, 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide (TPO), benzoin and its derivatives, etc., and those skilled in the art can select an appropriate initiator according to the specific components of the film-forming solution.

Preferably, the polyion film is separated from the cover plate by placing the cover plate with the polyion film attached into water and standing. Through the mode, the polyion film can be automatically separated from the cover plate, the operation is simple, and meanwhile, the yield is improved.

In step (4) of this embodiment, the cleaning includes performing ultrasonic cleaning in clean water, absolute ethyl alcohol, and clean water in sequence.

It is worth integrating, in step (1) of the embodiment of the present application, further comprising wetting the substrate with a solvent before spreading the tinfoil on the substrate. The purpose of wetting the substrate is to eliminate air between the substrate and the tinfoil, and the bonding force between the substrate and the tinfoil is increased through the bonding property of the solvent and the tinfoil, so that the tinfoil is easier to smooth, and the flatness of the surface of the tinfoil is improved. The solvent for wetting the substrate may be various, but is preferably water, ethanol or a mixed solvent thereof from the viewpoint of source, cost and environmental protection.

In step (2) of an embodiment, the deposition solution may be prepared by:

(a) fully mixing the ionic liquid monomer;

(b) adding a cross-linking agent and an initiator, and then carrying out ultrasonic treatment to obtain a film-forming solution;

preferably, in the embodiment of the present application, in the step (a), after fully mixing the ionic liquid monomer, the obtained mixed solution is subjected to ultrasonic treatment. More preferably, the sonication is carried out for 10min to 30 min.

Preferably, in step (b), the sonication is carried out for 10min to 30 min.

In the above step (a), the ionic liquid monomer includes bromobutane, vinylimidazole and acrylonitrile. Preferably, the crosslinker is N, N-Methylenebisacrylamide (MBA) and the initiator is 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide (TPO).

Specifically, in this example, the molar ratio of bromobutane to vinylimidazole is from 2: 1 to 1: 1; preferably 1: 1. Considering the reaction ratio, conversion rate and dosage of the two and the subsequent cleaning treatment process, the molar ratio of the bromobutane to the vinyl imidazole is 1: 1.

Preferably, in this example, in step (a), to ensure completion of the reaction, the mass of acrylonitrile is greater than or equal to the sum of the masses of bromobutane and vinylimidazole. Considering the reaction ratio, the conversion rate, the dosage of the three and the subsequent cleaning treatment process, the mass of the acrylonitrile is the sum of the mass of the bromobutane and the mass of the vinyl imidazole.

Preferably, in step (b) of the process provided herein, the mass of the cross-linking agent is 8 wt% to 12 wt%, calculated on the total mass of the bromobutane, the vinylimidazole and the acrylonitrile, and may be, for example, 8 wt%, 9 wt%, 10 wt%, 12 wt%, etc. The mass of the initiator is 0.5 to 2 wt%, for example, 0.5, 1, 1.5, 2, etc. calculated on the total mass of bromobutane, vinylimidazole and acrylonitrile.

Specifically, in step (2) of the method provided in this example, the deposition solution can be prepared by the following steps:

(a) mixing bromobutane and vinyl imidazole in equal molar ratio, and carrying out ultrasonic treatment on the obtained mixed solution for 15min until the bromobutane and the vinyl imidazole are fully mixed; then adding acrylonitrile with the mass sum of the bromobutane and the vinyl imidazole equal to that of the bromobutane and the vinyl imidazole; if the surface of the mixed solution has floating impurities, the impurities can be removed through a suction pipe or a pipette;

(b) adding 8 wt% of N, N-Methylene Bisacrylamide (MBA) and 1.0 wt% of 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide (TPO) according to the total mass of the bromobutane, the vinylimidazole and the acrylonitrile, and carrying out ultrasonic treatment for 15min to obtain a membrane forming solution.

In step (a), the ultrasonic treatment may add an energy field to the mixed solution of bromobutane and vinylimidazole, thereby accelerating the reaction.

The method provided by the embodiment of the invention further comprises the step of immersing the obtained polyion film with the patterned surface in a dye solution with a dye to obtain the polyion film which can be used for pH detection.

The dye used above may be a dye commonly used in the art as long as it can be stably bonded to the film substrate and safety is secured. For example, the dye may be selected from one of Bromocresol Green (BG), Cresol Red (CR), Methyl Orange (MO). After the micromolecular dyes BG, CR or MO are exchanged with the film, the micromolecular dyes BG, CR or MO have responsiveness to pH values, present different molecular structures under different pH conditions, show different ultraviolet spectrum absorption peaks in a microscopic mode, and show different colors in a macroscopic mode.

Preferably, the dye solution is a solution of dye dissolved in a water-ethanol mixed solvent, wherein the volume ratio of water to ethanol in the water-ethanol mixed solvent is 4: 1-1: 8. For example, the ratio of water to ethanol is 4: 1, 2: 1, 1: 2, 1: 4, 1: 6, 1: 8.

Preferably, the concentration of the dye in the dye solution is 0.5-8 mg/ml. For example, the concentration of the dye is 0.5mg/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, 8.0 mg/ml. Preferably, the concentration of the dye is 3.95 mg/ml.

Therefore, the present invention also provides a polyion film, which is obtained by the preparation method in the above embodiment.

Therefore, the invention also provides a detection kit, which comprises the polyion film obtained after the dye is impregnated.

In one embodiment of the preferred test kit of the present invention, the test kit comprises a color chart and the above polyion film. Through the change of the color of the polyion film, the pH value of the detected liquid can be quickly detected by contrasting a color comparison card which is manufactured in advance.

The following examples are provided to describe the preparation of polyion films and the specific applications of polyion films in detail.