CN115141410A - Porous polymer pressure-sensitive film, preparation method and application thereof - Google Patents
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Abstract
The invention discloses a porous polymer pressure-sensitive film, a preparation method and application thereof, wherein the porous polymer pressure-sensitive film is prepared from filling particles, ionic liquid, polymer and organic solvent, and holes are randomly distributed on the porous polymer pressure-sensitive film; the filling particles, the ionic liquid and the holes are uniformly dispersed in the polymer; the mass ratio of the polymer to the filler particles is 100:0.01 to 95; the mass ratio of the polymer to the ionic liquid is 100:0.5 to 150; the porosity of the pores in the polymer is the volume of the polymer: pore volume =100:5 to 300. The preparation method of the porous polymer pressure-sensitive film is characterized by preparing through solution synthesis, synthesizing a phase in situ, having simple method, good hydrophobic property and high contact efficiency of the conductive filler, keeping the ductility of the flexible pressure material and improving the sensitivity.
Description
Technical Field
The invention relates to the field of flexible piezoresistive materials, in particular to a porous polymer pressure-sensitive film, and a preparation method and application thereof.
Background
With the development of sensing technology, electronic equipment and artificial intelligence, the flexible pressure sensor as a novel electronic device has greater advantages than a rigid sensor in the application fields of human-computer interaction, medical health, robot touch and the like, but also puts more strict requirements on materials. For example, it requires that the material from which the device is constructed be thin, soft, and in some cases conformable to the skin surface of a human or implantable in the body, which further requires that the material be biocompatible and mechanically compatible with biological tissue. In terms of device performance, the design of the flexible pressure sensor mainly focuses on improving the performances such as sensitivity, response time, detection limit and stability. Recently, researchers have expanded the attention to the pressure response range, pressure resolution, spatial resolution, tensile property and the like of the device, so that the sensor has a wider application prospect.
The traditional flexible pressure sensor, such as a polymer conductive composite material, is an important sensitive material of a piezoresistive flexible pressure sensor, and such a material has a good piezoresistive response, but due to the limitation of the polymer material, the piezoresistive sensitive material has low sensitivity and cannot sense small pressure, such as wrist pulse vibration, sound vibration, and the like.
In order to improve the sensitivity of the sensor, a method for preparing microstructures on the surface of a polymer material and enabling the sensor to have piezoresistive properties by means of contact resistance between the microstructures is provided. For example, an etched silicon wafer or a blade with a microstructure is used as a mold, a flexible polymer material such as PDMS is coated on the mold, the mold is peeled off after being cured, a microstructure is formed on the polymer material, and then a conductive film such as a graphene layer is attached to the microstructure; or forming a microstructure on the surface of the smooth flexible polymer substrate by using a laser etching or ozone/ultraviolet etching method, and attaching a conductive film on the surface of the microstructure. Most of the sensors utilizing the principle of contact resistance change among the microstructures are complex in manufacturing process and small in measuring range.
All be non-porous structure above, lead to under the pressure effect, the contact efficiency of electrically conductive filler is not high, makes it unable scene demand that satisfies high accuracy perception pressure, and non-porous structure's hydrophobic performance is relatively poor for porous structure simultaneously, is difficult to satisfy high humid environment's application demand.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a porous polymer pressure-sensitive film, a preparation method and application thereof, and solves the problems of low sensitivity, low contact efficiency of conductive filler, low pressure-sensitive performance, poor hydrophobic effect and the like of the traditional flexible pressure sensing material at present.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention provides a porous polymer pressure-sensitive film, which is prepared from filling particles, ionic liquid, polymer and organic solvent, wherein holes are randomly distributed on the porous polymer pressure-sensitive film; the filling particles, the ionic liquid and the holes are uniformly dispersed in the polymer; the mass ratio of the polymer to the filler particles is 100:0.01 to 95; the mass ratio of the polymer to the ionic liquid is 100:0.5 to 150; the porosity of the pores in the polymer is the volume of the polymer: pore volume =100:5 to 300.
Further, the filling particles are selected from any one or a combination of more than two of carbon nano tubes, graphene, graphite, silver particles, gold particles, zinc oxide particles, copper particles, aluminum particles, carbon black or coal.
Further, the size of the filler particles is in the range of 10nm to 1000 μm in at least one dimension.
Further, the polymer is any one or combination of more than two of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer P, polyvinyl acetate, cellulose acetate, polysulfone, aromatic Polyamide (PA), polyimide, polyacrylonitrile, polycarbonate, polystyrene, polyurethane, ethylene propylene diene monomer, polymethyl methacrylate and polyethylene.
Further, the chemical structural formula of the ionic liquid is LT, wherein the cation L + Is Li + 、Na + 、K + 、Rb + 、Cs + Ion, at least one of formula (I) to formula (XIX), an anion T - Is F - 、Cl - 、Br - 、I - At least one of ion, formula (XX) to formula (XXIX); the formulae (I) to (XXIX) are:
wherein R1, R2, R3, R4 and R5 are general formula C n H 2n+1 (20. Gtoreq.n.gtoreq.1) saturated alkyl group, or general formula C n H 2n-1 Unsaturated alkyl groups (20 is more than or equal to n and more than or equal to 2), or aromatic groups, or H atoms; r6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R25, R26, R27, R28, R29, R30, R31, R33 are of the formula C n H 2n+1 Saturated alkyl group (20. Gtoreq. N.gtoreq.1), or general formula C n H 2n-1 Is an unsaturated alkyl group (20 is more than or equal to n and more than or equal to 2), or is an aromatic group, or is an H atom, or is C n H 2n NH 3 Saturated alkylamine halogen salt of X (20 is more than or equal to n is more than or equal to 1, X is any one of Cl, br and I), or is C n H 2n-2 NH 3 Unsaturated alkylamine halogen salt of X (20 is more than or equal to n is more than or equal to 2, X is any one of Cl, br and I), or is C n H 2n NH 2 Saturated alkylamine (20 is more than or equal to n is more than or equal to 1) or is represented by the general formula C n H 2n-2 NH 2 Unsaturated alkylamine (20 is more than or equal to n is more than or equal to 2) or has a general formula of C n+m H 2m F 2n+1 Saturated fluorine-containing terminal alkyl group (20 ≥n is more than or equal to 0, and m is more than or equal to 20 and more than or equal to 1); or is of the general formula C n H 2n COOC m H 2m+1 The saturated carboxyl-containing group (n is more than or equal to 20 and more than or equal to 0, m is more than or equal to 20 and more than or equal to 0); or is of the general formula C n H 2n SO 3 Saturated sulfo group of H (20 is more than or equal to n and more than or equal to 0); r23, R24, R32 are of the formula C n H 2n Saturated alkyl groups (20. Gtoreq. N.gtoreq.1), or formula C n H 2n-1 Unsaturated alkyl group (20 is more than or equal to n and more than or equal to 2); n is more than or equal to 1 when 20 in the molecular formulas XII and XIII are more than or equal to 1;
the formulae (XX) to (XXIX) are:
wherein R34, R35, R36, R37 are of the general formula C n H 2n+1 Saturated alkyl group (20 is more than or equal to n and more than or equal to 1) or general formula C n H 2n-1 Is an unsaturated alkyl group (20 is more than or equal to n and more than or equal to 2), or is an aromatic group, or is an H atom, or is C n H 2n NH 3 Saturated alkylamine halogen salt of X (20 is more than or equal to n is more than or equal to 1, X is any one of Cl, br and I), or is C n H 2n-2 NH 3 Unsaturated alkylamine halogen salt of X (20 is more than or equal to n is more than or equal to 2, X is any one of Cl, br and I), or is C n H 2n NH 2 Saturated alkylamine (20 is more than or equal to n and more than or equal to 1) or the general formula C n H 2n-2 NH 2 Unsaturated alkylamine (20 is more than or equal to n is more than or equal to 2) or is represented by the general formula C n+m H 2m F 2n+1 The saturated fluorine-containing end group alkyl group (n is more than or equal to 20 and is more than or equal to 0, and m is more than or equal to 20 and is more than or equal to 0).
Further, the ionic liquid is 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-vinylimidazole bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylimidazole hydrogensulfate, 1-butyl-3-methylimidazole methanesulfonate, 1-butyl-3-methylimidazole chloride salt, triethylsulfonium bis (trifluoromethanesulfonyl) imide, tributylmethylphosphonium bis (trifluoromethanesulfonyl) imide, tetrapentylammonium iodide, 1-methylimidazole trifluoromethanesulfonate, 1-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, 1-methyl-3- (4-sulfobutyl) imidazolium bis (trifluoromethanesulfonyl) imide, 1-methyl-3-propylimidazolium bromide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-3-n-octylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium tetrachloroferrate, 1-ethyl-3-methylimidazolium dicyanamide salt, (fluorosulfonyl) (trifluoromethanesulfonyl) lithium imide, (fluorosulfonyl) (trifluoromethanesulfonyl) imino potassium, bistrifluoromethanesulfonylimide, lithium bis (pentafluoroethanesulfonyl) imide salt, or lithium bis (pentafluoroethanesulfonyl) imide salt.
Further, the contact angle of the porous polymer pressure-sensitive film and water is 50-175 degrees; the resistivity of the porous polymer pressure-sensitive film is 1 x 10 -6 Ohm meter (omega. M) -1X 10 8 Ohm meter (omega. M), the stretching rate of the porous polymer pressure-sensitive film is 0.01-3000%, and the size of the holes in the porous polymer pressure-sensitive film is 50 nm-0.5 mm in at least one dimension.
It is another object of the present invention to provide a method for preparing a porous polymeric pressure sensitive film, comprising the steps of:
s1: dissolving a polymer in an organic solvent, wherein the mass ratio of the polymer to the organic solvent is 1: 1-50, stirring for 1-48 hours by ultrasonic or magnetic force to completely dissolve the polymer to obtain a uniform and clear polymer solution, adding ionic liquid into the polymer solution, and adding the following components in percentage by mass: ionic liquid =100: 0.5-150, stirring for 30 minutes-48 hours by ultrasonic or magnetic force, and mixing uniformly to obtain a solution H;
s2: uniformly mixing the filling particles with an organic solvent, wherein the mass ratio of the filling particles to the organic solvent is 1: 1-100, and carrying out ultrasonic or magnetic stirring treatment for 15 minutes after mixing to obtain a mixed solution K;
s3: mixing the solution H obtained in the step S1 and the solution K obtained in the step S2, and controlling the volume ratio of the solution H: filtrate K =1: (0.01-10), mixing for 1 minute to 24 hours at the temperature of 15 ℃ to 150 ℃ by ultrasonic or magnetic force, and obtaining a precursor solution L after uniform mixing;
s4: transferring the precursor solution L in the third step into a substrate or a mold through a spin coating method, a blade coating method, an electrostatic spinning method, a dip-coating method, a spraying method, an ultrasonic spraying method, a solution sinking method or a casting method, uniformly dispersing the precursor solution L in the substrate or the mold, controlling the thickness of the precursor solution L in the substrate or the mold to be 100 nm-6 cm, then placing the substrate or the mold coated with the precursor solution L on a vacuum drying oven or a heating table, controlling the air pressure of the vacuum drying oven to be 0.001-0.2 MPa and the temperature to be 30-120 ℃, drying for 0.1-60 hours, and removing the organic solvent to obtain the porous polymer pressure-sensitive film; if the porous polymer pressure-sensitive film is placed on a heating hot table, the temperature of the hot table is between 30 and 120 ℃, the drying is carried out for 0.1 to 60 hours, and the organic solvent is removed, thus obtaining the porous polymer pressure-sensitive film.
Further, the organic solvent is one or a combination of more than two of trimethyl phosphate, triethyl phosphate, N-dimethylformamide, dimethyl sulfoxide, butyrolactone, tetrahydrofuran, toluene, N-methylpyrrolidone, ethanol, methanol, isopropanol, acetonitrile or dimethylacetamide.
A third object of the present invention is to provide a use of a porous polymer pressure sensitive film as a flexible piezoresistive material, the strain sensor is applied to piezoresistive pressure sensors, stress sensors, strain sensors, touch sensors, array pressure sensors, array stress sensors and array strain sensors.
The invention has the beneficial effects that:
1. according to the porous polymer pressure-sensitive film, due to the interaction between the ionic liquid and the polymer, and in the solvent volatilization process, the crystallization behavior is not uniform, so that holes are generated. Compared with the non-porous pressure-sensitive performance, the porous pressure-sensitive performance is superior to the non-porous pressure-sensitive performance, the existence of the pores endows the material with new performance, the ductility of the flexible pressure material is increased, the hydrophobicity is increased, and the sensitivity is improved at the same time, the sensitivity range of the invention is 20-3000 omega.N according to the difference of the film thickness, and the pressure induction range is as follows: 0.01Pa to 1000GPa;
2. the preparation method of the porous polymer pressure-sensitive film is prepared by solution synthesis, can synthesize a phase in situ, and is simple.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a porous polymeric pressure sensitive film of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a porous polymeric pressure sensitive film of example 1;
FIG. 3 is a schematic representation of the pressure sensitive properties of the apertured polymeric pressure sensitive film of example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a non-porous polymeric pressure sensitive film of comparative example 1;
FIG. 5 is a schematic representation of the pressure sensitive properties of a non-porous polymeric pressure sensitive film of comparative example 1;
FIG. 6 is a schematic contact angle diagram of a porous polymeric pressure sensitive film of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention is prepared by solution synthesis, and the problems of low sensitivity, low contact efficiency of conductive filler, low pressure-sensitive performance, poor hydrophobic effect and the like of the traditional flexible pressure sensing material are solved by in-situ synthesis.
Example 1
As shown in fig. 1 to 3 and 6, a porous polymer pressure-sensitive film is prepared by dissolving a polymer in an organic solvent, wherein the mass ratio of the polymer to the organic solvent is as follows: organic solvent =1: and 6, magnetically stirring for 3 hours, obtaining a polymer solution after the polymer is completely dissolved, and then adding ionic liquid into the polymer solution, wherein the mass ratio of the polymer to the ionic liquid is as follows: polymer (b): ionic liquid =100: and 10, magnetically stirring for 2 hours, and uniformly mixing to obtain a solution as a first solution. The polymer is: thermoplastic polyurethane elastomer rubber (TPU); the organic solvent is: n, N-Dimethylformamide (DMF); the ionic liquid is as follows: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt.
Adding the filling particles into an organic solvent, wherein the mass ratio of the added organic solvent is as follows: filler particles =1:0.01, uniformly stirring by magnetic force after mixing to obtain a mixed solution, and then taking the solution subjected to ultrasonic treatment as a second solution. The filled carbon nanotube particles in this step have the following dimensions: length 10 microns, diameter 500 nanometers; the organic solvent is: n, N-Dimethylformamide (DMF).
Mixing the first solution and the second solution according to the volume ratio: a first solution: second solution =1:0.01, and magnetically stirring for 3 hours at the temperature of 60 ℃ to obtain a precursor solution which is uniformly mixed.
Spin-coating the precursor solution obtained in the step 3 on a transparent glass sheet by a spin-coating method to realize uniform dispersion, controlling the thickness of the precursor solution on the transparent glass sheet to be 250 micrometers, then putting the transparent glass sheet coated with the precursor solution into a vacuum drying oven, controlling the atmospheric pressure in the vacuum drying oven to be 0.01MPa, controlling the temperature to be 35 ℃, carrying out vacuum drying, drying for 2 hours, removing an organic solvent N, N-Dimethylformamide (DMF), and obtaining a porous polymer pressure-sensitive film which can be torn off from the glass sheet; in order to measure the piezoresistive performance, conductive silver paste with the thickness of 100 microns is uniformly coated on the upper side and the lower side of the film to form electrodes, then pressure with different magnitudes is applied, the resistance change of the film is measured by a universal meter, and the performance of the film is shown in figure 1; the stretching ratio of the porous polymer pressure-sensitive film is 150 percent; as shown in FIG. 3The contact angle of the porous polymer pressure sensitive film with water is 146 degrees; as shown in the Scanning Electron Microscope (SEM) picture of the film of FIG. 2, the pores in the porous polymer pressure-sensitive film have a size of 500 nm. + -. 100nm and are randomly and uniformly distributed; porosity is the volume of the polymeric thermoplastic polyurethane elastomer rubber (TPU): pore volume =100:30, of a nitrogen-containing gas; resistivity of 1.4X 10 5 Ohm meter (Ω · m).
Example 2
Dissolving a polymer in an organic solvent, wherein the mass ratio of the polymer to the organic solvent is as follows: organic solvent =1:10, magnetically stirring for 3 hours, obtaining a polymer solution after the polymer is completely dissolved, and then adding ionic liquid into the polymer solution, wherein the mass ratio of the polymer to the ionic liquid is as follows: polymer (b): ionic liquid =10:1, stirring by magnetic force for 2 hours, and uniformly mixing to obtain a solution as a first solution. The polymer comprises the following steps: polyvinyl acetate (PVAc); the organic solvent is: trimethyl phosphate (TMP); the ionic liquid is as follows: 1-vinylimidazole bis (trifluoromethanesulfonyl) imide.
Adding the filling particles into an organic solvent, wherein the mass ratio of the organic solvent is as follows: filler particles =1:0.01, uniformly stirring by magnetic force after mixing to obtain a mixed solution, and then taking the solution subjected to ultrasonic treatment as a second solution. The filled carbon nanotubes in this step have the following dimensions: length 10 microns, diameter 500 nanometers; the organic solvent is: trimethyl phosphate (TMP).
Mixing the first solution and the second solution according to the volume ratio: a first solution: second solution =1:0.1, magnetically stirring for 3 hours at the temperature of 60 ℃ to obtain a precursor solution which is uniformly mixed.
Spin-coating the precursor solution on a transparent glass sheet by a spin-coating method to realize uniform dispersion, controlling the thickness of the precursor solution on the transparent glass sheet to be 250 micrometers, then putting the transparent glass sheet coated with the precursor solution into a vacuum drying oven, controlling the atmospheric pressure in the vacuum drying oven to be 0.01MPa and the temperature to be 35 ℃, carrying out vacuum drying, removing an organic solvent trimethyl phosphate (TMP) after drying for 2 hours to obtain a porous polymer pressure-sensitive film, wherein the film can be a porous polymer pressure-sensitive filmTearing off the glass sheet; in order to measure the piezoresistive performance of the film, conductive silver paste with the thickness of 100 microns is uniformly coated on the upper side and the lower side of the film to form electrodes, then different pressures are applied, the resistance change of the film is measured by a universal meter, the stretching rate of the porous polymer pressure-sensitive film is 160%, and the contact angle between the porous polymer pressure-sensitive film and water is 140 degrees; the size of pores in the porous polymer pressure-sensitive film is 520nm +/-100 nm and is randomly and uniformly distributed; porosity is polyvinyl acetate (PVAc) volume: pore volume =100:35; resistivity of 1.2X 10 4 Ohm meter (Ω · m).
Comparative example 1
For comparison, we prepared a non-porous polymer pressure-sensitive film, which has the same process flow as the above-mentioned porous polymer pressure-sensitive film, and the scanning electron microscope image thereof is shown in fig. 4, except that no ionic liquid is added: 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt.
The pores are generated as a result of the interaction of the ionic liquid and the polymer, and during the solvent evaporation, the crystallization behavior is not uniform, resulting in the formation of pores. The non-porous polymer pressure-sensitive film has no holes and no similar lotus leaf hydrophobic effect, and has a contact angle of 76 DEG and a resistivity of 9 x 10 4 Ohm meter (. Omega. M), elongation 75%.
From a comparison of the pressure sensitive properties of fig. 3 and 5, it is clear that the porous pressure sensitive properties (fig. 3) are superior to the non-porous pressure sensitive properties (fig. 5) over the same pressure range, the results of fig. 3 showing a sensitivity of 2000 ohms/newton for the porous polymer pressure sensitive film and the results of fig. 5 showing a sensitivity of 1000 ohms/newton for the non-porous polymer pressure sensitive film.
The ionic liquid is mainly added to enable the synthesized film to have a porous structure, and the existence of the pores leads to the improvement of pressure-sensitive performance, extensibility and hydrophobic performance. The sensitivity range of the invention is 20-3000 omega.N according to the film thickness, the lowest pressure is sensed to be 0.01Pa, the induction range is as follows: 0.01Pa to 1000GPa. The presence of the pores in the polymeric pressure sensitive material of the present invention imparts new properties over the non-porous material of comparative example 1, increased ductility and sensitivity, and increased hydrophobicity.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A porous polymer pressure-sensitive film is characterized by being prepared from filling particles, ionic liquid, polymer and organic solvent, wherein holes are randomly distributed on the filling particles; the filling particles, the ionic liquid and the holes are uniformly dispersed in the polymer; the mass ratio of the polymer to the filler particles is 100:0.01 to 95; the mass ratio of the polymer to the ionic liquid is 100:0.5 to 150; the porosity of the pores in the polymer is the volume of the polymer: pore volume =100:5 to 300.
2. The porous polymer pressure-sensitive film according to claim 1, wherein the filler particles are selected from one or more of carbon nanotubes, graphene, graphite, silver particles, gold particles, zinc oxide particles, copper particles, aluminum particles, carbon black, and coal.
3. A porous polymeric pressure sensitive film according to claim 1, wherein said filler particles have a size in the range of 10nm to 1000 μm in at least one dimension.
4. A porous polymeric pressure sensitive film according to claim 1, wherein: the polymer is any one or the combination of more than two of polyvinylidene fluoride, polyvinylidene fluoride and trifluoroethylene copolymer P, polyvinyl acetate, cellulose acetate, polysulfone, aromatic Polyamide (PA), polyimide, polyacrylonitrile, polycarbonate, polystyrene, polyurethane, ethylene propylene diene monomer, polymethyl methacrylate and polyethylene.
5. The porous polymeric pressure sensitive sheet of claim 1The membrane is characterized in that the chemical structural formula of the ionic liquid is LT, wherein the cation L + Is Li + 、Na + 、K + 、Rb + 、Cs + Ion, at least one of formula (I) to formula (XIX), an anion T - Is F - 、Cl - 、Br - 、I - At least one of ion, formula (XX) to formula (XXIX); the formulae (I) to (XXIX) are:
wherein R1, R2, R3, R4 and R5 are general formula C n H 2n+1 20 is more than or equal to n and more than or equal to 1, or has a general formula of C n H 2n-1 20 is more than or equal to n and more than or equal to 2, or is an aromatic group or is an H atom; r6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R25, R26, R27, R28, R29, R30, R31, R33 are of the formula C n H 2n+1 20 is more than or equal to n and more than or equal to 1, or the general formula is C n H 2n-1 20 is more than or equal to n and more than or equal to 2, or is an aromatic group, or is an H atom, or is represented by the general formula C n H 2n NH 3 X is 20-1, X is any one of Cl, br and I, or is C n H 2n-2 NH 3 The unsaturated alkylamine halogen salt of X is more than or equal to 20 and n is more than or equal to 2, X is any one of Cl, br and I, or is C n H 2n NH 2 20 is more than or equal to n and more than or equal to 1, or is represented by the general formula C n H 2n-2 NH 2 Unsaturated alkylamine, 20 is more than or equal to n is more than or equal to 2, or is represented by the general formula C n+m H 2m F 2n+1 N is more than or equal to 20 and is more than or equal to 0, and m is more than or equal to 20 and is more than or equal to 1; or is of the general formula C n H 2n COOC m H 2m+1 The saturated carboxyl-containing group is more than or equal to 20 and more than or equal to n and more than or equal to 0, and m is more than or equal to 20 and more than or equal to 0; or is of the general formula C n H 2n SO 3 N is more than or equal to 20 and more than or equal to 0 in saturated sulfo groups of H; r23, R24, R32 are of the formula C n H 2n 20. Gtoreq.n.gtoreq.1, or of the general formula C n H 2n-1 20 is more than or equal to n and more than or equal to 2; n is more than or equal to 1 when 20 in the molecular formulas XII and XIII are more than or equal to 1;
the formulae (XX) to (XXIX) are:
wherein R34, R35, R36, R37 are of the general formula C n H 2n+1 20 is more than or equal to n and more than or equal to 1, or the general formula is C n H 2n-1 20 is more than or equal to n and more than or equal to 2, or is an aromatic group, or is an H atom, or is represented by the general formula C n H 2n NH 3 X is 20 or more and n is more than or equal to 1, X is any one of Cl, br and I, or is C n H 2n-2 NH 3 The unsaturated alkylamine halogen salt of X is more than or equal to 20 and n is more than or equal to 2, X is any one of Cl, br and I, or is C n H 2n NH 2 20 is more than or equal to n and more than or equal to 1, or is represented by the general formula C n H 2n-2 NH 2 20 is more than or equal to n is more than or equal to 2, or is represented by the general formula C n+m H 2m F 2n+1 The saturated fluorine-containing terminal alkyl group is more than or equal to 20 and more than or equal to 0, and more than or equal to 20 and more than or equal to 0.
6. The porous polymeric pressure sensitive film of claim 1, wherein: the ionic liquid is 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-vinylimidazole bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylimidazole hydrogen sulfate, 1-butyl-3-methylimidazole methanesulfonate, 1-butyl-3-methylimidazole chloride salt, triethylsulfonium bis (trifluoromethanesulfonyl) imide, tributylmethylphosphonium bis (trifluoromethanesulfonyl) imide, tetrapentyl ammonium iodide, 1-methylimidazole trifluoromethanesulfonate, 1-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, 1-methyl-3- (4-sulfobutyl) imidazolium bis (trifluoromethanesulfonyl) imide, 1-methyl-3-propylimidazolium bromide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-3-n-octylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium tetrachloroferrate, 1-ethyl-3-methylimidazolium dicyanamide salt, (fluorosulfonyl) (trifluoromethanesulfonyl) lithium imide, (fluorosulfonyl) (trifluoromethanesulfonyl) imino potassium, bistrifluoromethanesulfonylimide, lithium bis (pentafluoroethanesulfonyl) imide salt, or lithium bis (pentafluoroethanesulfonyl) imide salt.
7. A porous polymeric pressure sensitive film according to claim 1, wherein the porous polymeric pressure sensitive film has a contact angle with water of 100 ° to 175 °; the resistivity of the porous polymer pressure-sensitive film is 1 x 10 2 Ω·m～1×10 8 Omega m, the stretching ratio of the porous polymer pressure-sensitive film is 80-3000%, the sensitivity range of the pressure-sensitive film is 20-3000 omega N, and the size of the pore in the porous polymer pressure-sensitive film is 50 nm-0.5 mm in at least one dimension.
8. A method of making a porous polymeric pressure sensitive film according to claim 1, comprising the steps of:
s1: weighing the components according to the mass ratio, dissolving a polymer in an organic solvent, wherein the mass ratio of the polymer to the organic solvent is 1: 1-50, stirring to completely dissolve the polymer to obtain a uniform and clear polymer solution; adding an ionic liquid into a polymer solution, wherein the mass ratio of the polymer to the ionic liquid is 100: 0.5-150, stirring and mixing uniformly to obtain solution H;
s2: uniformly mixing filling particles and an organic solvent, wherein the mass ratio of the filling particles to the organic solvent is 1: 1-100, mixing and uniformly stirring to obtain a solution K;
s3: mixing the solution H of the step S1 and the solution K of the step S2, wherein the ratio of the solution H: the mixing volume ratio of the filtrate K is 1:0.01 to 10, and obtaining a precursor solution L after uniform mixing;
s4: and (4) transferring the precursor solution L in the step (S3) into a substrate or a mold, uniformly dispersing the precursor solution L in the substrate or the mold, wherein the thickness of the precursor solution L in the substrate or the mold is 100 nm-6 cm, and then removing the organic solvent from the substrate or the mold coated with the precursor solution L to obtain the porous polymer pressure-sensitive film.
9. The method as claimed in claim 8, wherein the organic solvent is one or more selected from the group consisting of trimethylphosphate, triethylphosphate, N-dimethylformamide, dimethylsulfoxide, butyrolactone, tetrahydrofuran, toluene, N-methylpyrrolidone, ethanol, methanol, isopropanol, acetonitrile and dimethylacetamide.
10. Use of a porous polymeric pressure sensitive film according to claim 1 as a flexible piezoresistive material in piezoresistive pressure sensors, stress sensors, strain sensors, tactile sensors, array pressure sensors, array stress sensors, array strain sensors.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070181856A1 (en) * | 2006-02-06 | 2007-08-09 | Jong-Jin Park | Conductive wet coating composition and thin-film prepared therefrom |
| CN103151113A (en) * | 2013-01-31 | 2013-06-12 | 中国科学院化学研究所 | Preparation method of pressure-sensitive conductive membrane |
| CN109785995A (en) * | 2018-12-07 | 2019-05-21 | 深圳大学 | A kind of porous, electrically conductive slurry and its preparation method and application being used to prepare flexible piezoresistive transducer |
| CN113308109A (en) * | 2021-05-21 | 2021-08-27 | 江苏烨湫传感科技有限公司 | Flexible perovskite quantum dot polymer film and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070181856A1 (en) * | 2006-02-06 | 2007-08-09 | Jong-Jin Park | Conductive wet coating composition and thin-film prepared therefrom |
| CN103151113A (en) * | 2013-01-31 | 2013-06-12 | 中国科学院化学研究所 | Preparation method of pressure-sensitive conductive membrane |
| CN109785995A (en) * | 2018-12-07 | 2019-05-21 | 深圳大学 | A kind of porous, electrically conductive slurry and its preparation method and application being used to prepare flexible piezoresistive transducer |
| CN113308109A (en) * | 2021-05-21 | 2021-08-27 | 江苏烨湫传感科技有限公司 | Flexible perovskite quantum dot polymer film and preparation method and application thereof |
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