CN112932412B - Self-adhesion electronic skin based on multiple reversible bonding effect and preparation method and application thereof - Google Patents
Self-adhesion electronic skin based on multiple reversible bonding effect and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses self-adhesive electronic skin based on multiple reversible bonding, and a preparation method and application thereof. The method comprises the following steps: dissolving formylphenylboric acid, polyhydroxy benzaldehyde and amino-terminated prepolymer in an organic solvent, reacting at room temperature to 90 ℃ for 30 min-72 h, adding metal salt for coordination, pouring the obtained polymer solution on a conductive layer, and removing the solvent to obtain a polymer elastomer; and connecting flexible electrodes at two ends of the conductive layer to obtain the self-adhesive electronic skin. The electronic skin obtained by the invention has high conductivity and high responsiveness to various deformations of human bodies, and has wide application prospects in the fields of flexible wearable equipment, flexible patch electrodes, intelligent robots, health monitoring and the like.
Description
Technical Field
The invention belongs to the field of wearable strain sensors, and particularly relates to self-adhesion electronic skin based on multiple reversible bond actions, and a preparation method and application thereof.
Background
The electronic skin is a flexible electronic sensing material which can be directly attached to the surface of the skin and record the health condition of a human body in real time by collecting the change of various health indexes of the human body. Compared with the traditional hospital-type health examination, the electronic skin can meet the requirement that a user monitors and records physiological health information anytime and anywhere, avoids the complicated medical procedure of a hospital, has the advantages of convenience, high efficiency, comfort and the like, and has important research value and application prospect in the fields of future health monitoring, remote nursing, human-computer interaction, portable wearable equipment and the like. In recent years, the development of high-sensitivity electronic skin has been the focus of attention of researchers. However, because the surface structure of the human skin as the detection object is complex, deformation (such as heart beat and pulse) of certain parts is weak, the problems of weak output signal, high noise and the like often exist in the practical wearing application of the high-sensitivity electronic skin, and therefore, the interface action between the electrons and the skin has higher requirements. The premise of capturing pulse signals is the transmission of force and deformation to the electronic skin, which requires high adhesion (surface roughness ratio is less than or equal to 50%), self adhesion (skin adhesion is more than or equal to 1 kPa) and later de-adhesion between the electronic skin material and the skin. However, most electronic skins cannot meet the requirement at present, and the attachment and fixation of the electronic skins still need to be realized by means of glue. In addition, considering the complexity of the human activity environment, besides the use of the conventional environment, the adhesion and the de-adhesion of the human body during perspiration and under water are required to be simultaneously considered, the prior reported adhesive electronic skin can only meet the use of a single scene, and can not meet the adhesion and the de-adhesion under the multiple scenes at the same time, so that the further application of the electronic skin is greatly limited. Therefore, the design of the electronic skin with multiple scenes (dry environment, high humidity environment and underwater environment) and self-adhesion and reversible adhesion release capabilities has important significance.
Disclosure of Invention
To solve the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a method for preparing self-adhesive electronic skin based on multiple reversible bonding.
It is another object of the present invention to provide a self-adhesive electronic skin based on multiple reversible bonding processes as prepared by the above process.
The self-adhesive elastomer electronic skin based on the multiple reversible bonding effect comprises three reversible bonding effects of reversible ring opening and cyclization of a boron-oxygen hexaring, reversible coordination of phenolic hydroxyl and metal ions and reversible reaction of phenylboronic acid and catechol, wherein the boron-oxygen hexaring structure can be subjected to reversible ring opening in the presence of a small amount of water, so that the modulus of the elastomer is reduced, the fluidity is increased, the integrity of the electronic skin in the state is ensured by the metal coordination effect, the skin surface of the elastomer can be secondarily shaped in the state, and the shaped elastomer can fully infiltrate the skin, namely the high fit of the electronic skin to the human skin is realized. By further removing the moisture, the boron-oxygen bond is re-bonded to form a six-ring structure, so that the modulus of the elastomer is increased, and the adhesion locking on the skin surface is realized. When water is applied to the bonding interface again, the adhesion and the stability of the electronic skin are maintained due to the existence of the phenolic hydroxyl and coordination action, so that the use of underwater and perspiration states is ensured; and under alkaline conditions, the bonding of the phenolic hydroxyl group and the phenylboronic acid can occur to realize the de-adhesion of the electronic skin. The problems existing in the existing electronic skin can be well solved by ingenious application of multiple reversible bonding actions.
It is a further object of the present invention to provide a self-adhesive electronic skin application based on multiple reversible bonding.
The invention aims at realizing the following technical scheme:
a preparation method of self-adhesive electronic skin based on multiple reversible bonding effect comprises the following steps:
(1) Uniformly mixing formylphenylboric acid, polyhydroxy benzaldehyde and amino-terminated prepolymer by taking an organic solvent as a reaction medium, reacting for 30 min-72 h at the temperature of room temperature to 90 ℃, and adding metal salt for coordination to obtain a polymer mixed solution;
(2) Depositing a conductive layer on a template substrate, pouring the polymer mixed solution in the step (1) on the conductive layer, and removing the solvent, wherein boron-oxygen bonds react with each other to generate covalent boron-oxygen hexacyclic rings, so as to obtain a polymer elastomer;
(3) And removing the template substrate to obtain a conductive self-adhesive elastomer with the surface coated with a conductive layer, and connecting flexible electrodes at two ends of the conductive layer to obtain the self-adhesive electronic skin based on multiple reversible bonding.
Preferably, the organic solvent in the step (1) is at least one of absolute ethanol, methanol, dimethylformamide, tetrahydrofuran and dichloromethane.
Preferably, the formylphenylboronic acid in the step (1) is at least one of 2-formylphenylboronic acid, 3-formylphenylboronic acid and 4-formylphenylboronic acid.
Preferably, the polyhydroxybenzaldehyde in the step (1) is at least one of 2, 3-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2,3, 4-trihydroxybenzaldehyde and 3,4, 5-trihydroxybenzaldehyde.
Preferably, the amino-terminated prepolymer in the step (1) is at least one of amino-terminated polysiloxane, amino-terminated polyurethane and amino-terminated polyethylene glycol.
Preferably, the weight average molecular weight of the amino terminated prepolymer in the step (1) is 2000 to 12000.
Preferably, the molar ratio of formylphenylboronic acid to polyhydroxy benzaldehyde in step (1) is 1: 5-5: 1, the molar ratio of the total mole number of formylphenylboronic acid to polyhydroxy benzaldehyde to the mole number of the amino terminated prepolymer is 2:1 to 2.2:1, wherein the molar ratio of the metal salt to the polyhydroxy benzaldehyde is 1: 3-1: 2.
preferably, the molar ratio of the formylphenylboronic acid to the organic solvent in the step (1) is 1:30 to 100.
Preferably, the metal salt in the step (1) is at least one of ferric chloride, vanadium chloride, aluminum chloride, magnesium chloride, zinc chloride and calcium chloride.
Preferably, the template substrate in the step (2) is at least one of a glass substrate, a silicon substrate, a polytetrafluoroethylene substrate and a polyimide substrate.
Preferably, before the depositing in the step (2), a release agent or a sacrificial layer may be deposited on the surface of the template substrate in advance in order to facilitate the release of the cured elastomer.
Preferably, the deposition mode of the conductive layer in the step (2) is at least one of evaporation, magnetron sputtering, chemical vapor deposition, spraying, spin coating, printing and in-situ growth.
Preferably, the conductive layer material in the step (2) is at least one of a metal material, a metal oxide material, a carbon material and a conductive polymer material; more preferably at least one of polypyrrole, nanogold, indium tin oxide, graphene, nano silver, carbon nanotube and silver nanowire.
Preferably, the thickness of the conductive layer in the step (2) is 0.1-100 μm, and the thickness of the polymer elastomer layer obtained by casting is 100-2000 μm.
Preferably, the method for removing the solvent in the step (2) is natural volatilization or heating volatilization, and the temperature of the heating volatilization is 35-90 ℃.
Preferably, the flexible electrode in the step (3) is a conductive composite material with certain flexibility, and more preferably an organosilicon system conductive silver paste and/or a polyurethane system conductive silver paste.
The self-adhesive electronic skin prepared by the method is based on multiple reversible bonding.
The application of the self-adhesive electronic skin based on the multiple reversible bonding effect in the fields of flexible wearable equipment, flexible patch electrodes and intelligent robots.
When the electronic skin is actually attached to human skin, a certain amount of water is applied to the surface of the human skin in advance to moisten the skin, then the electronic skin is attached to the surface of the human skin, at the moment, the boron-oxygen hexaring is opened under the action of the water, the viscosity of an elastomer system is reduced, the shaping capability is obtained, a metal coordination bond is still stable under the action of the water, the whole electronic skin maintains the shape, the elastomer is further applied under the pressure to conform to the fold change of the surface of the skin so as to fully infiltrate the surface of the human skin, after the moisture is completely volatilized under the dual actions of the pressure and the human body temperature, the boron-oxygen hexaring is regenerated, the elastomer structure returns to high strength, and the electronic skin can be firmly adhered to the surface of the human skin.
When the electronic skin obtained by the invention is used in a dry environment, the elastomer is bonded by physical infiltration; when the adhesive is used under water, the boron-oxygen bond is opened, the overall modulus of the elastomer is reduced, and the phenolic hydroxyl of the elastomer is bonded.
The electronic skin provided by the invention has self-repairing and repeatable shaping capabilities besides adhesiveness.
Compared with the prior art, the invention has the following advantages:
1) The electronic skin can support adhesion of the skin surface in various states such as dryness, wetness, underwater, perspiration and the like.
2) The electronic skin can realize free adhesion under mild conditions.
3) The electronic skin prepared by the invention has self-repairing and repeatable shaping capabilities.
Drawings
FIG. 1 is a schematic diagram showing reversible ring opening of a boroxine structure.
FIG. 2 is a schematic diagram showing reversible coordination of catechol structure with metal ions.
FIG. 3 is a schematic diagram showing the reversible reaction of catechol with phenylboronic acid.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The specific conditions are not noted in the examples of the present invention, and are carried out according to conventional conditions or conditions suggested by the manufacturer. The raw materials, reagents, etc. used, which are not noted to the manufacturer, are conventional products commercially available.
Example 1
1) Dissolving 2-formylphenylboric acid, 2, 3-dihydroxybenzaldehyde and aminopropyl polysiloxane (weight average molecular weight 2000) in absolute ethyl alcohol (the molar ratio of 2-formylphenylboric acid to absolute ethyl alcohol is 1:50) according to the molar ratio of 5:1:3, fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding metal salt ferric chloride with the molar ratio of 2, 3-dihydroxybenzaldehyde to carry out complexation to obtain a polymer mixed solution;
2) Depositing a layer of 10 mu m silver nanowire conducting network on a polytetrafluoroethylene template substrate in advance by adopting a spraying mode, pouring the obtained polymer mixed solution on the silver nanowire, and then placing the silver nanowire into a vacuum oven at 45 ℃ to fully volatilize ethanol to generate a polysiloxane elastomer with the thickness of 1000 mu m;
3) Tearing off the completely cured polysiloxane elastomer (the solvent is completely volatilized, namely, completely cured) together with the following silver nanowires, namely, removing a template substrate to obtain a surface-coated silver nanowire conductive self-adhesive elastomer, and connecting organic silicon system conductive silver paste at two ends of a silver nanowire conductive layer to serve as a flexible electrode to obtain the required self-adhesive electronic skin;
4) Electrons prepared by the methodThe skin can be subjected to surface softening on the surface of moist skin, and can be tightly adhered to the skin of a human body after the moisture is completely volatilized, and the adhesive strength (25+/-2) kPa; the initial conductivity of the electronic skin obtained by compounding the silver nano wire can reach 5-10 4 S cm -1 About, the tensile rate of 150% at maximum can be born, and the sensitivity is more than 110 (150%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 2
1) Dissolving 3-formylphenylboric acid, 3, 4-dihydroxybenzaldehyde and amine-terminated propyl polysiloxane (weight average molecular weight 2000) in dimethylformamide (wherein the molar ratio of 3-formylphenylboric acid to dimethylformamide is 1:30) according to a molar ratio of 1:1:1, fully mixing, reacting the mixed solution at 90 ℃ for 30min, and adding aluminum chloride as a metal salt with a molar ratio of 1:3 to 3 to obtain a polymer mixed solution;
2) Depositing a layer of 10 mu m graphene conductive network on a silicon substrate in advance by adopting a spin coating mode, pouring the obtained polymer mixed solution on graphene, and then placing the graphene mixed solution in a vacuum oven at 90 ℃ to fully volatilize dimethylformamide to generate a polysiloxane elastomer with the thickness of 1000 mu m;
3) Tearing the completely cured polysiloxane elastomer (namely completely cured solvent) together with the following graphene, namely removing a template substrate to obtain a conductive self-adhesive elastomer of the graphene coated on the surface, and connecting the two ends of a graphene conductive layer with organic silicon system conductive silver paste as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be subjected to surface softening on the surface of moist skin, and can realize tight adhesion strength (25+/-2) kPa with human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding graphene can reach 3-10 3 S cm -1 About, the maximum stretching rate of 50% can be born, and the sensitivity is more than 90 (50%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 3
1) 3-formylphenylboronic acid, 2,3, 4-trihydroxybenzaldehyde, and aminopropyl polysiloxane (weight average molecular weight 12000) were dissolved in methanol at a molar ratio of 1:5:3 (wherein the molar ratio of 3-formylphenylboronic acid to methanol was 1:80 Fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding metal salt vanadium chloride with the molar ratio of 2,3, 4-trihydroxybenzaldehyde being 1:3 for coordination to obtain a polymer mixed solution;
2) In order to facilitate demolding of the cured elastomer, depositing a layer of release agent on the surface of a polyimide template substrate in advance, and printing a layer of 50 mu m carbon nanotube conductive network on a silicon substrate in a screen printing mode; pouring the polymer mixed solution on a carbon nano tube, and then placing the carbon nano tube in a vacuum oven at 35 ℃ to fully volatilize methanol to generate a polysiloxane elastomer with the thickness of 1000 mu m;
3) Tearing off the polysiloxane elastomer after complete solidification (namely complete volatilization of the solvent) and the following carbon nano tubes, namely removing the template substrate to obtain a carbon nano tube conductive self-adhesive elastomer coated on the surface, and connecting the two ends of the carbon nano tube conductive layer with organic silicon system conductive silver paste as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be subjected to surface softening on the surface of moist skin, and can be tightly adhered to the skin of a human body after the moisture is completely volatilized, and the adhesive strength (55+/-5) kPa; the initial conductivity of the electronic skin obtained by the composite carbon nano tube can reach 5 to 10 3 S cm -1 About, the maximum stretching rate of 10% can be born, and the sensitivity is more than 40 (10%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 4
1) Dissolving 4-formylphenylboric acid, 3,4, 5-trihydroxybenzaldehyde and amine-terminated polyurethane (weight average molecular weight 8000) in tetrahydrofuran (the molar ratio of the 4-formylphenylboric acid to the tetrahydrofuran is 1:100) according to the molar ratio of 1.1:1.1:1, fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding magnesium chloride which is a metal salt with the molar ratio of 3,4, 5-trihydroxybenzaldehyde being 1:2 for coordination to obtain a polymer mixed solution;
2) In order to facilitate demolding of the cured elastomer, depositing a sacrificial layer on the surface of a polyimide substrate in advance, printing a 100 mu m nano silver conductive network on the polyimide substrate in a printing mode, pouring the obtained polymer mixed solution on nano silver, and then placing the nano silver mixed solution in a vacuum oven at 35 ℃ to fully volatilize tetrahydrofuran to generate a polyurethane elastomer with the thickness of 2000 mu m;
3) Tearing the polyurethane elastomer after complete solidification (namely complete volatilization of the solvent) and the nano silver below, namely removing the template substrate to obtain a nano silver conductive self-adhesive elastomer coated on the surface, and connecting conductive silver paste of a polyurethane system at two ends of a nano silver conductive layer to serve as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be subjected to surface softening on the surface of moist skin, and can realize tight adhesion strength (35+/-5) kPa with human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding nano silver can reach 6-10 4 S cm -1 About, the maximum stretching rate of 10% can be born, and the sensitivity is more than 380 (10%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 5
1) Dissolving 4-formylphenylboric acid, 3, 4-dihydroxybenzaldehyde and amine-terminated polyurethane (weight average molecular weight 2000) in methylene dichloride (the molar ratio of 4 formylphenylboric acid to methylene dichloride is 1:80) according to the molar ratio of 1.1:1.1:1, fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding zinc chloride metal salt with the molar ratio of 3, 4-dihydroxybenzaldehyde of 1:2 for coordination to obtain a polymer mixed solution;
2) Depositing a layer of 0.1 mu m graphene conductive network on a glass substrate in advance by adopting a chemical vapor deposition mode, pouring the obtained polymer mixed solution on graphene, and then placing the graphene mixed solution in a vacuum oven at 35 ℃ to fully volatilize dichloromethane to generate a polyurethane elastomer with the thickness of 100 mu m;
3) Tearing the polyurethane elastomer after complete solidification (namely complete volatilization of the solvent) and the following graphene together, namely removing the template substrate to obtain a graphene conductive self-adhesive elastomer coated on the surface, and connecting conductive silver paste of a polyurethane system at two ends of a graphene conductive layer to serve as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be subjected to surface softening on the surface of moist skin, and can realize tight adhesion strength (35+/-5) kPa with human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding graphene can reach 6-10 3 S cm -1 About, the maximum 5% stretching rate can be born, and the sensitivity is more than 330 (5%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 6
1) Dissolving 4-formylphenylboric acid, 3, 4-dihydroxybenzaldehyde, amino-terminated polyethylene glycol (weight average molecular weight 2000) and amino-terminated polysiloxane (weight average molecular weight 3000) in dimethylformamide (the molar ratio of 4-formylphenylboric acid to dimethylformamide is 1:80) according to the molar ratio of 1:1:0.5:0.5, fully mixing, reacting the mixed solution at 50 ℃ for 48 hours, and adding metal salt calcium chloride with the molar ratio of 3, 4-dihydroxybenzaldehyde of 1:2 for complexation to obtain a polymer mixed solution;
2) Depositing a layer of 0.1 mu m Indium Tin Oxide (ITO) conductive network on a silicon substrate in advance by adopting an evaporation mode, pouring the obtained polymer mixed solution on the ITO, and then placing the ITO mixed solution in a vacuum oven at 90 ℃ to fully volatilize dimethylformamide to generate a polyethylene glycol-polysiloxane copolymerized elastomer with the thickness of 100 mu m;
3) Tearing the fully cured (fully volatilized solvent is fully cured) copolymerized elastomer and the underlying ITO together, namely removing a template substrate to obtain an ITO conductive self-adhesive elastomer coated on the surface, and connecting the two ends of an ITO conductive layer with organosilicon system conductive silver paste as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be applied on moist skin surfaceThe raw surface is softened, and the tight adhesion strength (35+/-5) kPa with human skin is realized after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding ITO can reach 1 x 10 4 S cm -1 About, the maximum stretching rate of 1% can be born, and the sensitivity is more than 1000 (1%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 7
1) Dissolving 4-formylphenylboric acid, 3, 4-dihydroxybenzaldehyde and amine-terminated propyl polysiloxane (weight average molecular weight 2000) in dimethylformamide (the molar ratio of 4-formylphenylboric acid to dimethylformamide is 1:80) according to the molar ratio of 1:1:1, fully mixing, reacting the mixed solution at 60 ℃ for 24 hours, and adding metal salt ferric chloride with the molar ratio of 3, 4-dihydroxybenzaldehyde of 1:3 for coordination to obtain a polymer mixed solution;
2) Depositing a layer of 0.1 mu m nano gold conductive network on a silicon substrate in advance by adopting a magnetron sputtering mode, pouring the obtained polymer mixed solution on the nano gold, and then placing the nano gold mixed solution in a vacuum oven at 90 ℃ to fully volatilize dimethylformamide to generate a polysiloxane elastomer with the thickness of 100 mu m;
3) Tearing off the polysiloxane elastomer after complete solidification (namely complete volatilization of the solvent) and the nano gold below, namely removing the template substrate to obtain a nano gold conductive self-adhesive elastomer coated on the surface, and connecting the two ends of the nano gold conductive layer with organic silicon system conductive silver paste as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be subjected to surface softening on the surface of moist skin, and can be tightly adhered to the skin of a human body after the moisture is completely volatilized, and the adhesive strength (55+/-5) kPa; the initial conductivity of the electronic skin obtained by compounding the nano gold can reach 1-10 5 S cm -1 About, the tensile rate of 1% at maximum can be born, and the sensitivity is more than 1100 (1%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
Example 8
1) Dissolving 2-formylphenylboric acid, 3, 4-dihydroxybenzaldehyde and aminopropyl polysiloxane (weight average molecular weight 3000) in ethanol (the molar ratio of 2-formylphenylboric acid to ethanol is 1:80) according to a molar ratio of 1:1:1, fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding metal salt ferric chloride with a molar ratio of 1:3 with 3, 4-dihydroxybenzaldehyde for coordination to obtain a polymer mixed solution;
2) Growing a layer of polypyrrole conductive network with the thickness of 2000 mu m on a silicon substrate in an in-situ growth mode, pouring the polymer mixed solution on the polypyrrole, and then placing the polypyrrole mixed solution in a vacuum oven with the temperature of 45 ℃ to fully volatilize ethanol to generate a polysiloxane elastomer;
3) Tearing off the polysiloxane elastomer after complete solidification (namely complete volatilization of the solvent) and polypyrrole below, namely removing the template substrate to obtain a polypyrrole conductive self-adhesive elastomer coated on the surface, and connecting the two ends of the polypyrrole conductive layer with organic silicon system conductive silver paste as a flexible electrode to obtain the required self-adhesive electronic skin;
4) The electronic skin prepared by the method can be subjected to surface softening on the surface of moist skin, and can be tightly adhered to the skin of a human body after the moisture is completely volatilized, and the adhesive strength (58+/-5) kPa; the initial conductivity of the electronic skin obtained by compounding polypyrrole can reach 8-10 2 S cm -1 About, the tensile rate of 10% at maximum can be born, and the sensitivity is more than 500 (10%); the electronic skin can be peeled off from the surface of the human skin by using alkaline water (ph=9 or so).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the self-adhesive electronic skin based on the multiple reversible bonding effect is characterized by comprising the following steps of:
(1) Uniformly mixing formylphenylboric acid, polyhydroxy benzaldehyde and amino-terminated prepolymer by taking an organic solvent as a reaction medium, reacting for 30 min-72 h at the temperature of between room temperature and 90 ℃, and adding metal salt for coordination to obtain a polymer mixed solution;
(2) Depositing a conductive layer on a template substrate, pouring the polymer mixed solution in the step (1) on the conductive layer, and removing the solvent, wherein boron-oxygen bonds react with each other to generate covalent boron-oxygen hexacyclic rings, so as to obtain a polymer elastomer;
(3) Removing the template substrate to obtain a conductive self-adhesive elastomer coated with a conductive layer on the surface, and connecting flexible electrodes at two ends of the conductive layer to obtain self-adhesive electronic skin based on multiple reversible bonding;
the molar ratio of the formylphenylboronic acid to the polyhydroxy benzaldehyde in the step (1) is 1: 5-5: 1, the molar ratio of the total mole number of formylphenylboronic acid to polyhydroxy benzaldehyde to the mole number of the amino terminated prepolymer is 2:1 to 2.2:1, wherein the molar ratio of the metal salt to the polyhydroxy benzaldehyde is 1: 3-1: 2;
the formylphenyl boric acid in the step (1) is at least one of 2-formylphenyl boric acid, 3-formylphenyl boric acid and 4-formylphenyl boric acid; the polyhydroxy benzaldehyde is at least one of 2, 3-dihydroxybenzaldehyde, 3, 4-dihydroxybenzaldehyde, 2,3, 4-trihydroxybenzaldehyde and 3,4, 5-trihydroxybenzaldehyde; the amino-terminated prepolymer is at least one of amino-terminated polysiloxane, amino-terminated polyurethane and amino-terminated polyethylene glycol; the weight average molecular weight of the amino-terminated prepolymer is 2000-12000; the metal salt is at least one of ferric chloride, vanadium chloride, aluminum chloride, magnesium chloride, zinc chloride and calcium chloride.
2. The method for preparing self-adhesive electronic skin based on multiple reversible bonding according to claim 1, wherein the molar ratio of formylphenylboronic acid to organic solvent in step (1) is 1: 30-100; the thickness of the conductive layer in the step (2) is 0.1-100 mu m, and the thickness of the polymer elastomer layer obtained by casting is 100-2000 mu m.
3. The method for preparing self-adhesive electronic skin based on multiple reversible bonding according to claim 1, wherein the conductive layer material in step (2) is at least one of a metal material, a metal oxide material, a carbon material and a conductive polymer material; the deposition mode of the conductive layer is at least one of evaporation, magnetron sputtering, chemical vapor deposition, spraying, spin coating, printing and in-situ growth.
4. The method for preparing self-adhesive electronic skin based on multiple reversible bonding according to claim 3, wherein the conductive layer material in the step (2) is at least one of polypyrrole, nano gold, indium tin oxide, graphene, nano silver, carbon nanotubes and silver nanowires.
5. The method for preparing self-adhesive electronic skin based on multiple reversible bonding according to claim 1, wherein the method for removing the solvent in step (2) is natural volatilization or heating volatilization, and the temperature of the heating volatilization is 35-90 ℃; and (3) the flexible electrode is organic silicon system conductive silver paste and/or polyurethane system conductive silver paste.
6. The method for preparing self-adhesive electronic skin based on multiple reversible bonding according to claim 1, wherein the organic solvent in step (1) is at least one of absolute ethanol, methanol, dimethylformamide, tetrahydrofuran and dichloromethane; the template substrate in the step (2) is at least one of a glass substrate, a silicon substrate, a polytetrafluoroethylene substrate and a polyimide substrate; and (3) depositing a release agent or a sacrificial layer on the surface of the template substrate in advance before the deposition in the step (2).
7. A self-adhesive electronic skin based on multiple reversible bonding made by the method of any one of claims 1-6.
8. The use of a self-adhesive electronic skin based on multiple reversible bonding in the fields of flexible wearable devices, flexible patch electrodes and intelligent robotics according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110072300.0A CN112932412B (en) | 2021-01-20 | 2021-01-20 | Self-adhesion electronic skin based on multiple reversible bonding effect and preparation method and application thereof |
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| CN202110072300.0A CN112932412B (en) | 2021-01-20 | 2021-01-20 | Self-adhesion electronic skin based on multiple reversible bonding effect and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112932412A CN112932412A (en) | 2021-06-11 |
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