CN112932412A - Self-adhesion electronic skin based on multiple reversible bonding effects and preparation method and application thereof - Google Patents
Self-adhesion electronic skin based on multiple reversible bonding effects 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 effects and a preparation method and application thereof. The method comprises the following steps: dissolving formyl phenylboronic 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 conducting 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 a human body, 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-adhesive electronic skin based on multiple reversible bonding effects, 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 can 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 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 complex 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 skins has been the focus of attention of researchers. However, since the surface structure of human skin as a detection object is complex, some parts are weak in deformation (such as heartbeat and pulse), and the high-sensitivity electronic skin has the problems of weak output signals, high noise and the like in practical wearing application, the high-sensitivity electronic skin has higher requirements on the interface action of the electrons and the skin. The precondition for capturing the pulse signal is the transmission of force and deformation to the electronic skin, which requires high adhesion (surface roughness ratio less than or equal to 50%), self-adhesion (skin adhesion more than or equal to 1kPa) and later-stage de-adhesion between the electronic skin material and the skin. However, most of the 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, in consideration of the complexity of the human activity environment, besides the use in the conventional environment, the adhesion and the de-adhesion of the human body during sweating and underwater are also required to be considered, the existing reported adhesive electronic skin can only meet the use of a single scene, but cannot meet the adhesion and the de-adhesion under the above multiple scenes, and 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
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of self-adhesive electronic skin based on multiple reversible bonding effects.
The invention also aims to provide the self-adhesive electronic skin based on multiple reversible bonding effects, which is prepared by the method.
The self-adhesion elastomer electronic skin based on multiple reversible bonding effects specifically comprises three reversible bonding effects of reversible ring opening and ring forming of boratoxylon, reversible coordination of phenolic hydroxyl groups and metal ions, and reversible reaction of phenylboronic acid and catechol, wherein the boratoxylon structure can undergo reversible ring opening in the presence of a small amount of water, so that the modulus of the elastomer is reduced, and the fluidity of the elastomer is increased, and the metal coordination ensures the integrity of the electronic skin in the state, so that the elastomer can be subjected to secondary shaping on the skin surface in the state, and the shaped elastomer can be fully infiltrated into the skin, namely the high adhesiveness of the electronic skin to the human skin is realized. By further removing moisture, the boron-oxygen bonds are re-bonded to form a six-ring structure, so that the modulus of the elastomer is increased, and adhesion locking on the skin surface is achieved. 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 the coordination, so that the use in underwater and sweating states is ensured; and the bonding of the phenolic hydroxyl and the phenylboronic acid can occur under alkaline conditions to realize the electronic skin detackification. Therefore, the problems of the existing electronic skin can be well solved through the ingenious application of multiple reversible bonding effects.
It is a further object of the present invention to provide the above use of self-adhesive electronic skins based on multiple reversible bonding.
The purpose of the invention is realized by the following technical scheme:
a preparation method of self-adhesive electronic skin based on multiple reversible bonding effects comprises the following steps:
(1) uniformly mixing formylphenylboronic acid, polyhydroxy benzaldehyde and an amino-terminated prepolymer by taking an organic solvent as a reaction medium, reacting at room temperature to 90 ℃ for 30 min-72 h, and adding metal salt for coordination to obtain a polymer mixed solution;
(2) depositing a conducting layer on a template substrate, pouring the polymer mixed solution obtained in the step (1) on the conducting layer, removing the solvent, and reacting boron-oxygen bonds with each other to generate covalent boron-oxygen hexacyclic rings to obtain a polymer elastomer;
(3) and removing the template substrate to obtain the conductive self-adhesion elastomer with the surface coated with the conductive layer, and connecting the flexible electrodes at two ends of the conductive layer to obtain the self-adhesion electronic skin based on the multiple reversible bonding effects.
Preferably, the organic solvent in 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 of 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 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 2000-12000.
Preferably, the mole ratio of the formylphenylboronic acid to the polyhydroxy benzaldehyde in the step (1) is 1: 5-5: 1, the molar ratio of the total moles of the formylphenylboronic acid and the polyhydroxybenzaldehyde to the mole of the amino-terminated prepolymer is 2: 1-2.2: 1, the molar ratio of the metal salt to the polyhydroxy benzaldehyde is 1: 3-1: 2.
preferably, the mole ratio of the formylphenylboronic acid to the organic solvent in the step (1) is 1:30 to 100.
Preferably, the metal salt in 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 step (2) is at least one of a glass substrate, a silicon substrate, a teflon substrate and a polyimide substrate.
Preferably, before the deposition in 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 conductive layer in step (2) is deposited by 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, nanosilver, carbon nanotube, and silver nanowire.
Preferably, the thickness of the conducting 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 step (3) is a conductive composite material with certain flexibility, and more preferably, the conductive silver paste is a silicone 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 effects.
The self-adhesive electronic skin based on the multiple reversible bonding effects is applied to the fields of flexible wearable equipment, flexible patch electrodes and intelligent robots.
When the electronic skin is actually attached to human skin for use, 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 boratoxyclones are opened under the action of the water, the viscosity of an elastomer system is reduced, the shaping capacity is obtained, metal coordination bonds are still stable under the action of the water, the shape of the electronic skin is integrally maintained, the elastomer conforms to the wrinkle change of the skin surface under the further application of pressure to fully infiltrate the surface of the human skin, after the water is completely volatilized under the double actions of the pressure and the body temperature, the boratoxyclones are regenerated, the elastomer structure returns to high strength, and then the electronic skin can be firmly attached 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 elastomer is further used underwater, the boron-oxygen bond is opened, the integral modulus of the elastomer is reduced, and the phenolic hydroxyl group of the elastomer is bonded.
The electronic skin disclosed by the invention has self-repairing and repeatable shaping capabilities besides adhesiveness.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the electronic skin can support skin surface adhesion in various states such as dry, moist, underwater, sweating and the like.
2) The electronic skin can realize free detackification under mild conditions.
3) The electronic skin prepared by the method has self-repairing and repeatable shaping capabilities.
Drawings
FIG. 1 is a schematic diagram of reversible ring opening and cyclization of a boron-oxygen hexacyclic structure.
FIG. 2 is a schematic diagram showing the reversible coordination of catechol structure and metal ions.
FIG. 3 is a schematic diagram of 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 the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
1) Dissolving 2-formylphenylboronic acid, 2, 3-dihydroxybenzaldehyde and terminal aminopropyl polysiloxane (weight average molecular weight 2000) in the molar ratio of 5:1:3 in absolute ethyl alcohol (the molar ratio of the 2-formylphenylboronic acid to the absolute ethyl alcohol is 1:50), fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding metal salt ferric chloride with the molar ratio of the 2, 3-dihydroxybenzaldehyde of 1:3 for coordination to obtain a polymer mixed solution;
2) pre-depositing a layer of 10-micrometer silver nanowire conductive network on a polytetrafluoroethylene template substrate in a spraying manner, pouring the obtained polymer mixed solution on a silver nanowire, and then putting the silver nanowire conductive network in a vacuum oven at 45 ℃ to fully volatilize ethanol to generate a polysiloxane elastomer with the thickness of 1000 micrometers;
3) tearing off the completely cured (completely volatilized solvent is completely cured) polysiloxane elastomer and the underlying silver nanowires, namely removing the template substrate to obtain the silver nanowire conductive self-adhesion elastomer coated on the surface, and connecting organosilicon system conductive silver paste at two ends of a silver nanowire conductive layer to be used as flexible electrodes to obtain the required self-adhesion electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface, and can realize close adhesion with the human skin after the moisture is completely volatilized, and the bonding strength is (25 +/-2) kPa; the initial conductivity of the electronic skin obtained by compounding the silver nanowires can reach 5 x 104S cm-1About, can bear the maximum tensile rate of 150%, the degree of sensitivity is above 110 (150%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 2
1) Dissolving 3-formylphenylboronic acid, 3, 4-dihydroxybenzaldehyde and terminal aminopropyl polysiloxane (weight average molecular weight 2000) in dimethylformamide (wherein the molar ratio of the 3-formylphenylboronic acid to the dimethylformamide is 1:30) according to the molar ratio of 1:1:1, fully mixing, reacting the mixed solution at 90 ℃ for 30min, and adding metal salt aluminum chloride with the molar ratio of the 3, 4-dihydroxybenzaldehyde being 1:3 for coordination to obtain a polymer mixed solution;
2) depositing a layer of 10-micron graphene conductive network on a silicon substrate in advance in 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 microns;
3) tearing off the completely cured (completely volatilized solvent is completely cured) polysiloxane elastomer and the underlying graphene, namely removing the template substrate to obtain a conductive self-adhesive elastomer of the graphene coated on the surface, and connecting organosilicon system conductive silver paste at two ends of a graphene conductive layer to be used as flexible electrodes to obtain the required self-adhesive electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface and realize the close adhesion and bonding strength (25 +/-2) kPa with the human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding graphene can reach 3 x 103S cm-1About, can bear the maximum 50% elongation, the degree of sensitivity is above 90 (50%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 3
1) 3-formylphenylboronic acid, 2,3, 4-trihydroxybenzaldehyde and terminal aminopropylpolysiloxane (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) mixing and fully mixing, reacting the mixed solution at room temperature for 72 hours, and adding vanadium chloride which is a metal salt with the molar ratio of 2,3, 4-trihydroxybenzaldehyde being 1:3 to perform coordination action to obtain a polymer mixed solution;
2) in order to facilitate demoulding of the cured elastomer, a layer of mould release agent is deposited on the surface of the polyimide template substrate in advance, and a layer of 50-micron carbon nanotube conductive network is printed on the silicon substrate in a screen printing mode; pouring the obtained 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 completely cured (completely volatilized solvent is completely cured) polysiloxane elastomer and the underlying carbon nano tube, namely removing the template substrate to obtain the carbon nano tube conductive self-adhesion elastomer coated on the surface, and connecting organosilicon system conductive silver paste at two ends of a carbon nano tube conductive layer to be used as flexible electrodes to obtain the required self-adhesion electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface, and can realize tight adhesion with the human skin after the moisture is completely volatilized, and the bonding strength is (55 +/-5) kPa; electronic skin initiation by compounding carbon nanotubesThe conductivity can reach 5 x 103S cm-1About, can bear the maximum 10% elongation, the degree of sensitivity is above 40 (10%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 4
1) Dissolving 4-formylphenylboronic acid, 3,4, 5-trihydroxybenzaldehyde and amino-terminated polyurethane (weight average molecular weight 8000) in tetrahydrofuran (molar ratio of 4-formylphenylboronic acid to tetrahydrofuran is 1:100) according to a molar ratio of 1.1:1.1:1, fully mixing, reacting the mixed solution at room temperature for 72h, and adding magnesium chloride which is a metal salt with a molar ratio of 1:2 of 3,4, 5-trihydroxybenzaldehyde to perform coordination to obtain a polymer mixed solution;
2) in order to facilitate demoulding of the cured elastomer, a sacrificial layer is deposited on the surface of a polyimide base in advance, a 100-micron nano silver conductive network is printed on the polyimide base in a printing mode, the obtained polymer mixed solution is poured on the nano silver, and then the nano silver mixed solution is placed in a vacuum oven at 35 ℃ to fully volatilize tetrahydrofuran to generate the polyurethane elastomer, wherein the thickness of the polyurethane elastomer is 2000 microns;
3) tearing off the polyurethane elastomer after complete curing (solvent is completely volatilized, namely, complete curing) together with the underlying nano silver, namely, removing the template substrate to obtain the nano silver conductive self-adhesion elastomer coated on the surface, and connecting polyurethane system conductive silver paste at two ends of the nano silver conductive layer to be used as flexible electrodes to obtain the required self-adhesion electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface and realize the close adhesion and bonding strength (35 +/-5) kPa with the human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding the nano silver can reach 6 x 104S cm-1About, can bear the maximum 10% elongation, the degree of sensitivity is above 380 (10%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 5
1) Dissolving 4-formylphenylboronic acid, 3, 4-dihydroxybenzaldehyde and amino-terminated polyurethane (weight average molecular weight 2000) in dichloromethane (the molar ratio of the 4-formylphenylboronic acid to the dichloromethane 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 which is a metal salt with the molar ratio of 1:2 of the 3, 4-dihydroxybenzaldehyde to perform 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 putting the graphene in a vacuum oven at 35 ℃ to fully volatilize dichloromethane to generate a polyurethane elastomer with the thickness of 100 mu m;
3) tearing off the completely cured (completely volatilized solvent is completely cured) polyurethane elastomer and the underlying graphene, namely removing the template substrate to obtain a graphene conductive self-adhesion elastomer coated on the surface, and connecting polyurethane system conductive silver paste at two ends of a graphene conductive layer to be used as flexible electrodes to obtain the required self-adhesion electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface and realize the close adhesion and bonding strength (35 +/-5) kPa with the human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding graphene can reach 6 x 103S cm-1About, can bear the maximum 5% elongation, the degree of sensitivity is above 330 (5%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 6
1) Dissolving 4-formylphenylboronic acid, 3, 4-dihydroxybenzaldehyde, terminal amino polyethylene glycol (weight average molecular weight 2000) and terminal amino polysiloxane (weight average molecular weight 3000) in a molar ratio of 1:1:0.5:0.5 in dimethylformamide (the molar ratio of 4-formylphenylboronic acid to dimethylformamide is 1:80), fully mixing, reacting the mixed solution at 50 ℃ for 48 hours, and adding calcium chloride which is a metal salt and has a molar ratio of 1:2 with 3, 4-dihydroxybenzaldehyde to perform coordination 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 method, pouring the obtained polymer mixed solution on the ITO, and then putting the ITO into 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 off the completely cured (completely volatilized solvent is completely cured) copolymerized elastomer and the ITO below, namely removing the template substrate to obtain the ITO conductive self-adhesive elastomer coated on the surface, and connecting organosilicon system conductive silver paste at two ends of the ITO conductive layer to be used as flexible electrodes to obtain the required self-adhesive electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface and realize the close adhesion and bonding strength (35 +/-5) kPa with the human skin after the moisture is completely volatilized; the initial conductivity of the electronic skin obtained by compounding the ITO can reach 1 x 104S cm-1About, can bear the maximum 1% elongation, the degree of sensitivity is above 1000 (1%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 7
1) Dissolving 4-formylphenylboronic acid, 3, 4-dihydroxybenzaldehyde and terminal aminopropylpolysiloxane (weight average molecular weight 2000) in a molar ratio of 1:1:1 in dimethylformamide (the molar ratio of the 4-formylphenylboronic acid to the dimethylformamide is 1:80), fully mixing, reacting the mixed solution at 60 ℃ for 24 hours, and adding metal salt ferric chloride with the molar ratio of the 3, 4-dihydroxybenzaldehyde being 1:3 for coordination to obtain a polymer mixed solution;
2) pre-depositing a layer of 0.1 mu m nano-gold conductive network on a silicon substrate in a magnetron sputtering mode, pouring the obtained polymer mixed solution on the nano-gold, and then putting the nano-gold into a vacuum oven at 90 ℃ to fully volatilize dimethylformamide so as to generate a polysiloxane elastomer with the thickness of 100 mu m;
3) tearing off the completely cured (completely volatilized solvent is completely cured) polysiloxane elastomer and the underlying nanogold, namely removing the template substrate to obtain the nanogold conductive self-adhesive elastomer coated on the surface, and connecting organosilicon system conductive silver paste at two ends of a nanogold conductive layer to be used as flexible electrodes to obtain the required self-adhesive electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface, and can realize tight adhesion with the human skin after the moisture is completely volatilized, and the bonding strength is (55 +/-5) kPa; the initial conductivity of the electronic skin obtained by compounding the nano-gold can reach 1 x 105S cm-1About, can bear the maximum tensile rate of 1%, the degree of sensitivity is above 1100 (1%); the electronic skin can be peeled off from the surface of human skin by using alkaline water (pH is about 9).
Example 8
1) Dissolving 2-formylphenylboronic acid, 3, 4-dihydroxybenzaldehyde and terminal aminopropyl polysiloxane (weight average molecular weight 3000) in ethanol (the molar ratio of the 2-formylphenylboronic acid to the ethanol is 1:80) according to the 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 the molar ratio of the 3, 4-dihydroxybenzaldehyde being 1:3 for coordination to obtain a polymer mixed solution;
2) growing a layer of 100-micron polypyrrole conductive network on a silicon substrate in an in-situ growth mode, pouring the obtained polymer mixed solution on polypyrrole, and then putting the polypyrrole conductive network on a 45-DEG C vacuum oven to fully volatilize ethanol to generate a polysiloxane elastomer with the thickness of 2000 microns;
3) tearing off the completely cured polysiloxane elastomer (completely volatilizing the solvent, namely completely curing) together with the underlying polypyrrole, namely removing the template substrate to obtain a polypyrrole conductive self-adhesion elastomer coated on the surface, and connecting organosilicon system conductive silver paste at two ends of a polypyrrole conductive layer to be used as flexible electrodes to obtain the required self-adhesion electronic skin;
4) the electronic skin prepared by the method can soften the surface of the wet skin surface, and can realize close adhesion with the human skin after the moisture is completely volatilized, and the bonding strength is (58 +/-5) kPa; the initial conductivity of the electronic skin obtained by compounding the polypyrrole can reach 8 x 102S cm-1About, can bear the maximum 10% elongation, the degree of sensitivity is above 500 (10%); the electronic skin and the skin surface of human body can be treated with alkaline water (pH of about 9)Peeling occurs.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of self-adhesive electronic skin based on multiple reversible bonding effects is characterized by comprising the following steps:
(1) uniformly mixing formylphenylboronic acid, polyhydroxy benzaldehyde and an amino-terminated prepolymer by taking an organic solvent as a reaction medium, reacting at room temperature to 90 ℃ for 30 min-72 h, and adding metal salt for coordination to obtain a polymer mixed solution;
(2) depositing a conducting layer on a template substrate, pouring the polymer mixed solution obtained in the step (1) on the conducting layer, removing the solvent, and reacting boron-oxygen bonds with each other to generate covalent boron-oxygen hexacyclic rings to obtain a polymer elastomer;
(3) and removing the template substrate to obtain the conductive self-adhesion elastomer with the surface coated with the conductive layer, and connecting the flexible electrodes at two ends of the conductive layer to obtain the self-adhesion electronic skin based on the multiple reversible bonding effects.
2. The method for preparing self-adhesive electronic skin based on multiple reversible bonding effects according to claim 1, wherein the mole ratio of formylphenylboronic acid to polyhydroxybenzaldehyde in step (1) is 1: 5-5: 1, the molar ratio of the total moles of the formylphenylboronic acid and the polyhydroxybenzaldehyde to the mole of the amino-terminated prepolymer is 2: 1-2.2: 1, the molar ratio of the metal salt to the polyhydroxy benzaldehyde is 1: 3-1: 2.
3. the method for preparing self-adhesive electronic skin based on multiple reversible bonding effects according to claim 1, wherein the formylphenylboronic acid in the step (1) is at least one of 2-formylphenylboronic acid, 3-formylphenylboronic acid and 4-formylphenylboronic acid; the polyhydroxy benzaldehyde is at least one of 2, 3-dihydroxy benzaldehyde, 3, 4-dihydroxy benzaldehyde, 2,3, 4-trihydroxy benzaldehyde and 3,4, 5-trihydroxy benzaldehyde; 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 trichloride, vanadium chloride, aluminum chloride, magnesium chloride, zinc chloride and calcium chloride.
4. The method for preparing self-adhesive electronic skin based on multiple reversible bonding effects according to claim 1, wherein the mole ratio of the formylphenylboronic acid to the organic solvent in the step (1) is 1: 30-100 parts; the thickness of the conducting 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.
5. The method for preparing self-adhesive electronic skin based on multiple reversible bonding effects according to claim 1, wherein 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; the deposition mode of the conducting layer is at least one of evaporation, magnetron sputtering, chemical vapor deposition, spraying, spin coating, printing and in-situ growth.
6. The method for preparing the self-adhesive electronic skin based on the multiple reversible bonding effects according to claim 5, wherein the conductive layer material in the step (2) is at least one of polypyrrole, nanogold, indium tin oxide, graphene, nanosilver, carbon nanotubes and silver nanowires.
7. The preparation method of the self-adhesive electronic skin based on the multiple reversible bonding effects as claimed in claim 1, wherein the solvent removal method in the step (2) is natural volatilization or heating volatilization, and the temperature of the heating volatilization is 35-90 ℃; and (3) the flexible electrode is organosilicon system conductive silver paste and/or polyurethane system conductive silver paste.
8. The method for preparing self-adhesive electronic skin based on multiple reversible bonding effects according to claim 1, wherein the organic solvent in step (1) is at least one of absolute ethyl alcohol, 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; before the deposition in the step (2), a layer of release agent or a sacrificial layer can be deposited on the surface of the template substrate in advance.
9. A self-adhesive electronic skin based on multiple reversible bonding prepared by the method of any one of claims 1 to 8.
10. The use of the self-adhesive electronic skin based on multiple reversible bonding effects of claim 9 in the fields of flexible wearable devices, flexible patch electrodes and smart robots.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563559A (en) * | 2021-07-20 | 2021-10-29 | 陕西科技大学 | Self-repairing polyurethane based on boron-oxygen hexacyclic ring and preparation method thereof |
| CN115594815A (en) * | 2022-09-30 | 2023-01-13 | 香港中文大学（深圳）（Cn） | High-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, preparation method, recycling method, degradation method and surgical operation line thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205551A (en) * | 2018-11-01 | 2019-01-15 | 深圳先进技术研究院 | A kind of tapered array flexible electrode and preparation method thereof |
| CN109338716A (en) * | 2018-09-28 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of fibrous composite and preparation method for robot electronic skin |
| KR20190092073A (en) * | 2018-01-30 | 2019-08-07 | 광운대학교 산학협력단 | Method of Manufacturing Electrode for Measuring Biosignal Based on Low Temperature Solution Process, Electrode for Measuring Biosignal, and Apparatus for Measuring Biosignal Using Same |
| CN110231056A (en) * | 2019-06-14 | 2019-09-13 | 齐鲁工业大学 | Utilize the method and electronic skin sensor of ink jet printing flexibility micro-structure surface preparation micro-structure electrode |
-
2021
- 2021-01-20 CN CN202110072300.0A patent/CN112932412B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190092073A (en) * | 2018-01-30 | 2019-08-07 | 광운대학교 산학협력단 | Method of Manufacturing Electrode for Measuring Biosignal Based on Low Temperature Solution Process, Electrode for Measuring Biosignal, and Apparatus for Measuring Biosignal Using Same |
| CN109338716A (en) * | 2018-09-28 | 2019-02-15 | 成都新柯力化工科技有限公司 | A kind of fibrous composite and preparation method for robot electronic skin |
| CN109205551A (en) * | 2018-11-01 | 2019-01-15 | 深圳先进技术研究院 | A kind of tapered array flexible electrode and preparation method thereof |
| CN110231056A (en) * | 2019-06-14 | 2019-09-13 | 齐鲁工业大学 | Utilize the method and electronic skin sensor of ink jet printing flexibility micro-structure surface preparation micro-structure electrode |
Non-Patent Citations (1)
| Title |
|---|
| 包春阳: "基于氮配位硼氧六环的自修复与可循环利用聚合物材料", 中国博士学位论文全文数据库（工程科技I辑）, no. 2019, pages 1 - 5 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563559A (en) * | 2021-07-20 | 2021-10-29 | 陕西科技大学 | Self-repairing polyurethane based on boron-oxygen hexacyclic ring and preparation method thereof |
| CN113563559B (en) * | 2021-07-20 | 2022-06-21 | 陕西科技大学 | Self-repairing polyurethane based on boron-oxygen hexacyclic ring and preparation method thereof |
| CN115594815A (en) * | 2022-09-30 | 2023-01-13 | 香港中文大学（深圳）（Cn） | High-strength tear-resistant degradable temperature-sensitive polyurethane elastomer, preparation method, recycling method, degradation method and surgical operation line thereof |
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