CN112961487B - Polyaniline composite liquid, nuclear layer atomized spray liquid, artificial bionic skin and preparation method - Google Patents
Polyaniline composite liquid, nuclear layer atomized spray liquid, artificial bionic skin and preparation method Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/10—Hair or skin implants
- A61F2/105—Skin implants, e.g. artificial skin
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract
The invention belongs to the field of water-based high-molecular functional materials, and particularly relates to a water-soluble polyaniline composite liquid, a nuclear layer atomized spray liquid, an artificial bionic skin and a preparation method thereof. The polyaniline composite liquid is synthesized by adopting a high-molecular acid doping mode and is used as a network path to transmit nuclear layer dielectric signals, so that the skin is endowed with an electric sensing effect; the artificial bionic skin is prepared from the core-shell atomized liquid spray and the shell layer atomized liquid spray prepared from alcohol-soluble cationic fluorinated polyurethane through a core-shell electrostatic atomization technology, and has the advantages of air permeability, moisture permeability, water and oil repellency, antibiosis, high strength, high flexibility, high conductivity and low resistance.
Description
Technical Field
The invention belongs to the field of synthesis and preparation of aqueous high-molecular functional materials, and particularly relates to a water-soluble polyaniline composite liquid and a preparation method thereof, a core-layer atomized liquid spray prepared from the water-soluble polyaniline composite liquid, an artificial bionic skin prepared from the core-layer atomized liquid spray and a preparation method thereof.
Background
As is known, skin is an important component of human organs, can assist in defending microorganisms and other harmful substances in the external environment, and has the functions of perspiring, regulating human moisture, excreting metabolic products of human body, maintaining human body temperature and the like. The skin of a person is the most directly contacted with the organs of the external environment, so that the skin is the most vulnerable part, for example, the skin is damaged or even permanently damaged by impact of hard objects, high temperature or fire burn, fungal infection, acute trauma and the like, and a medical treatment means which is relatively quick is skin grafting repair, so that the demand for artificial bionic skin in the medical field is increasing. In addition, with the rapid development of artificial intelligence using 5G communication technology as a carrier, electronic skins facing bionic robots, which can cover complex three-dimensional surfaces and movable joints of robots, are also receiving high attention from the market.
Polyurethane is a polar high polymer containing a large number of carbamate groups, which is formed by alternately inlaying soft segments and hard segments on a molecular main chain, is an environment-friendly high polymer material which is rapidly developed in recent years, and has wide application value in the medical field by the characteristics of excellent physical and mechanical properties, good biological tissue compatibility, good blood compatibility, low toxicity, no teratogenicity, high flexibility and ductility and the like. However, the resistance of the artificial skin conductive medium prepared by the prior art is usually more than or equal to 800 Ω, the piezoelectric sensing effect is not provided, the possibility of providing electric signal transmission of robot skin or human heartbeat monitoring application in the medical field is limited, and seamless connection and coating of three-dimensional objects and joints are difficult to realize in the preparation and application process.
Disclosure of Invention
The invention aims to overcome the defects that the artificial skin has no piezoelectric sensing effect and is difficult to realize seamless connection and coating of three-dimensional objects and joints in the prior art, and provides a water-soluble polyaniline composite liquid and a preparation method thereof, a nuclear layer atomized liquid spray prepared from the water-soluble polyaniline composite liquid, an artificial bionic skin prepared from the nuclear layer atomized liquid spray and a preparation method thereof.
In order to solve the technical problem, the technical scheme is that the preparation method of the water-soluble polyaniline composite liquid specifically comprises the following steps;
respectively adding high molecular acid and aniline into distilled water, wherein the molar ratio of the high molecular acid to the aniline to the distilled water is (0.1-2.5):1 (1-10), then introducing 15-50min of nitrogen, placing the nitrogen and stirring at a constant speed for 1-5h at the temperature of 0-10 ℃, slowly dropwise adding an ammonium persulfate aqueous solution or a hydrochloric acid solution, controlling the dropwise adding time to be 1.5-3h, and then continuously reacting for 8-15h to obtain a high molecular acid doped polyaniline solution;
taking 50 parts by mass of polymer acid doped polyaniline solution, sequentially adding a carbon nano tube and graphene loaded with alumina nano particles, wherein the total mass of the carbon nano tube and the graphene loaded with the alumina nano particles is 2-15 parts, ball milling the graphene loaded with the alumina nano particles for 30-50min by using a ball mill before adding, mechanically stirring the mixed solution, and ultrasonically mixing for 0.5-1.5h to prepare the water-soluble polyaniline composite solution.
The preparation method of the water-soluble polyaniline complex liquid is further improved as follows:
preferably, the polymeric acid is one or a combination of two or more of sodium poly (styrene sulfonate), sodium polystyrene sulfonate, sodium poly (toluene sulfonate) and polystyrene sulfonic acid.
In order to solve another technical problem of the invention, the technical scheme is that the water-soluble polyaniline composite solution prepared by the preparation method is adopted.
In order to solve another technical problem, the technical scheme adopted is that the core layer atomized spray liquid is prepared from the water-soluble polyaniline composite liquid;
as a further improvement of the above-mentioned nucleus layer atomized liquid spray:
preferably, the core layer atomized spray liquid is prepared by adding 5-10 parts by mass of high molecular weight polyacrylamide and 1-5 parts by mass of surfactant into 50-100 parts by mass of water-soluble polyaniline composite liquid and uniformly stirring.
In order to solve another technical problem, the technical scheme is that the method for preparing the artificial bionic skin by the nuclear layer atomized liquid spray comprises the following steps: the artificial bionic skin is prepared by using a PET (polyethylene terephthalate) plate or PDMS (polydimethylsiloxane) base material with the thickness of 0.5-1mm as a supporting layer, using a core-shell double-layer spray head and a shell layer spray head as base materials, and performing electrostatic atomization spraying on the supporting layer by using an electrostatic spray gun with a core-shell double-layer spray head, wherein the core-shell double-layer spray head comprises a core layer spray head and a shell layer spray head sleeved outside the core layer spray head, the core layer spray head is used for spraying the core layer atomized spray head, the shell layer spray head is used for spraying the shell layer atomized spray head, the inner diameter of the core-shell spray head is 0.3-0.8mm, the inner diameter of the shell layer spray head is 0.5-2.5mm, the input voltage of the electrostatic spray gun is 15-50V, the spraying speed is 1-5ml/min, and then placing the sprayed supporting layer in an environment at the room temperature of 25-35 ℃ for natural drying for 15-24 hours.
The preparation method of the artificial bionic skin is further improved as follows:
preferably, the shell layer atomized spray liquid is prepared from alcohol-soluble cationic fluorinated polyurethane with the molecular weight of 3-8 ten thousand, and the specific steps are as follows: adding a defoaming agent into alcohol-soluble cationic fluorinated polyurethane, curing for 10-30h at 35-70 ℃, adding water-soluble high-molecular-weight polyacrylamide and/or polyvinyl alcohol into the system, stirring at a high speed and mixing uniformly, and ultrasonically dispersing to prepare an atomized stock solution which takes ethanol as a solvent and has a solid content of 35-45%, namely the shell atomized spray liquid.
Preferably, the preparation method of the alcohol-soluble cationic fluorinated polyurethane is as follows: firstly, carrying out vacuum dehydration treatment on polyol with biocompatibility at 90-105 ℃, then cooling to 45-55 ℃, adding isocyanate, heating to 80-90 ℃, fully reacting for 1-5 hours, testing that the residual NCO group reaches the theoretical residual value, reducing the temperature to 50-70 ℃, sequentially adding a fluorinated micromolecule chain extender, a cationic hydrophilic alcohol chain extender, polysiloxane, a fluorinated alcohol monomer and a catalyst, continuing to carry out heat preservation reaction for 1-5 hours, introducing protective gas during the reaction, continuing to reduce the temperature to 45-55 ℃ after the reaction reaches the set theoretical value of NCO, then adding a non-hydrophilic alcohol micromolecule chain extender and a crosslinking agent, continuing to carry out heat preservation reaction for 1-5 hours, reducing the temperature to 25-40 ℃ after the reaction does not change the test set residual NCO value any more, adding an acid neutralizer and ethanol, and emulsifying under the action of high-speed shearing force, and (3) obtaining a cationic fluorinated polyurethane-ethanol solvent mixed system, then dropwise adding an emulsifier and a rear chain extender into the mixed system, emulsifying and stirring for a period of time, and emulsifying at the temperature of 35-55 ℃ for 1-2h to obtain the alcohol-soluble cationic fluorinated polyurethane with the molecular weight of 3-8 ten thousand.
Preferably, the preparation of the alcohol-soluble cationic fluorinated polyurethane comprises the following raw materials in parts by mass: 95-200 parts of biocompatible polyol, 30-150 parts of aliphatic polyisocyanate, 5-30 parts of fluorinated micromolecule chain extender, 5-25 parts of cationic hydrophilic alcohol chain extender, 1-25 parts of polysiloxane, 5-30 parts of fluorinated alcohol monomer, 0.1-10 parts of catalyst, 8-20 parts of non-hydrophilic alcohol micromolecule chain extender, 0.1-10 parts of cross-linking agent, 5-30 parts of acid neutralizing agent, 80-500 parts of ethanol, 0.1-8 parts of emulsifier and 5-8 parts of post chain extender.
In order to solve the last technical problem of the invention, the technical scheme is that the artificial bionic skin prepared by the preparation method is adopted.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, a high-molecular acid doping mode is adopted to synthesize water-soluble polyaniline composite liquid, nitrogen is introduced into a mixed system to remove dissolved oxygen in the system, and the water-soluble polyaniline composite liquid has the functions of being used as a network path to transmit nuclear layer dielectric signals in artificial bionic skin, endowing a skin layer with a good piezoelectric sensing effect and providing possibility for later-stage electric signal transmission of robot skin or human heartbeat monitoring applied in the medical field;
(2) preparing core layer atomized spray liquid: the synthesized mixed system of the water-soluble polyaniline, the carbon nano tube particles and the graphene particles is difficult to realize uniform mixing at a molecular level, and has the condition of local agglomeration;
(3) synthesis of high molecular weight alcohol-soluble cationic fluorinated polyurethane:
the invention adopts an environment-friendly alcohol-soluble method to synthesize high molecular weight polyurethane with the molecular weight of 3-8 ten thousand, and adopts a polyol soft segment with good biocompatibility to synthesize cationic fluorinated polyurethane in the synthesis process;
the fluorinated alcohol monomer is used for introducing fluorine-carbon bonds into a polyurethane molecular chain structure, so that the surface energy of a material interface is further reduced.
The cationic hydrophilic alcohol chain extender aims to introduce tertiary amination groups on a synthetic polyurethane chain segment, then carry out tertiary amination,
the polysiloxane material mainly reduces the surface energy of the material and improves the water and oil resistance of the material;
the non-lipophilic small molecular chain extender mainly has the function of further improving the molecular weight of the synthesized fluorinated polyurethane;
the cross-linking agent is a micromolecule cross-linking agent which further improves the strength and the stretch and tear resistance of the material layer;
the acid neutralizing agent has the function that part of the acid neutralizing agent provides a neutralizing effect, and can dissolve biological components of chitosan and natural fibroin so as to be introduced into a system, thereby playing the roles of antibiosis, antiphlogosis and biodegradability;
(4) the preparation method of the shell atomized spray liquid is characterized in that on the basis of synthesizing high molecular weight alcohol-soluble cationic fluorinated polyurethane, water-soluble high molecular polyacrylamide or polyethylene pure and a polyurethane-ethanol system are uniformly stirred and mixed at high speed by adopting an AK dispersing agent, and are prepared into 35-45% atomized stock solution through ultrasonic dispersion to be used as the shell atomized spray liquid for later use.
(5) The electrostatic atomization artificial bionic skin spray layer mainly adopts a shell layer atomized spray liquid and a core layer atomized spray liquid as base materials, and simultaneously adopts a PET plate or PDMS base material as a supporting layer; then carrying out electrostatic atomization spraying by using an electrostatic spray gun with a core-shell double-layer spray head, and then naturally drying at room temperature to obtain the coating; the artificial bionic skin spray layer has soft surface touch, high flexibility, ductility and good adhesion force, and can be expected to be applied to the fields of artificial bionic skin transplantation of medical wound surfaces, robot electronic skin and the like. The artificial bionic skin layer prepared by the method has the advantages of antibiosis, moisture absorption and sweat release, and the core layer is further endowed with electric conductivity through the introduction of the multi-wall carbon nano tube, the graphene loaded with the alumina nano particles and the polyaniline, so that the artificial bionic skin layer can be used for the aspects of robot skin sensing, human heartbeat monitoring and the like.
(6) Aiming at the requirements of the current market on artificial bionic skin, the invention firstly synthesizes alcohol-soluble cationic fluorinated polyurethane with high biocompatibility and high molecular weight by polylactic acid polyol, bombyx mori silk fibroin, polylactide-co-caprolactone polyol, polysiloxane and aliphatic hard segment, and realizes the preparation of the artificial bionic skin by a core-shell electrostatic atomization technology. The prepared artificial bionic skin has good air and moisture permeability, and simultaneously has the advantages of hydrophobicity and oleophobicity, antibiosis, high strength, high flexibility (the elongation rate can reach 1800 percent), high conductivity and low resistance less than or equal to 50 omega, the resistance of the existing artificial skin without introducing polyaniline and graphene conductive media is more than or equal to 800 omega, the artificial bionic skin can be applied to repairing of medical wound skin, and the prepared handheld core-shell electrostatic atomizer can be used for spraying a three-dimensional object at any angle, so that the coating of a three-dimensional mechanical structure and joints of a robot can be realized, and the core layer can be directly sprayed on the heart or wrist part of a human body due to the excellent conductivity of the core layer, so that the heartbeat monitoring of the human body can be tracked.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
In the preparation of the alcohol-soluble cationic fluorinated polyurethanes, preferred species of the respective starting materials are as follows:
the polyol with biocompatibility is a combination of polyether polyol, polyester polyol and polylactic acid polyol, and the mass ratio of the polyether polyol to the polylactic acid polyol is (30-50) to (50-100) to (15-50).
The polyether glycol is one or the combination of two or more of polyoxyethylene glycol, polytetrahydrofuran ether glycol, soybean oil polyether glycol, palm oil polyether glycol, castor oil polyether glycol and Mannich polyether glycol; the polyester polyol is one or the combination of two or more of polycaprolactone diol, polylactide-co-caprolactone polyol, poly epsilon-caprolactone polyether polyol and poly propylene carbonate polyol; the polylactic acid polyol is a biodegradable polyol soft segment.
The isocyanate is aliphatic polyisocyanate, and specifically comprises one or a combination of two or more of isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,6 hexyl diisocyanate, tetramethylcyclohexyl methane diisocyanate, methylcyclohexyl diisocyanate and norbornane diisocyanate.
The fluorinated alcohol monomer is fluorinated micromolecule monohydric alcohol, fluorinated micromolecule dihydric alcohol or long-chain fluorine-containing dihydric alcohol; the fluorine-containing dihydric alcohol is one or the combination of two or more of PEVE type, fluorine-containing polyester glycol and fluorine-containing polyether glycol.
The fluorinated micromolecule chain extender is one or a combination of two or more of fluorinated diol and fluorinated diamine.
The cationic hydrophilic chain extender aims at introducing a tertiary amination group on a synthetic polyurethane chain segment and then carrying out tertiary amination, and the specific tertiary amine compound hydrophilic chain extender is one or the combination of two or more of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, tert-butyldiethanolamine, dimethylethanolamine and bis (2-hydroxypropyl) aniline.
The polysiloxane material specifically includes: one or a combination of two or more of epoxy-polysiloxane, polydimethylsiloxane, polyether siloxane and fluoroalkyl polysiloxane.
The catalyst is one or the combination of two or more of dibutyltin dilaurate, zinc carboxylate, bismuth carboxylate and tetrabutyl titanate.
The non-hydrophilic small molecular chain extender is specifically selected from one or a combination of two or more of 1,4 butanediol, ethylene glycol, diethylene glycol, neopentyl glycol and amine terminated polyether.
The cross-linking agent comprises trimethylolpropane, 1,2, 6-hexanetriol, methyl glucoside and one or the combination of two or more of sucrose and a silane coupling agent KH550/KH 560.
The acid neutralizing agent is one or the combination of two or more of glacial acetic acid, glycolic acid and acetic anhydride, and natural biological components including fibroin and/or chitosan dissolved by the acid neutralizing agent are added while the acid neutralizing agent is added.
The emulsifier is at least one or the combination of two or more of OP-10 and sodium dodecyl benzene sulfonate.
The rear chain extender is one or the combination of two of ethylenediamine and isophorone diamine.
The ethanol is an ethanol solution with the industrial grade concentration of more than or equal to 95 percent.
Example 1
The invention provides a preparation method of shell atomized spray liquid, which specifically comprises the following steps:
s1, synthesis of alcohol-soluble high molecular weight cationic fluorinated polyurethane: firstly, 35 parts of polyoxyethylene glycol, 60 parts of polycaprolactone diol and 25 parts of polylactic acid polyol are subjected to vacuum dehydration for 1-1.5h at the temperature of 90-105 ℃; then cooling to 45-55 ℃, adding 85 parts of weighed isophorone diisocyanate, heating to 90 ℃, keeping the temperature for full reaction for 3 hours, testing that the residual NCO group reaches the theoretical residual value, cooling to 60 ℃, sequentially adding 7 parts of fluorinated micromolecule monohydric alcohol, 6 parts of fluorinated diol, 6 parts of N-methyldiethanolamine, 10 parts of polydimethylsiloxane and 3 parts of bismuth carboxylate catalyst, continuing to keep the temperature for reaction for 3 hours, introducing protective gas during the reaction, continuing to reduce the temperature to 45 ℃ after the reaction reaches the set theoretical value of NCO, then adding 8 parts of ethylene glycol chain extender and 1 part of trimethylolpropane, continuing to keep the temperature for reaction for 4 hours, reducing the temperature to 25-40 ℃ after the reaction does not change the residual NCO value, adding 9.5 parts of glacial acetic acid for neutralization for 5-8 minutes, and simultaneously adding 10 parts of glacial acetic acid for dissolving for 3 days, 2 parts of chitosan natural biological component, then adding 400 parts of 95% diluted viscosity-reducing ethanol, emulsifying under the action of high-speed shearing force, then dropwise adding 2 parts of OP-10 emulsifier and 5 parts of ethylenediamine rear chain extender, and then continuing to emulsify and stir for a period of time to obtain high-molecular-weight alcohol-soluble fluorinated polyurethane;
s2, adding 1 part of polysiloxane copolymer defoaming agent into the alcohol-soluble fluorinated polyurethane solution, curing the synthesized alcohol-soluble polyurethane at 50 ℃ for 24 hours, weighing 100 parts of the polyurethane alcohol solution, adding 5 parts of polyacrylamide with the molecular weight of 50W, dispersing and stirring the polyacrylamide and AK dispersing agent at a high speed for 0.5 hour on the basis of preparing the high molecular weight alcohol-soluble fluorinated polyurethane, and performing ultrasonic dispersion for 0.5 hour to prepare the shell atomized spray liquid.
Example 2
The invention provides a preparation method of a nuclear layer atomized spray liquid, which specifically comprises the following steps:
s1, preparing water-soluble polyaniline composite liquid, and introducing a conductive nano medium: respectively adding high molecular acid and aniline into distilled water, wherein the molar ratio of the high molecular acid to the aniline to the distilled water is 1.5:1:5, and introducing nitrogen into a mixed system for 30min to remove dissolved oxygen in the system; then placing the mixture at 5 ℃ for heat preservation reaction for 4 hours, then dropwise adding 2mmol/L ammonium persulfate aqueous solution by using a dropping funnel, wherein the molar ratio of ammonium persulfate to aniline is 1:1, the dropwise adding time is controlled to be 1.5 hours, and continuing the reaction for 8 hours after the dropwise adding is finished to obtain an acid-doped polyaniline aqueous solution; then weighing 50 parts of polyaniline solution, adding 3 parts of multi-walled carbon nanotubes and 2 parts of graphene loaded with alumina nanoparticles (the graphene and the carbon nanotubes are ball-milled for 30min on a ball mill), and then performing AK high-speed dispersion and ultrasonic dispersion for 0.5h to prepare water-soluble polyaniline composite solution;
s2, in order to prevent the nano-particle medium from settling and mixing uneven agglomeration, 5 parts of 100w molecular weight polyacrylamide and 1 part of sodium dodecyl benzene sulfonate are added into the polyaniline mixed solution, and the mixture is stirred and mixed evenly to prepare the core-layer atomized spray liquid.
Example 3
The invention provides a method for preparing artificial bionic skin by using shell layer atomized liquid spray and core layer atomized liquid spray prepared in examples 1 and 2, which specifically comprises the following steps:
preparing an electrostatic atomization artificial bionic skin spray layer: in order to facilitate the collection and test of the bionic layer, the invention adopts an ore oxygen red copper plate as a negative electrode substrate (so as to form a stable electric field to collect atomized particles), and then a PET plate or PDMS base layer with the thickness of 0.5-1mm is covered on the negative electrode substrate as a supporting layer; then a simple handheld electrostatic spray gun (35V battery pack) self-made by a laboratory and a core-shell double layer (a core layer and a shell layer are respectively fixed in the spray gun by a 15ml disposable injector, the injection speed is 1.5ml/min, the inner diameter of a core-shell spray head of the injector is 0.3-0.8mm for the core layer and 0.5-2.5mm for the shell layer), continuous electrostatic atomization spraying is carried out for 10min at 90 degrees vertically downwards, and then the spray head is naturally dried for 15-24h at the room temperature of 25-35 ℃ to obtain the artificial bionic skin; the spraying method of the invention only adopts vertical downward spraying for testing performance, and adopts a handheld electrostatic atomization spray gun to spray at any angle in practical application so as to be convenient for being tightly attached to a three-dimensional object or an interface;
the mechanical property test of the prepared artificial bionic layer is mainly carried out by adopting an Instron tensile machine, the figure layer is sprayed on a PET plate or a PDMS plate and is taken off after being naturally dried, and then the figure layer is cut into strips with the width of 10mm and the length of 5-8cm to carry out a mechanical tensile test. And (3) carrying out the performance test of the resistance value and the conductivity of the bionic skin layer by adopting a double-electrical-measurement four-probe method. The elongation of the bionic layer tested by the embodiment is 1300%, the strength is 50MPa, and the resistance value is 50 omega.
Example 4
The invention provides a preparation method of shell atomized spray liquid, which specifically comprises the following steps:
the invention relates to a preparation method of an artificial bionic skin based on alcohol-soluble water-based resin, which specifically comprises the following steps:
s1, synthesis of alcohol-soluble high-molecular-weight cationic fluorinated polyurethane: firstly, dehydrating 35 parts of polytetrahydrofuran ether glycol, 70 parts of polylactide-co-caprolactone polyol and 45 parts of polylactic acid polyol at 90-105 ℃ for 1.5 hours in vacuum; then cooling to 45 ℃, adding 105 parts of weighed isophorone diisocyanate, heating to 90 ℃, keeping the temperature for sufficient reaction for 4 hours, testing that the residual NCO group reaches the theoretical residual value, reducing the temperature to 60 ℃, adding 10 parts of fluorinated micromolecule monohydric alcohol, 5 parts of fluorinated diol, 6 parts of N-methyldiethanolamine and 8 parts of polydimethylsiloxane, simultaneously adding 5 parts of organic bismuth catalyst, continuing to keep the temperature for reaction for 3 hours, introducing protective gas during the reaction, continuing to reduce the temperature to 45 ℃ after the reaction reaches the set theoretical value of NCO, then adding 10 parts of ethylene glycol chain extender and 2.5 parts of trimethylolpropane, continuing to keep the temperature for reaction for 4 hours, reducing the temperature to 25 ℃ after the reaction is not changed until the residual NCO value set in the test is not changed, adding 6 parts of glacial lactic acid for neutralization for 5-8 minutes, and simultaneously adding 10 parts of glacial acetic acid for dissolving for 3 days, 2 parts of chitosan natural biological component, then adding 450 parts of 95% diluted viscosity-reducing ethanol, emulsifying under the action of high-speed shearing force, then dropwise adding 2 parts of OP-10 emulsifier and 5 parts of isophorone diamine and then chain extender, and then continuing to emulsify and stir for a period of time to obtain high-molecular-weight alcohol-soluble fluorinated polyurethane;
and S2, finally adding 1.5 parts of polysiloxane copolymer defoaming agent, curing the synthesized alcohol-soluble polyurethane at 50 ℃ for 24h, weighing 100 parts of the polyurethane alcohol solution, adding 5 parts of polyacrylamide with the molecular weight of 50W, dispersing and stirring the mixture with AK dispersant at high speed for 0.5h on the basis of preparing the high-molecular-weight alcohol-soluble fluorinated polyurethane, and performing ultrasonic dispersion for 0.5h to prepare shell atomized spray liquid for later use.
Example 5
The invention provides a preparation method of a nuclear layer atomized spray liquid, which specifically comprises the following steps:
s1, preparing water-soluble polyaniline composite liquid, and introducing a conductive nano medium: respectively adding high molecular acid and aniline into distilled water, wherein the molar ratio of the high molecular acid to the aniline to the distilled water is 2:1:8, and introducing nitrogen into a mixed system for 30min to remove dissolved oxygen in the system; then placing the mixture at 5 ℃ for heat preservation reaction for 4 hours, then dropwise adding 3mmol/L ammonium persulfate solution by using a dropping funnel, wherein the molar ratio of ammonium persulfate to aniline is 1:0.5, the dropwise adding time is controlled to be 2 hours, and continuing the reaction for 8 hours after the dropwise adding is finished to obtain an acid-doped polyaniline aqueous solution; weighing 50 parts of polyaniline solution, adding 5 parts of multi-walled carbon nanotubes and 5 parts of graphene loaded with alumina nanoparticles (the graphene and the carbon nanotubes are ball-milled for 30min in a ball mill), and performing AK high-speed dispersion for 1h to prepare water-soluble polyaniline composite solution;
s2, in order to prevent the nano-particle medium from settling and mixing uneven agglomeration, 5 parts of 100w molecular weight polyacrylamide, 1 part of sodium dodecyl benzene sulfonate and 1 part of OP-10 are added into the polyaniline mixed solution, and the mixture is stirred and mixed evenly to prepare the nuclear layer atomized spray liquid.
Example 6
The invention provides a method for preparing artificial bionic skin by using shell layer atomized liquid spray and core layer atomized liquid spray prepared in examples 4 and 5, which specifically comprises the following steps:
preparing an electrostatic atomization artificial bionic skin spray layer: in order to facilitate the collection and test of the bionic layer, the invention adopts an ore oxygen red copper plate as a negative electrode substrate (so as to form a stable electric field to collect atomized particles), and then a PET plate or PDMS base layer with the thickness of 0.5-1mm is covered on the negative electrode substrate as a supporting layer; then a simple handheld electrostatic spray gun (35V battery pack) self-made by a laboratory and a core-shell double layer (a core layer and a shell layer are respectively fixed in the spray gun by a 15ml disposable injector, the injection speed is 1.5ml/min, the inner diameter of a core-shell nozzle of the injector is that the core layer is 0.3-0.8mm, the shell layer is 0.5-2.5mm), the nozzle is subjected to vertical downward 90-degree continuous electrostatic atomization spraying for 10min, and then the artificial bionic skin can be obtained after the artificial bionic skin is naturally dried for 15-24h at the room temperature of 25-35 ℃; the spraying method of the invention only adopts vertical downward spraying for testing performance, and adopts a handheld electrostatic atomization spray gun to spray at any angle in practical application so as to be convenient for being tightly attached to a three-dimensional object or an interface;
the mechanical property test of the prepared artificial bionic layer is mainly carried out by adopting an Instron tensile machine, the figure layer is sprayed on a PET plate or a PDMS plate and is taken off after being naturally dried, and then the figure layer is cut into strips with the width of 10mm and the length of 5-8cm to carry out a mechanical tensile test. And (3) carrying out the performance test of the resistance value and the conductivity of the bionic skin layer by adopting a double-electrical-measurement four-probe method. The elongation of the bionic layer tested by the embodiment is 1500%, the strength is 56MPa, and the resistance value is 45 omega.
Example 7
The invention provides a preparation method of shell atomized spray liquid, which specifically comprises the following steps:
s1, synthesis of alcohol-soluble high-molecular-weight cationic fluorinated polyurethane: firstly, dehydrating 10 parts of polytetrahydrofuran ether glycol, 20 parts of palm oil polyether polyol, 20 parts of soybean oil polyether polyol, 80 parts of poly-epsilon-caprolactone polyether diol and 50 parts of polylactic acid polyol at 90-105 ℃ for 1.5 hours in vacuum; then cooling to 45 ℃, adding 125 parts of weighed isophorone diisocyanate, heating to 90 ℃, keeping the temperature for sufficient reaction for 5 hours, testing that the residual NCO group reaches the theoretical residual value, reducing the temperature to 60 ℃, adding 12 parts of fluorinated micromolecule monohydric alcohol, 5 parts of fluorinated diol, 15 parts of N-methyldiethanolamine and 9.5 parts of polydimethylsiloxane, simultaneously adding 6 parts of bismuth carboxylate catalyst in the total amount of the materials, keeping the temperature for reaction for 4.5 hours, introducing protective gas during the reaction, keeping the temperature to 55 ℃ after the reaction reaches the set theoretical value of NCO, adding 10 parts of 1, 4-butanediol chain extender and 3 parts of trimethylolpropane, keeping the temperature for reaction for 4 hours, reducing the temperature to 35 ℃ after the reaction is not changed until the test set residual NCO value is not changed, adding 6 parts of glacial lactic acid for neutralization for 5-8 minutes, simultaneously adding 15 parts of glacial acetic acid for dissolving for 5 days, adding fibroin, and stirring, 2 parts of chitosan natural biological component, then adding 500 parts of 95% diluted viscosity-reducing ethanol, emulsifying under the action of high-speed shearing force, then dropwise adding 2 parts of OP-10 emulsifier, 5 parts of isophorone diamine and 3 parts of ethylene diamine post-chain extender, and then continuing to emulsify and stir for a period of time to obtain high-molecular-weight alcohol-soluble fluorinated polyurethane;
s2, finally adding 2 parts of polysiloxane copolymer defoaming agent, curing the synthesized alcohol-soluble polyurethane at 50 ℃ for 24h, weighing 100 parts of the polyurethane alcohol solution, adding 5 parts of polyacrylamide with the molecular weight of 50W, dispersing and stirring with AK dispersing agent at high speed for 0.5h on the basis of preparing the high-molecular-weight alcohol-soluble fluorinated polyurethane, and performing ultrasonic dispersion for 0.5h to prepare the shell layer atomized spray liquid.
Example 8
The invention provides a preparation method of a nuclear layer atomized spray liquid, which specifically comprises the following steps:
s1, preparing water-soluble polyaniline composite liquid, and introducing a conductive nano medium: respectively adding high molecular acid and aniline into distilled water, wherein the molar ratio of the high molecular acid to the aniline to the distilled water is 1.8:1:10, and introducing nitrogen into a mixed system for 30min to remove dissolved oxygen in the system; then placing the mixture at 5 ℃ for heat preservation reaction for 4 hours, then dropwise adding 5mmol/L ammonium persulfate solution by using a dropping funnel, wherein the molar ratio of ammonium persulfate to aniline is 1:0.5, the dropwise adding time is controlled to be 2 hours, and continuing the reaction for 8 hours after the dropwise adding is finished to obtain an acid-doped polyaniline aqueous solution; weighing 50 parts of polyaniline solution, adding 5 parts of multi-walled carbon nanotubes and 5 parts of graphene loaded with alumina nanoparticles (the graphene and the carbon nanotubes are ball-milled for 30min in a ball mill), and performing AK high-speed dispersion for 1h to prepare water-soluble polyaniline composite solution;
s2, in order to prevent the nano-particle medium from settling and mixing uneven agglomeration, adding 6 parts of 100w molecular weight polyacrylamide, 2.5 parts of sodium dodecyl benzene sulfonate and 1 part of OP-10 into the polyaniline mixed solution, and stirring and mixing uniformly to obtain the core-layer atomized spray liquid.
Example 9
The invention provides a method for preparing artificial bionic skin by using the shell layer atomized liquid spray and the core layer atomized liquid spray prepared in the embodiments 7 and 8, which specifically comprises the following steps:
preparing an electrostatic atomization artificial bionic skin spray layer: in order to facilitate the collection and test of the bionic layer, the invention adopts an ore oxygen red copper plate as a negative electrode substrate (so as to form a stable electric field to collect atomized particles), and then a PET plate or PDMS base layer with the thickness of 0.5-1mm is covered on the negative electrode substrate as a supporting layer; then a simple handheld electrostatic spray gun (35V battery pack) self-made by a laboratory and a core-shell double layer (a core layer and a shell layer are respectively fixed in the spray gun by a 15ml disposable injector, the injection speed is 1ml/min, the inner diameter of a core-shell nozzle of the injector is that the core layer is 0.3-0.8mm, the shell layer is 0.5-2.5mm), the nozzle is subjected to continuous electrostatic atomization spraying for 15min at 90 degrees vertically downwards, and then the artificial bionic skin can be obtained after the artificial bionic skin is placed in an environment with the room temperature of 25-35 ℃ and is naturally dried for 15-24 h; the spraying method of the invention only adopts vertical downward spraying for testing performance, and adopts a handheld electrostatic atomization spray gun to spray at any angle in practical application so as to be convenient for being tightly attached to a three-dimensional object or an interface;
the mechanical property test of the prepared artificial bionic layer is mainly carried out by adopting an Instron tensile machine, the figure layer is sprayed on a PET plate or a PDMS plate and is taken off after being naturally dried, and then the figure layer is cut into strips with the width of 10mm and the length of 5-8cm to carry out a mechanical tensile test. And (3) carrying out the performance test of the resistance value and the conductivity of the bionic skin layer by adopting a double-electrical-measurement four-probe method. The elongation of the bionic layer tested by the embodiment is 1800%, the strength is 60MPa, and the resistance value is 43 omega.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of water-soluble polyaniline composite liquid is characterized by comprising the following steps:
respectively adding polystyrene sulfonic acid and aniline into distilled water, wherein the molar ratio of the polystyrene sulfonic acid to the aniline to the distilled water is (0.1-2.5):1 (1-10), then introducing 15-50min of nitrogen, placing the mixture in an environment at 0-10 ℃, stirring the mixture at a constant speed for 1-5h, slowly dropwise adding an ammonium persulfate aqueous solution, controlling the dropwise adding time to be 1.5-3h, and then continuously reacting for 8-15h to obtain a polyaniline solution doped with the polystyrene sulfonic acid;
taking 50 parts by mass of polyaniline solution doped with polystyrene sulfonic acid, sequentially adding carbon nano tubes and graphene loaded with alumina nano particles, wherein the total mass of the carbon nano tubes and the graphene loaded with the alumina nano particles is 2-15 parts, ball milling the graphene loaded with the alumina nano particles for 30-50min by using a ball mill before adding, mechanically stirring the mixed solution, and ultrasonically mixing for 0.5-1.5h to prepare the water-soluble polyaniline composite solution.
2. A water-soluble polyaniline composite liquid obtained by the production method according to claim 1.
3. A core-layer atomized spray liquid prepared from the water-soluble polyaniline composite liquid as described in claim 2.
4. The core-layer atomized spray of claim 3, wherein the core-layer atomized spray is prepared by adding 5 to 10 parts by mass of the high molecular weight polyacrylamide and 1 to 5 parts by mass of the surfactant to 50 to 100 parts by mass of the water-soluble polyaniline composite solution and stirring them uniformly.
5. A method for preparing an artificial biomimetic skin from the atomized spray of the core layer of claim 3, comprising the steps of: the artificial bionic skin is prepared by using a PET (polyethylene terephthalate) plate or PDMS (polydimethylsiloxane) base material with the thickness of 0.5-1mm as a supporting layer, using a core-shell double-layer spray head and a shell layer spray head as base materials, and performing electrostatic atomization spraying on the supporting layer by using an electrostatic spray gun with a core-shell double-layer spray head, wherein the core-shell double-layer spray head comprises a core layer spray head and a shell layer spray head sleeved outside the core layer spray head, the core layer spray head is used for spraying the core layer atomized spray head, the shell layer spray head is used for spraying the shell layer atomized spray head, the inner diameter of the core-shell spray head is 0.3-0.8mm, the inner diameter of the shell layer spray head is 0.5-2.5mm, the input voltage of the electrostatic spray gun is 15-50V, the spraying speed is 1-5ml/min, and then placing the sprayed supporting layer in an environment at the room temperature of 25-35 ℃ for natural drying for 15-24 hours.
6. The preparation method of the artificial bionic skin as claimed in claim 5, wherein the shell layer atomized spray is prepared from alcohol-soluble cationic fluorinated polyurethane with molecular weight of 3-8 ten thousand, and the specific steps are as follows: adding a defoaming agent into alcohol-soluble cationic fluorinated polyurethane, curing for 10-30h at 35-70 ℃, adding water-soluble high-molecular-weight polyacrylamide and/or polyvinyl alcohol into the system, stirring at a high speed and mixing uniformly, and preparing atomized stock solution with the solid content of 35-45% by ultrasonic dispersion, namely shell atomized spray liquid; the preparation method of the alcohol-soluble cationic fluorinated polyurethane comprises the following steps: firstly, carrying out vacuum dehydration treatment on polyol with biocompatibility at 90-105 ℃, then cooling to 45-55 ℃, adding isocyanate, heating to 80-90 ℃, fully reacting for 1-5 hours, testing that the residual NCO group reaches the theoretical residual value, reducing the temperature to 50-70 ℃, sequentially adding a fluorinated micromolecule chain extender, a cationic hydrophilic alcohol chain extender, polysiloxane, a fluorinated alcohol monomer and a catalyst, continuing to carry out heat preservation reaction for 1-5 hours, introducing protective gas during the reaction, continuing to reduce the temperature to 45-55 ℃ after the reaction reaches the set theoretical value of NCO, then adding a non-hydrophilic alcohol micromolecule chain extender and a crosslinking agent, continuing to carry out heat preservation reaction for 1-5 hours, reducing the temperature to 25-40 ℃ after the reaction does not change the test set residual NCO value any more, adding an acid neutralizer and ethanol, and emulsifying under the action of high-speed shearing force, obtaining a cationic fluorinated polyurethane-ethanol solvent mixed system, then dropwise adding an emulsifier and a rear chain extender into the mixed system, emulsifying and stirring for a period of time, and emulsifying at 35-55 ℃ for 1-2h to obtain alcohol-soluble cationic fluorinated polyurethane with the molecular weight of 3-8 ten thousand;
the fluorinated micromolecule chain extender is one or a combination of two or more of fluorinated diol and fluorinated diamine; the cationic hydrophilic chain extender aims at introducing a tertiary amination group on a synthetic polyurethane chain segment and then carrying out tertiary amination, and the specific tertiary amine compound hydrophilic chain extender is one or the combination of two or more of diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, tert-butyldiethanolamine, dimethylethanolamine and bis (2-hydroxypropyl) aniline.
7. The method for preparing the artificial bionic skin according to claim 6, wherein the alcohol-soluble cationic fluorinated polyurethane is prepared from the following raw materials in parts by mass: 95-200 parts of biocompatible polyol, 30-150 parts of aliphatic polyisocyanate, 5-30 parts of fluorinated micromolecule chain extender, 5-25 parts of cationic hydrophilic alcohol chain extender, 1-25 parts of polysiloxane, 5-30 parts of fluorinated alcohol monomer, 0.1-10 parts of catalyst, 8-20 parts of non-hydrophilic alcohol micromolecule chain extender, 0.1-10 parts of cross-linking agent, 5-30 parts of acid neutralizing agent, 80-500 parts of ethanol, 0.1-8 parts of emulsifier and 5-8 parts of post chain extender;
the non-hydrophilic small molecular chain extender is specifically selected from one or a combination of two or more of 1,4 butanediol, ethylene glycol, diethylene glycol and neopentyl glycol.
8. An artificial biomimetic skin prepared by the preparation method of any one of claims 5-7.
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