CN114854046A - Triple-stimulus-responsive double-layer hydrogel actuator and preparation method thereof - Google Patents
Triple-stimulus-responsive double-layer hydrogel actuator and preparation method thereof Download PDFInfo
- Publication number
- CN114854046A CN114854046A CN202210495989.2A CN202210495989A CN114854046A CN 114854046 A CN114854046 A CN 114854046A CN 202210495989 A CN202210495989 A CN 202210495989A CN 114854046 A CN114854046 A CN 114854046A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- layer
- isopropylacrylamide
- actuator
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/22—All layers being foamed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0242—Acrylic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0257—Polyamide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/12—Gel
- B32B2266/122—Hydrogel, i.e. a gel containing an aqueous composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—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
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—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
- C08J2333/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—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
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a triple stimulus-responsive double-layer hydrogel actuator and a preparation method thereof. The two hydrogel networks are respectively formed by combining polyacrylic acid-polyacrylamide hydrogel and poly N-isopropylacrylamide-carboxymethyl cellulose hydrogel. The polyacrylic acid-polyacrylamide layer hydrogel is initiated to polymerize by a lignin-potassium persulfate-metal ion initiation system, and the graphene oxide nanobelt is added into the polyacrylic acid-polyacrylamide layer hydrogel to improve the mechanical property, the self-healing capability and the electric conductivity of the polyacrylic acid-polyacrylamide layer hydrogel and provide the photothermal conversion capability for the double-layer hydrogel. The poly-N-isopropylacrylamide-carboxymethylcellulose layer employs light-initiated polymerization to provide temperature response and pH response capabilities to the bilayer hydrogel. Based on the characteristics, the double-layer hydrogel actuator has the performance of triple stimulus response of temperature, pH and near infrared light, and has potential application in the fields of soft robots, valve switches and the like.
Description
Technical Field
The invention relates to the field of intelligent driving materials, in particular to a triple-stimulus-responsiveness double-layer hydrogel actuator and a preparation method thereof.
Background
The hydrogel is a polymer gel with a three-dimensional network structure and rich in moisture. At present, the hydrogel is widely used in the fields of food preservation, biomedicine, tissue engineering and the like. Hydrogel actuators are devices made of hydrogels that are responsive to a particular environment. Environmental stimuli-responsive hydrogel actuators composed of a variety of polymers have shown great potential for applications in areas such as soft robotics, drug delivery, smart sensing, and the like. The dynamics of such a responsive actuator are typically derived from a heterostructure of two layers of hydrogel. Under different conditions, the difference of swelling and swelling elimination generated by the heterostructure drives the heterostructure to move such as bending. However, hydrogel actuators are typically manufactured to consist essentially of an active layer and an inert layer, i.e., the active layer receives and contracts or swells in response to an environmental stimulus. The inert layer has no response capability and forms a heterostructure with the active layer to play a supporting role, so that the shrinkage motion of the hydrogel of the active layer is converted into the bending motion of the double-layer heterogeneous hydrogel. The problem with this bilayer hydrogel is that it can only respond by relying on one of the active layer hydrogels, with a single actuation condition. Therefore, constructing a multi-responsive hydrogel remains somewhat challenging.
Poly-N-isopropyl acrylamide is a widely used thermal response polymer, and the molecular chain of the poly-N-isopropyl acrylamide contains hydrophilic amide groups and hydrophobic isopropyl groups at the same time. When the external temperature is higher than the lower critical dissolution temperature (approximately 32 ℃) of the poly-N-isopropylacrylamide, the hydrophilic action of the amide groups is dominant, the hydrogen bonding action between the amide groups and water molecules enables the hydrogel to absorb a large amount of water so as to expand the hydrogel, and when the external temperature is higher than the lower critical dissolution temperature, the hydrophobic action of the isopropyl groups is dominant, the water in the hydrogel is discharged, and the hydrogel shrinks.
Polyacrylic acid is a common synthetic polymer hydrogel, molecular chains of which contain a large amount of carboxyl groups, and the polyacrylic acid is easy to carry out structural design and chemical modification so that the hydrogel material has more functionality, and is widely applied to the fields of drug controlled release, separation and extraction, sensors, bionics and the like. In an acidic environment, protonation of carboxyl groups in polyacrylic acid causes hydrogel network to shrink, and partial water is discharged, i.e. polyacrylic acid has certain pH responsiveness.
The gel initiation system formed by the calcium lignosulfonate-persulfate-metal ions has the characteristic of stably, quickly and uniformly initiating the polymerization reaction, and the initiation of the polymerization reaction can be realized without adding an accelerator or heating a hydrogel system. In addition, phenolic hydroxyl groups on the calcium lignosulphonate can form hydrogen bonds with carboxyl groups of polyacrylic acid, and metal ions can also form coordinate bonds with the carboxyl groups, and the bonds and the functions can endow the hydrogel with good mechanical properties and self-healing performance.
The graphene oxide nanobelt is prepared from a multi-walled carbon nanotube by a simple oxidation process and has a belt-shaped structure. The graphene oxide nanoribbon extends the good physical and chemical properties of the carbon nanomaterial, such as chemical stability, electrical conductivity, photo-thermal conversion performance and the like. Compared with graphene and carbon nanotubes, the extremely high aspect ratio and the characteristic edge effect of the graphene oxide nanoribbon make the graphene oxide nanoribbon have more flexible and adjustable properties. In the field of intelligent hydrogel, the addition of the graphene oxide nanoribbon can improve the mechanical property of the hydrogel and can be combined with thermal-responsive hydrogel to enable the hydrogel to have the near-infrared light response capability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a triple-responsiveness hydrogel actuator and a preparation method thereof, which can make corresponding responses to triple stimuli of temperature, pH and near infrared light, and meet the use requirements of underwater robots, grippers, valve switches and the like. Another object of the present invention is to provide an application of the above-mentioned triple-response hydrogel actuator.
In order to solve the technical problems, the invention adopts the technical scheme that:
the multi-walled carbon nano tube is oxidized and stripped into a graphene oxide nano belt by a simple oxidation process, and the graphene oxide nano belt is added into a polyacrylic acid-polyacrylamide network to improve the mechanical property, the self-healing property, the strain sensing property and the like of the hydrogel. And (3) taking the polyacrylic acid-polyacrylamide hydrogel as a first layer, and taking the poly N-isopropylacrylamide-carboxymethyl cellulose hydrogel added with the graphene oxide nanobelt as a second layer to obtain the double-layer hydrogel actuator. The two layers of hydrogel respectively generate volume contraction or expansion under different conditions, namely the two layers of hydrogel are an active layer and an inert layer under different conditions. Based on the properties of the hydrogels described above, a two-layer hydrogel actuator can respond to three environmental conditions of temperature, pH, and near-infrared light and can achieve large-angle reversible bending of almost 360 °. In addition, the hydrogel layer containing polyacrylic acid shows strong self-healing performance and strain sensing performance. Therefore, the triple-response double-layer hydrogel can be used in the fields of underwater robots, holders, valve switches and the like.
The preparation method of the triple-responsiveness hydrogel actuator comprises the following steps:
1) dispersing a certain mass of multi-walled carbon nanotubes in concentrated sulfuric acid, slowly adding potassium permanganate into the concentrated sulfuric acid, stirring the mixture evenly under magnetic stirring, and then heating the system to a certain temperature for continuous stirring. Ice water containing hydrogen peroxide was added to complete the reaction. Standing, separating a product, and sequentially washing with deionized water, a hydrochloric acid solution, ethanol and diethyl ether for several times to obtain a graphene oxide nanobelt;
2) adding two monomers of acrylic acid and acrylamide, dispersing agents and a pre-initiation system with different amounts and the graphene oxide nano belt prepared in the step 1) into a beaker, adding water and stirring uniformly. Adding a metal ion solution under the condition of ice-water bath, stirring vigorously for a short time, pouring into a mould for polymerization, and controlling the thickness of the hydrogel layer;
3) placing N-isopropylacrylamide, a cross-linking agent, a graphene oxide nano-belt and carboxymethyl cellulose in deionized water, stirring, adding a certain amount of photoinitiator, and stirring for a certain time in an ice-water bath. Pouring the obtained pre-gel solution on the polyacrylic acid-polyacrylamide layer prepared in the step 2), standing for a period of time, and carrying out photo-initiated polymerization under an ultraviolet lamp to obtain a double-layer hydrogel;
4) and cutting the double-layer hydrogel into strips, bending the strips towards the layer containing the poly-N-isopropylacrylamide under the irradiation of near infrared light or in a hot water environment, and bending the double-layer hydrogel towards the layer containing the polyacrylic acid after the bent strips are placed in an acid solution.
The preparation method of the triple-responsiveness hydrogel actuator is characterized by comprising the following steps:
in the step 1), the mass of the multi-wall carbon nano tube is 0.5-1.5g, the volume of concentrated sulfuric acid is 150-.
In the step 2), the used dispersing agent comprises polyvinylpyrrolidone and sodium dodecyl sulfate, and the initiation system is calcium lignosulfonate-potassium persulfate-metal ions, wherein the metal ions comprise iron ions and silver ions.
In the step 2), the mass fraction of the graphene oxide nanobelt is 0.1-0.5%, the mass fraction of two monomers, namely acrylic acid and acrylamide is 10-15%, the mass fraction of the dispersing agent is 1-3%, the mass fraction of calcium lignosulfonate is 0.3-0.5%, the mass fraction of potassium persulfate is 0.5-1%, and the concentration of metal ions is 0.01-0.02 mM.
The mould used for controlling the thickness of the two layers of hydrogel consists of two glass plates coated with hydrophobic materials and rubber gaskets with different thicknesses, and the thickness of the rubber gaskets is between 0.3 and 1 mm.
In the step 3), the cross-linking agent is N, N' -methylene bisacrylamide, and the photoinitiator is 1-hydroxycyclohexyl phenyl ketone dissolved in methanol.
In the step 3), the concentration of N-isopropylacrylamide is 10-20%, the mass of the cross-linking agent is 0.15-2% of that of the N-isopropylacrylamide, the mass fraction of the graphene oxide nanobelt is 0.1-0.5%, the mass of the carboxymethyl cellulose is 10-15% of that of the N-isopropylacrylamide, and the mass of the 1-hydroxycyclohexyl phenyl ketone is 0.5-1% of that of the N-isopropylacrylamide.
The double-layer hydrogel is responsive to three environmental stimuli, namely temperature, pH and near infrared light. Wherein the response to temperature is derived from the property of poly-N-isopropylacrylamide that shrinks under heat by itself, and the response to pH is derived from the difference in protonation of carboxyl groups in polyacrylic acid and carboxymethyl cellulose. The ability to respond to near-infrared light results from the combination of photothermal conversion of graphene oxide nanoribbons with the thermal response properties of poly-N-isopropylacrylamide.
The bilayer hydrogel bends toward the poly-N-isopropylacrylamide-containing layer when placed in near-infrared irradiation or in water at a temperature greater than 32 ℃, and bends toward the poly-acrylic acid-containing layer when placed in an acidic solution.
The method is simple and easy to operate, and the obtained double-layer hydrogel actuator has good mechanical property and good and rapid response to temperature, pH and near infrared light. And the polyacrylic acid layer hydrogel also shows excellent self-healing performance and strain sensing performance. The triple stimuli-responsive double-layer hydrogel actuator has potential application in the fields of underwater robots, grippers and valve switches.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1) according to the invention, the graphene oxide nanoribbon is introduced into the hydrogel, so that the mechanical property, the self-healing property and the strain sensing property of the hydrogel containing polyacrylic acid can be obviously improved, and the double-layer hydrogel is endowed with high-efficiency photo-thermal conversion capability.
2) The double-layer hydrogel actuator prepared by the invention has triple responsiveness, and can quickly respond to temperature, pH and near infrared light.
3) The double-layer hydrogel is prepared by a simple two-step method, and the prepared double-layer hydrogel actuator has good mechanical properties, has stable response capability to three environmental stimuli, and can be used in the fields of soft robots, valve switches and the like.
Drawings
Figure 1 is a schematic representation of the response of a bi-layer hydrogel actuator to different environmental stimuli.
Detailed Description
The following examples, which are set forth to illustrate some, but not all, of the embodiments, will now be described in more detail. These examples are intended to illustrate the invention only and do not limit the scope of the invention.
Example 1
0.5g of multi-walled carbon nanotube is weighed and dispersed in 150mL of concentrated sulfuric acid, 2g of potassium permanganate is slowly added into the concentrated sulfuric acid, the system is heated to 50 ℃ after being uniformly stirred, the reaction is carried out for 1h, and then ice water containing 5% of hydrogen peroxide is used for stopping the experiment. And standing at room temperature for 24 hours, carrying out suction filtration, taking the upper-layer substance, and respectively and sequentially washing with deionized water, a 15% hydrochloric acid solution, ethanol and diethyl ether for several times to obtain the graphene oxide nanobelt. 1.5g of monomeric acrylamide, 0.045g of calcium lignosulfonate, 0.15g of polyvinylpyrrolidone, 0.075g of potassium persulfate and 1.5mL of monomeric acrylic acid are weighed out in a beaker, and 1mL of 1.5mg/mL graphene oxide nanobelt dispersion and 8mL of deionized water are added thereto. And (3) placing the beaker in an ice-water bath, stirring for 30min, adding 1mL of 0.1M iron ion solution to initiate polymerization, and quickly transferring the pre-gel solution to a mold after quickly stirring uniformly. Adding 1g of monomer N-isopropyl acrylamide, 0.0015g of cross-linking agent N, N' -methylene bisacrylamide and 0.1g of carboxymethyl cellulose into another beaker, adding 1mL of graphene oxide nanobelt dispersion liquid with the concentration of 1.5mg/mL and 9mL of deionized water, stirring uniformly, adding 0.0050g of 1-hydroxycyclohexyl phenyl ketone and 100 muL of methanol premixed solution, placing the beaker into an ice water bath, continuously stirring for 30min to form a pre-gel solution, pouring the pre-gel solution onto a polyacrylic acid-containing layer, standing for 30min, transferring the pre-gel solution to ultraviolet light for polymerization, and controlling the thickness of two layers of hydrogel to be 0.5mm and 0.5mm through a gasket. The hydrogel is designed into a long strip shape or a cross shape, under the irradiation of near infrared light or in deionized water at 40 ℃, the hydrogel is bent towards the layer containing the poly-N-isopropyl acrylamide, and in an acidic solution with the pH value of 1, the hydrogel is bent towards the layer containing the polyacrylic acid.
Example 2
0.75g of multi-walled carbon nanotube is weighed and dispersed in 180mL of concentrated sulfuric acid, 2.2g of potassium permanganate is slowly added into the concentrated sulfuric acid, the mixture is uniformly stirred, the temperature of the system is raised to 55 ℃, the reaction is carried out for 1h, and then ice water containing 20% of hydrogen peroxide is used for stopping the experiment. And standing at room temperature for 20h, performing suction filtration, taking an upper layer substance, and respectively and sequentially washing with deionized water, a 10% hydrochloric acid solution, ethanol and diethyl ether for several times to obtain the graphene oxide nanobelt. 2g of monomer acrylamide, 0.055g of calcium lignosulfonate, 0.25g of sodium dodecyl sulfate, 0.125g of potassium persulfate and 2mL of monomer acrylic acid are weighed out in a beaker, and 1.5mL of graphene oxide nanobelt dispersion with the concentration of 2mg/mL and 7mL of deionized water are added into the beaker. And (3) placing the beaker in an ice-water bath, stirring for 25min, adding 1.2mL of 0.1M silver ion solution to initiate polymerization, and quickly transferring the pre-gel solution into a mold after quickly stirring uniformly. Adding 1.4g of monomer N-isopropylacrylamide, 0.0028g of cross-linking agent N, N' -methylenebisacrylamide and 0.14g of carboxymethyl cellulose into another beaker, adding 1.5mL of graphene oxide nanobelt dispersion liquid with the concentration of 2mg/mL and 8mL of deionized water, stirring uniformly, adding 0.0120g of 1-hydroxycyclohexyl phenyl ketone and 90 muL of methanol premixed solution, placing the beaker into an ice water bath, continuously stirring for 10min to form a pre-gel solution, pouring the pre-gel solution onto a polyacrylic acid-containing layer, standing for 25min, transferring the pre-gel solution to ultraviolet light for polymerization, and controlling the thickness of the two layers of hydrogel to be 0.6mm and 0.6mm through a gasket. The hydrogel is designed into a long strip shape or a cross shape, under the irradiation of near infrared light or in deionized water at 45 ℃, the hydrogel is bent towards the layer containing the poly-N-isopropyl acrylamide, and in an acidic solution with the pH value of 2, the hydrogel is bent towards the layer containing the polyacrylic acid.
Example 3
Weighing 1g of multi-walled carbon nanotube, dispersing in 180mL of concentrated sulfuric acid, slowly adding 2.4g of potassium permanganate, uniformly stirring, heating the system to 60 ℃, reacting for 1h, and terminating the experiment by using ice water containing 15% of hydrogen peroxide. And standing at room temperature for 36h, performing suction filtration, taking an upper layer substance, and respectively and sequentially washing with deionized water, a 25% hydrochloric acid solution, ethanol and diethyl ether for several times to obtain the graphene oxide nanobelt. 1.75g of monomeric acrylamide, 0.05g of calcium lignosulfonate, 0.2g of polyvinylpyrrolidone, 0.1g of potassium persulfate and 1.75mL of monomeric acrylic acid are weighed out in a beaker, and 3mL of graphene oxide nanobelt dispersion with a concentration of 1.2mg/mL and 6mL of deionized water are added thereto. And (3) placing the beaker in an ice-water bath, stirring for 20min, adding 1.5mL of 0.1M iron ion solution to initiate polymerization, and quickly transferring the pre-gel solution into a mold after quickly stirring uniformly. Adding 1.2g of monomer N-isopropylacrylamide, 0.0024g of cross-linking agent N, N' -methylenebisacrylamide and 0.12g of carboxymethyl cellulose into another beaker, adding 3mL of oxidized graphene nanoribbon dispersion with the concentration of 1.2mg/mL and 7mL of deionized water, stirring uniformly, adding 0.0070g of 1-hydroxycyclohexyl phenyl ketone and 105 μ L of methanol premix, placing the beaker into an ice water bath, stirring continuously for 25min to form a pre-gel solution, pouring the pre-gel solution onto a polyacrylic acid-containing layer, standing for 18min, transferring the pre-gel solution to ultraviolet light for polymerization, and controlling the thickness of two layers of hydrogel to be 0.6mm and 0.3mm through a gasket. The hydrogel is designed into a long strip shape or a cross shape, under the irradiation of near infrared light or in deionized water at 55 ℃, the hydrogel is bent towards the layer containing the poly-N-isopropyl acrylamide, and in an acidic solution with the pH value of 5, the hydrogel is bent towards the layer containing the polyacrylic acid.
Example 4
Weighing 1.25g of multi-walled carbon nanotube, dispersing in 210mL of concentrated sulfuric acid, slowly adding 2.5g of potassium permanganate, uniformly stirring, heating the system to 65 ℃, reacting for 1h, and stopping the experiment by using ice water containing 12% of hydrogen peroxide. And standing at room temperature for 30h, performing suction filtration, taking an upper layer substance, and respectively and sequentially washing with deionized water, a 20% hydrochloric acid solution, ethanol and diethyl ether for several times to obtain the graphene oxide nanobelt. 2.25g of monomeric acrylamide, 0.06g of calcium lignosulfonate, 0.3g of sodium dodecyl sulfate, 0.15g of potassium persulfate and 2.25mL of monomeric acrylic acid are weighed out in a beaker, and 2.5mL of graphene oxide nanobelt dispersion with a concentration of 1.5mg/mL and 5mL of deionized water are added thereto. And (3) placing the beaker in an ice-water bath, stirring for 15min, adding 1.6mL of 0.1M silver ion solution to initiate polymerization, and quickly transferring the pre-gel solution into a mold after quickly stirring uniformly. Adding 1.6g of monomer N-isopropylacrylamide, 0.0032g of cross-linking agent N, N' -methylenebisacrylamide and 0.16g of carboxymethyl cellulose into another beaker, adding 2.5mL of graphene oxide nanobelt dispersion with the concentration of 1.5mg/mL and 6mL of deionized water, stirring uniformly, adding 0.0080g of 1-hydroxycyclohexyl phenyl ketone and 95 muL of methanol premixed solution, placing the beaker into an ice water bath, continuously stirring for 15min to form a pre-gel solution, pouring the pre-gel solution onto a polyacrylic acid-containing layer, standing for 25min, transferring the polyacrylic acid-containing layer to ultraviolet light for polymerization, and controlling the thickness of the two layers of hydrogel to be 0.4mm and 0.8mm through a gasket. The hydrogel is designed into a long strip shape or a cross shape, under the irradiation of near infrared light or in deionized water at 70 ℃, the hydrogel is bent towards the layer containing the poly-N-isopropyl acrylamide, and in an acidic solution with the pH value of 4, the hydrogel is bent towards the layer containing the polyacrylic acid.
Example 5
Weighing 1.5g of multi-walled carbon nanotube, dispersing in 250mL of concentrated sulfuric acid, slowly adding 2.7g of potassium permanganate, uniformly stirring, heating the system to 50 ℃, reacting for 1h, and stopping the experiment by using ice water containing 10% of hydrogen peroxide. And standing at room temperature for 32h, performing suction filtration, taking an upper layer substance, and respectively and sequentially washing with deionized water, a 30% hydrochloric acid solution, ethanol and diethyl ether for several times to obtain the graphene oxide nanobelt. 2g of monomer acrylamide, 0.05g of calcium lignosulfonate, 0.35g of polyvinylpyrrolidone, 0.125g of potassium persulfate and 2mL of monomer acrylic acid are weighed in a beaker respectively, and 3mL of graphene oxide nanobelt dispersion solution with the concentration of 2mg/mL and 4mL of deionized water are added into the beaker. And (3) placing the beaker in an ice-water bath, stirring for 30min, adding 2mL of 0.1M iron ion solution to initiate polymerization, and quickly transferring the pre-gel solution to a mold after quickly stirring uniformly. Adding 1.8g of monomer N-isopropylacrylamide, 0.0036g of cross-linking agent N, N' -methylenebisacrylamide and 0.2g of carboxymethyl cellulose into another beaker, adding 3mL of graphene oxide nanobelt dispersion liquid with the concentration of 2mg/mL and 5mL of deionized water, stirring uniformly, adding 0.0090g of 1-hydroxycyclohexyl phenyl ketone and 110 mu L of methanol premixed solution, placing the beaker into an ice water bath, continuously stirring for 20min to form a pre-gel solution, pouring the pre-gel solution onto a layer containing polyacrylic acid, standing for 15min, transferring the pre-gel solution to an ultraviolet light for polymerization, and controlling the thickness of the two layers of hydrogel to be 0.6mm and 0.8mm through a gasket. The hydrogel is designed into a long strip shape or a cross shape, under the irradiation of near infrared light or in deionized water at 65 ℃, the hydrogel is bent towards the layer containing the poly-N-isopropyl acrylamide, and in an acidic solution with the pH value of 4.5, the hydrogel is bent towards the layer containing the polyacrylic acid.
Example 6
Weighing 1g of multi-walled carbon nanotube, dispersing in 200mL of concentrated sulfuric acid, slowly adding 2.5g of potassium permanganate, uniformly stirring, heating the system to 65 ℃, reacting for 1h, and terminating the experiment by using ice water containing 15% of hydrogen peroxide. And standing at room temperature for 28h, performing suction filtration, taking an upper layer substance, and respectively and sequentially washing with deionized water, a 20% hydrochloric acid solution, ethanol and diethyl ether for several times to obtain the graphene oxide nanobelt. 1.8g of monomer acrylamide, 0.055g of calcium lignosulfonate, 0.45g of sodium dodecyl sulfate, 0.125g of potassium persulfate and 1.8mL of monomer acrylic acid are weighed out in a beaker, and 1.5mL of graphene oxide nanobelt dispersion with a concentration of 2.5mg/mL and 8mL of deionized water are added into the beaker. And (3) placing the beaker in an ice-water bath, stirring for 25min, adding 1.5mL of 0.1M silver ion solution to initiate polymerization, and quickly transferring the pre-gel solution into a mold after quickly stirring uniformly. Adding 2g of monomer N-isopropyl acrylamide, 0.004g of cross-linking agent N, N' -methylene bisacrylamide and 0.18g of carboxymethyl cellulose into another beaker, adding 1.5mL of graphene oxide nanobelt dispersion liquid with the concentration of 2.5mg/mL and 7mL of deionized water, stirring uniformly, adding 0.0080g of 1-hydroxycyclohexyl phenyl ketone and 90 muL of methanol premixed solution, placing the beaker into an ice water bath, continuously stirring for 25min to form a pre-gel solution, pouring the pre-gel solution onto a polyacrylic acid-containing layer, standing for 30min, transferring the pre-gel solution to an ultraviolet light for polymerization, and controlling the thickness of two layers of hydrogel to be 0.5mm and 1mm through a gasket. The hydrogel is designed into a long strip shape or a cross shape, under the irradiation of near infrared light or in deionized water at 60 ℃, the hydrogel is bent towards the layer containing the poly-N-isopropyl acrylamide, and in an acidic solution with the pH value of 3, the hydrogel is bent towards the layer containing the polyacrylic acid.
Claims (9)
1. A triple stimuli-responsive bilayer hydrogel actuator and a method of making the same, characterized by: the hydrogel actuator is composed of two layers of hydrogel. The first layer of hydrogel is composed of polyacrylic acid, polyacrylamide, graphene oxide nanoribbons and a dispersing agent, and polymerization is initiated by a lignin-potassium persulfate-metal ion initiation system. The second layer of hydrogel was composed of poly-N-isopropylacrylamide, carboxymethyl cellulose, and polymerization was initiated using a photoinitiated approach. The two layers of hydrogel show good mechanical properties based on the addition of the graphene oxide nanobelts and the construction of a double-network structure. In addition, the first layer of hydrogel also has good strain sensing performance and self-healing performance. The poly-N-isopropylacrylamide contains hydrophobic isopropyl and hydrophilic amide groups in a molecular chain and has excellent temperature response capability. The graphene oxide nanoribbons provide photothermal conversion capability for the bilayer hydrogel actuator, and the combination thereof with poly-N-isopropylacrylamide enables the bilayer hydrogel actuator to respond to near-infrared light. Both carboxymethyl cellulose and polyacrylic acid contain carboxyl groups, and thus can respond to a change in pH to impart pH responsiveness to the bilayer hydrogel.
2. The triple stimulus responsive bilayer hydrogel actuator of claim 1 and a method of making the same, comprising the steps of:
1) dispersing a certain mass of multi-walled carbon nanotubes in concentrated sulfuric acid, slowly adding potassium permanganate into the concentrated sulfuric acid, stirring the mixture evenly under magnetic stirring, and then heating the system to a certain temperature for continuous stirring. Ice water containing hydrogen peroxide was added to complete the reaction. Standing, separating a product, and sequentially washing with deionized water, a hydrochloric acid solution, ethanol and diethyl ether for several times to obtain a graphene oxide nanobelt;
2) adding two monomers of acrylic acid and acrylamide, dispersing agents and a pre-initiation system with different amounts and the graphene oxide nanobelt prepared in the step 1) into a beaker, adding water and stirring uniformly. Adding a metal ion solution under the condition of ice-water bath, stirring vigorously for a short time, pouring into a mould for polymerization, and controlling the thickness of the hydrogel layer;
3) placing N-isopropylacrylamide, a cross-linking agent, a graphene oxide nano-belt and carboxymethyl cellulose in deionized water, stirring, adding a certain amount of photoinitiator, and stirring for a certain time in an ice-water bath. Pouring the obtained pre-gel solution on the polyacrylic acid-polyacrylamide layer prepared in the step 2), standing for a period of time, and carrying out photo-initiated polymerization under an ultraviolet lamp to obtain a double-layer hydrogel;
4) and cutting the double-layer hydrogel into strips, bending the strips towards the layer containing the poly-N-isopropylacrylamide under the irradiation of near infrared light or in a hot water environment, and bending the double-layer hydrogel towards the layer containing the polyacrylic acid after the bent strips are placed in an acid solution.
3. The triple stimulus responsive bilayer hydrogel actuator of claim 2 and a method of making the same, wherein: in the step 1), the mass of the multi-wall carbon nano tube is 0.5-1.5g, the volume of concentrated sulfuric acid is 150-.
4. The triple stimulus responsive bilayer hydrogel actuator of claim 2 and a method of making the same, wherein: in the step 2), the used dispersing agent comprises polyvinylpyrrolidone and sodium dodecyl sulfate, and the initiation system is calcium lignosulfonate-potassium persulfate-metal ions, wherein the metal ions comprise iron ions and silver ions.
5. The triple stimuli-responsive bilayer hydrogel actuator and the method of manufacturing the same according to claim 2, wherein: in the step 2), the mass fraction of the graphene oxide nanobelt is 0.1-0.5%, the mass fraction of acrylic acid and acrylamide monomers is 10-15%, the mass fraction of the dispersing agent is 1-3%, the mass fraction of calcium lignosulfonate is 0.3-0.5%, the mass fraction of potassium persulfate is 0.5-1%, and the concentration of metal ions is 0.01-0.02 mmol.
6. The triple stimulus responsive bilayer hydrogel actuator of claim 2 and a method of making the same, wherein: the mould used for controlling the thickness of the two layers of hydrogel consists of two glass plates coated with hydrophobic materials and rubber gaskets with different thicknesses, and the thickness of each rubber gasket is 0.3-1 mm.
7. The triple stimulus responsive bilayer hydrogel actuator of claim 2 and a method of making the same, wherein: in the step 3), the cross-linking agent is N, N' -methylene-bisacrylamide, and the photoinitiator is 1-hydroxycyclohexyl phenyl ketone dissolved in methanol.
8. The triple stimulus responsive bilayer hydrogel actuator of claim 2 and a method of making the same, wherein: in the step 3), the concentration of N-isopropylacrylamide is 5-8%, the mass of the cross-linking agent is 0.15-2% of that of the N-isopropylacrylamide, the mass fraction of the graphene oxide nanobelt is 0.1-0.5%, the mass of the carboxymethyl cellulose is 10-15% of that of the N-isopropylacrylamide, and the mass of the 1-hydroxycyclohexyl phenyl ketone is 0.5-1% of that of the N-isopropylacrylamide.
9. The triple stimulus responsive bilayer hydrogel actuator of claim 2 and a method of making the same, wherein: the double-layer hydrogel is responsive to three environmental stimuli, namely temperature, pH and near infrared light. The bilayer hydrogel bends toward the poly-N-isopropylacrylamide-containing layer when placed in near-infrared irradiation or in water at a temperature greater than 32 ℃, and bends toward the poly-acrylic acid-containing layer when placed in an acidic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210495989.2A CN114854046A (en) | 2022-05-09 | 2022-05-09 | Triple-stimulus-responsive double-layer hydrogel actuator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210495989.2A CN114854046A (en) | 2022-05-09 | 2022-05-09 | Triple-stimulus-responsive double-layer hydrogel actuator and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114854046A true CN114854046A (en) | 2022-08-05 |
Family
ID=82637108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210495989.2A Pending CN114854046A (en) | 2022-05-09 | 2022-05-09 | Triple-stimulus-responsive double-layer hydrogel actuator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114854046A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975121A (en) * | 2023-02-07 | 2023-04-18 | 安徽理工大学 | Preparation method of bionic motion behavior driver made of double-layer composite material |
-
2022
- 2022-05-09 CN CN202210495989.2A patent/CN114854046A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975121A (en) * | 2023-02-07 | 2023-04-18 | 安徽理工大学 | Preparation method of bionic motion behavior driver made of double-layer composite material |
| CN115975121B (en) * | 2023-02-07 | 2024-06-04 | 安徽理工大学 | Preparation method of double-layer composite material bionic movement behavior driver |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Recent advances in designing conductive hydrogels for flexible electronics | |
| Wei et al. | Reprocessable 3D-printed conductive elastomeric composite foams for strain and gas sensing | |
| Wang et al. | Tough, adhesive, self-healable, and transparent ionically conductive zwitterionic nanocomposite hydrogels as skin strain sensors | |
| Zhang et al. | Flexible and wearable strain sensors based on conductive hydrogels | |
| CN109705370B (en) | Preparation method and application method of TEMPO nano-cellulose-polyacrylic acid gel | |
| CN108794773B (en) | Preparation method of conductive hydrogel | |
| CN110551297B (en) | Preparation method and application of gradient hydrogel soft driver | |
| CN107778514A (en) | A kind of graphene double-layer electric actuation membrane and preparation method thereof | |
| CN113999476B (en) | Dual-stimulation-responsive conductive composite hydrogel and preparation method and application thereof | |
| CN114854046A (en) | Triple-stimulus-responsive double-layer hydrogel actuator and preparation method thereof | |
| Yao et al. | Flexible, programable sensing system with poly (AAm-HEMA-SA) for human motion detection | |
| CN112985470B (en) | Flexible capacitance sensor based on silver nanowire material and preparation method | |
| Hasan et al. | Recent progress in hydrogel-based sensors and energy harvesters | |
| JP7063485B2 (en) | Composite material and its manufacturing method | |
| CN107698914B (en) | Preparation method of flexible memory polymer conductive composite hydrogel | |
| Lin et al. | Electric field sensitivity of conducting hydrogels with interpenetrating polymer network structure | |
| JP6964855B2 (en) | Conductive thin film, laminate, actuator element and its manufacturing method | |
| Huang et al. | Elastomeric polymers for conductive layers of flexible sensors: Materials, fabrication, performance, and applications | |
| CN113881068A (en) | Preparation method and application of high-performance thermoelectric hydrogel based on ion conduction | |
| Liu et al. | Novel multi-responsive soft actuator assembled with a graphene oxide nanoribbons doped strain hydrogel sensor with high sensitive and NIR-triggered performances | |
| CN114349980B (en) | Conductive hydrogel and preparation method and application thereof | |
| Li et al. | One-step in situ synthesis of tough and highly conductive ionohydrogels with water-retentive and antifreezing properties | |
| Zhao et al. | Preparation and electromechanical properties of the chitosan gel polymer actuator based on heat treating | |
| CN114656657B (en) | Preparation method of high-conductivity self-healing nano composite organic hydrogel | |
| Mo et al. | A Review of Conductive Hydrogel‐Based Wearable Temperature Sensors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |