CN111269439A - Chitosan/poly (acrylamide-acrylic acid) -Al3+Ionic hydrogel and preparation method and application thereof - Google Patents
Chitosan/poly (acrylamide-acrylic acid) -Al3+Ionic hydrogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a transparent, highly flexible, high-strength, completely self-recovering, anti-fatigue and ultrasensitive chitosan/poly (acrylamide-acrylic acid) -Al3+Ionic hydrogel and preparation method thereofMethods and applications in strain sensing devices. The invention uses AlCl3The solution realizes one-step dissolution and crosslinking of CS at high temperature to form Al3+-a CS complex. The complex is then introduced into the poly (acrylamide-acrylic acid) copolymer composite system as a double cross-linked network through the carboxyl groups on the copolymer chain and Al3+The ionic bond formed between the two groups further constructs another heavy physical crosslinking network to obtain the ionic hydrogel. The ionic hydrogel prepared by the method has the characteristics of transparency, high flexibility, high strength, complete self-recovery, fatigue resistance, ultrasensitiveness and the like, and the sensor prepared from the hydrogel realizes the collection of required key performance and can be used for wearable equipment to effectively monitor the motion of all parts of a human body.
Description
Technical Field
The invention belongs to the technical field of intelligent materials, and particularly relates to transparent, highly-telescopic, high-strength, completely self-recovery, anti-fatigue and ultrasensitive chitosan/poly (acrylamide-acrylic acid) -Al3+An ionic hydrogel, a preparation method thereof and application thereof in a strain sensing device.
Background
In the past decades, flexible smart sensor devices have shown an explosive growth trend due to their numerous applications in numerous fields such as medical monitoring, human-machine interfaces and soft robotics. At the same time, these great advances have correspondingly placed higher demands on the sensor device. The ideal next generation of "smart" sensor devices, especially visually interactive sensor devices, is characterized by a combination of transparency, sensitivity and mechanical properties (e.g., stretchability, strength, self-healing and fatigue resistance). Thus, despite the great advances made by sensor devices, it remains a great challenge to achieve their key combination of functions. An ionic hydrogel is a flexible water-based three-dimensional network polymer material with conductive salt ions inside. Recently, ionic hydrogels have shown great potential as new approaches to developing intelligent sensing devices due to their inherent conductivity, transparency, and scalability. However, the application of ionic hydrogels in wearable sensors also requires high mechanical strength, fast self-recovery properties and excellent fatigue resistance to achieve a wide range of strain sensing capability, cycling stability and durability of the sensor material.
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or disadvantages of the prior art, it is an object of the present invention to provide a chitosan/poly (acrylamide-acrylic acid) -Al3+An ionic hydrogel and a preparation method and application thereof. The hydrogel has the characteristics of transparency, high flexibility, high strength, complete self-recovery, fatigue resistance, ultrasensitiveness and the like, so that the sensing equipment prepared by utilizing the ionic hydrogel has the characteristics of stretchability, transparency, sensitivity and the like, and the technical problems of insufficient strength, poor self-recovery and fatigue resistance of the conventional ionic hydrogel sensing equipment are solved.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
chitosan/poly (acrylamide-acrylic acid) -Al3+The preparation method of the ionic hydrogel specifically comprises the following steps:
(1) adding Chitosan (CS) to AlCl3In solution, the resulting mixture is continuously stirred at high temperature for a certain time to ensure one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution;
(2) subjecting the Al of the step (1)3+Cooling the/CS compound solution to 40-70 ℃, and then sequentially adding acrylamide, acrylic acid and 2-hydroxy-2-methylacetophenone to the cooled Al3+Continuously stirring the solution of the/CS compound until all reactants are dissolved to obtain a mixed solution;
(3) finally, injecting the mixed solution obtained in the step (2) into a transparent mould, and polymerizing for a certain time under an ultraviolet lamp to form the chitosan/poly (acrylamide-acrylic acid) -Al3+An ionic hydrogel.
Further, in the above technical scheme, the chitosan and AlCl in step (1)3The dosage ratio of the solution is (0.05-0.65) by mass: (5-20) parts by volume, wherein: the mass part and the volume part are as follows: mL is used as a reference.
Further, the technical scheme and the steps(1) The AlCl3Al in solution3+The concentration of (b) is 0.025 to 0.25 mol/L.
Further, according to the technical scheme, the stirring temperature in the step (1) is 80-100 ℃.
Further, according to the technical scheme, the stirring time in the step (1) is 60-180 min.
Further, according to the technical scheme, the stirring temperature in the step (2) is 40-70 ℃.
Further, in the technical scheme, the molar ratio of the acrylamide to the acrylic acid in the step (2) is 1-60: 1, preferably 5-20: 1.
further, according to the technical scheme, the concentration of the acrylamide in the mixed solution in the step (2) is 1-6 mol/L.
Further, according to the technical scheme, the concentration of the acrylic acid in the mixed solution in the step (2) is 0.1-0.6 mol/L.
Further, in the technical scheme, the mass ratio of the 2-hydroxy-2-methylacetophenone in the step (2) to the chitosan is (0.02-0.2): (0.05-0.65).
Further, according to the technical scheme, the polymerization time in the step (3) is 0.5-3 h.
The second purpose of the invention is to provide the chitosan/poly (acrylamide-acrylic acid) -Al prepared by the method3+An ionic hydrogel.
The third purpose of the invention is to provide the chitosan/poly (acrylamide-acrylic acid) -Al prepared by the method3+The application of the ionic hydrogel can be used in wearable sensing equipment, such as a wearable strain sensor.
The invention further provides a preparation method of the wearable strain sensor, and specifically relates to chitosan/poly (acrylamide-acrylic acid) -Al connected with a lead by using an insulating tape3+The ionic hydrogel is fixed on each part of a human body.
A wearable strain sensor comprises the chitosan/poly (acrylamide-acrylic acid) -Al3+An ionic hydrogel.
The reaction mechanism of the invention is as follows: AlCl3The solution is used as a new solvent to realize one-step dissolution and crosslinking of CS at high temperature. In addition AlCl3The solution can provide abundant Al3+By Al3+Ion coordination interaction with hydroxyl and amino on CS molecule to form a reversible physical cross-linking network (Al)3+-CS complex). Subsequently, Al is added3+The CS complex is introduced into a poly (acrylamide-acrylic acid) copolymer composite system through carboxyl on a copolymer chain and Al3+The ionic bond formed between the two groups further constructs another heavy physical cross-linked network. Thus, the desired hydrogel with superior overall properties is produced by the synergistic effect of the dual ionic crosslinks.
Compared with the prior art, the chitosan/poly (acrylamide-acrylic acid) -Al provided by the invention3+An ionic hydrogel and a preparation method and application thereof. Has the following beneficial effects:
(1) colorless Al used in the invention3+The solution maintained the clarity of the ionic hydrogel prepared (up to 91.5% clarity).
(2) Al used in the invention3+With CS molecules and Al3+The double-ion cross-linked hydrogel and a poly (acrylamide-acrylic acid) chain form a double-ion cross-linked network, the mechanical property of the ionic hydrogel is greatly improved due to the mutual synergistic effect of the double-ion cross-linked network, the elongation rate reaches 1400%, the strength reaches 421.2kPa, and the ionic hydrogel has quick and complete self-recovery performance and good fatigue resistance.
(3) The large amount of ions in the ionic hydrogel prepared by the invention endows the hydrogel with excellent strain sensitivity (the sensitivity factor GF is as high as 9.6), and can repeatedly monitor movement and generate stable output signals.
(4) The ionic hydrogel sensor prepared by the invention realizes the combination of the required key characteristics, so that the sensor can be prepared into wearable equipment to safely and effectively monitor the movement of each part of a human body.
Drawings
FIG. 1 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+(CPA) ultraviolet transmission spectrum and physical display of ionic hydrogel.
FIG. 2 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+(CPA) tensile stress-strain curves of ionic hydrogels.
FIG. 3 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+Fast self-recovery and fatigue resistance profiles of (CPA) ionic hydrogels.
FIG. 4 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+Sensitivity factor and durability performance profiles of (CPA) ionic hydrogels.
FIG. 5 shows chitosan/poly (acrylamide-acrylic acid) -Al of example 1 of the present invention3+A sensor prepared from (CPA) ionic hydrogel is used for monitoring a relative resistance change curve graph when a human body moves around a wrist and swallows the throat.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The invention provides a transparent, highly-telescopic, high-strength, completely self-recovery, anti-fatigue and ultrasensitive ionic hydrogel sensor and a preparation method and application thereof. Using AlCl3The solution is used as a new solvent to realize one-step dissolution and crosslinking of CS at high temperature, thereby forming Al3+-a CS complex. Subsequently, Al is added3+the-CS complex is introduced into a poly (acrylamide-acrylic acid) copolymer composite system as a double-crosslinked network, and is reacted with Al through carboxyl on a copolymer chain3+The ionic bond formed between the two groups further constructs another heavy physical cross-linked network. Thus, passing Al3+With CS and Al3+The desired hydrogel is produced by the synergistic effect of the dual ionic crosslinks between the carboxyl groups on the copolymer chains. A large amount of Al3+Not only ensures excellent mechanical properties of the hydrogel, but also endows the hydrogel with high strain sensing performance. Furthermore, colorless Al3+The solution can also maintain good transparency of the prepared hydrogel strain sensor. Therefore, the strain sensor prepared from the hydrogel realizes the set of required key performances, and can be used for wearable equipment to effectively monitor the movement of all parts of the human body.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Chitosan/poly (acrylamide-acrylic acid) -Al of this example3+A method for preparing (CPA) ionic hydrogel, comprising the steps of:
(1) 0.3g of Chitosan (CS) was added to 10mL of Al3+AlCl with a concentration of 0.075mol/L3In aqueous solution, the resulting mixture was then continuously stirred at 90 ℃ for 90min to ensure one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution.
(2) Al obtained in the step (1)3+Cooling the/CS compound solution to 60 ℃, then sequentially adding acrylamide, acrylic acid and 0.04g of 2-hydroxy-2-methylacetophenone into the solution, and stirring at 60 ℃ until all reactants are dissolved to obtain a mixed solution; wherein: the concentration of the acrylamide in the mixed solution is 4 mol/L; the concentration of the acrylic acid in the mixed solution was 0.2 mol/L.
(3) And (3) finally, injecting the mixed solution obtained in the step (2) into a transparent mold, and polymerizing for 1h under an ultraviolet lamp to form the target CPA ionic hydrogel.
Example 2
Chitosan/poly (acrylamide-acrylic acid) -Al of this example3+A method for preparing (CPA) ionic hydrogel, comprising the steps of:
(1) 0.2g of Chitosan (CS) was added to 10mL of Al3+AlCl with concentration of 0.1mol/L3In aqueous solution, the resulting mixture was then continuously stirred at 80 ℃ for 120min to ensure one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution.
(2) Al obtained in the step (1)3+Cooling the/CS compound solution to 40 ℃, then sequentially adding acrylamide, acrylic acid and 0.04g of 2-hydroxy-2-methylacetophenone into the solution, and stirring at 40 ℃ until all reactants are dissolved to obtain a mixed solution; wherein: the concentration of the acrylamide in the mixed solution is 3 mol/L; the concentration of the acrylic acid in the mixed solution was 0.6 mol/L.
(3) And (3) finally, injecting the mixed solution obtained in the step (2) into a transparent mold, and polymerizing for 1h under an ultraviolet lamp to form the target CPA ionic hydrogel.
Example 3
Chitosan/poly (acrylamide-acrylic acid) -Al of this example3+A method for preparing (CPA) ionic hydrogel, comprising the steps of:
(1) 0.5g of Chitosan (CS) was added to 10mL of Al3+AlCl with concentration of 0.125mol/L3In aqueous solution, the resulting mixture was then stirred continuously at 100 ℃ for 180min to ensure one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution.
(2) Al obtained in the step (1)3+Cooling the/CS compound solution to 40 ℃, then sequentially adding acrylamide, acrylic acid and 0.06g of 2-hydroxy-2-methylacetophenone into the solution, and stirring at 40 ℃ until all reactants are dissolved to obtain a mixed solution; wherein: the concentration of the acrylamide in the mixed solution is 3 mol/L; the concentration of the acrylic acid in the mixed solution was 0.3 mol/L.
(3) And (3) finally, injecting the mixed solution obtained in the step (2) into a transparent mold, and polymerizing for 2 hours under an ultraviolet lamp to form the target CPA ionic hydrogel.
Example 4
Chitosan/poly (acrylamide-acrylic acid) -Al of this example3+A method for preparing (CPA) ionic hydrogel, comprising the steps of:
(1) 0.3g of Chitosan (CS) was added to 10mL of Al3+AlCl with concentration of 0.25mol/L3In aqueous solution, the resulting mixture was then continuously stirred at 80 ℃ for 150min to ensure one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution.
(2) Al obtained in the step (1)3+Cooling the/CS compound solution to 50 ℃, then sequentially adding acrylamide, acrylic acid and 0.04g of 2-hydroxy-2-methylacetophenone into the solution, and stirring at 50 ℃ until all reactants are dissolved to obtain a mixed solution; wherein: the concentration of the acrylamide in the mixed solution is 4 mol/L; the concentration of the acrylic acid in the mixed solution was 0.2 mol/L.
(3) And (3) finally, injecting the mixed solution obtained in the step (2) into a transparent mold, and polymerizing for 1h under an ultraviolet lamp to form the target CPA ionic hydrogel.
Example 5
Chitosan/poly (acrylamide-acrylic acid) -Al of this example3+A method for preparing (CPA) ionic hydrogel, comprising the steps of:
(1) 0.4g of Chitosan (CS) was added to 10mL of Al3+AlCl with a concentration of 0.075mol/L3In an aqueous solution, and then the resulting mixture was continuously stirred at 100 ℃ for 120min toEnsuring one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution.
(2) Al obtained in the step (1)3+Cooling the/CS compound solution to 60 ℃, then sequentially adding acrylamide, acrylic acid and 0.02g of 2-hydroxy-2-methylacetophenone into the solution, and stirring at 60 ℃ until all reactants are dissolved to obtain a mixed solution; wherein: the concentration of the acrylamide in the mixed solution is 2 mol/L; the concentration of the acrylic acid in the mixed solution was 0.6 mol/L.
(3) And (3) finally, injecting the mixed solution obtained in the step (2) into a transparent mold, and polymerizing for 1h under an ultraviolet lamp to form the target CPA ionic hydrogel.
And (3) performance testing:
(mono) chitosan/poly (acrylamide-acrylic acid) -Al3+Transparency of (CPA) Ionic hydrogels
FIG. 1 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+Graph of transparency test results for (CPA) ionic hydrogels. As shown in fig. 1, the transmittance of CPA ionic hydrogels can be as high as 91.5%, which shows its good transparency. The inset shows the university school badge under the CPA ionic hydrogel, which can be clearly and visually seen with the naked eye.
(II) tensile test experiment of CPA Ionic hydrogel
FIG. 2 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+(CPA) tensile stress-strain curves of ionic hydrogels. As can be seen from the figure, the tensile strength and elongation at break of the CPA ionic hydrogel are 421.2KPa, 1400%, respectively, showing high strength and highly stretchable properties.
(III) Chitosan/Poly (acrylamide-acrylic acid) -Al3+Self-recovery and fatigue resistance testing of (CPA) ionic hydrogels
FIG. 3 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+(CPA) self-recovery and fatigue resistance properties of ionic hydrogels. As shown in FIG. 3a, CPA ionic hydrogels were first subjected to a load-unload tensile test at 600% fixation strain and then allowed to stand at room temperatureThen self-recovery is performed. With the increase of the recovery time, the mechanical property of the CPA ionic hydrogel is gradually recovered, and when the recovery time is 50mins, the CPA ionic hydrogel is basically completely recovered to the original property, and the CPA ionic hydrogel shows quick and complete self-recovery property. As shown in fig. 3b, the CPA ionic hydrogel was subjected to ten consecutive cyclic loading and unloading tests under 600% fixed strain, and the CPA ionic hydrogel dissipated a large amount of energy in the first loading and unloading cycle and showed a substantially uniform dissipative hysteresis loop in the next nine times, which represents the good fatigue resistance of the CPA ionic hydrogel.
(tetra) Chitosan/Poly (acrylamide-acrylic acid) -Al3+Strain sensing performance test of (CPA) ionic hydrogel
FIG. 4 shows chitosan/poly (acrylamide-acrylic acid) -Al prepared in example 1 of the present invention3+(CPA) Strain sensing Performance testing of ionic hydrogels. FIG. 4a shows the relative resistance change (Δ R/R) of CPA ionic hydrogels0) Tensile strain (strain). The sensitivity factor (GF), defined as the slope of the curve of the relative resistance change versus tensile strain, is a fundamental parameter characterizing the sensing performance of the sensor. Therefore, the curve is further divided into three linear regions with different slopes, corresponding to GF of 2.6 (0-250%), 5.2(250- & ltSUB & gt 650%), 9.6(650- & ltSUB & gt 1000%), respectively, exhibiting high sensitivity factors. The CPA ionic hydrogel was subjected to 200 cycles of tensile release testing at a fixed 100% constant strain as shown in fig. 4b and produced a stable resistance change signal output indicating its sensing stability.
Application performance testing
The chitosan/poly (acrylamide-acrylic acid) -Al obtained in the above example 1 of the present invention was added3+(CPA) ionic hydrogels were made as wearable sensors and used for monitoring human motion tests.
The CPA ionic hydrogel sensor is connected to two sides of the CPA ionic hydrogel sensor by using a lead wire, is fixed to various parts of a human body such as fingers and throat by using an insulating adhesive tape, and measures generated electric signals along with the movement of the fingers and the throat. FIG. 5 shows chitosan/poly (acrylamide-acrylic acid) -Al using example 1 of the present invention3+(CPA) Ionic hydrogel preparationThe sensors are used for monitoring a test result graph of human body movement, and when a finger moves or the throat shakes, the hydrogel sensors attached to the finger or the throat are driven to stretch, so that signal change is generated. Meanwhile, due to different elongations of the hydrogel sensor caused by movement or vibration, the generated signals are different, so that different human body movements are effectively distinguished.
Claims (10)
1. Chitosan/poly (acrylamide-acrylic acid) -Al3+The preparation method of the ionic hydrogel is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) adding chitosan CS to AlCl3In solution, the resulting mixture is continuously stirred at high temperature for a certain time to ensure one-step dissolution and crosslinking of CS to form Al3+a/CS complex solution;
(2) subjecting the Al of the step (1)3+Cooling the/CS compound solution to 40-70 ℃, and then sequentially adding acrylamide, acrylic acid and 2-hydroxy-2-methylacetophenone to the cooled Al3+Continuously stirring the solution of the/CS compound until all reactants are dissolved to obtain a mixed solution;
(3) finally, injecting the mixed solution obtained in the step (2) into a transparent mould, and polymerizing for a certain time under an ultraviolet lamp to form the chitosan/poly (acrylamide-acrylic acid) -Al3+An ionic hydrogel.
2. Chitosan/poly (acrylamide-acrylic acid) -Al according to claim 13+The preparation method of the ionic hydrogel is characterized by comprising the following steps: the chitosan and AlCl in the step (1)3The dosage ratio of the solution is (0.05-0.65) by mass: (5-20) parts by volume, wherein: the mass part and the volume part are as follows: mL is used as a reference.
3. Chitosan/poly (acrylamide-acrylic acid) -Al according to claim 13+The preparation method of the ionic hydrogel is characterized by comprising the following steps: AlCl described in step (1)3Al in solution3+The concentration of (b) is 0.025 to 0.25 mol/L.
4. Chitosan/poly (acrylamide-acrylic acid) -Al according to claim 13+The preparation method of the ionic hydrogel is characterized by comprising the following steps: the stirring temperature in the step (1) is 80-100 ℃.
5. Chitosan/poly (acrylamide-acrylic acid) -Al according to claim 13+The preparation method of the ionic hydrogel is characterized by comprising the following steps: the mol ratio of the acrylamide to the acrylic acid in the step (2) is 1-60: 1.
6. chitosan/poly (acrylamide-acrylic acid) -Al according to claim 13+The preparation method of the ionic hydrogel is characterized by comprising the following steps: the mass ratio of the 2-hydroxy-2-methylacetophenone to the chitosan in the step (2) is (0.02-0.2): (0.05-0.65).
7. Chitosan/poly (acrylamide-acrylic acid) -Al according to claim 13+The preparation method of the ionic hydrogel is characterized by comprising the following steps: the polymerization time in the step (3) is 0.5-3 h.
8. Chitosan/poly (acrylamide-acrylic acid) -Al according to any one of claims 1 to 73+Preparation method of ionic hydrogel and prepared chitosan/poly (acrylamide-acrylic acid) -Al3+An ionic hydrogel.
9. Chitosan/poly (acrylamide-acrylic acid) -Al prepared by the method of any one of claims 1 to 73+Ionic hydrogel or chitosan/poly (acrylamide-acrylic acid) -Al according to claim 83+Use of an ionic hydrogel in a wearable strain sensor.
10. A wearable strain sensor, characterized by: comprises the chitosan/poly (acrylamide-acrylic acid) -Al prepared by the method of any one of claims 1 to 73+An ionic hydrogel or the chitosan/poly (propylene) of claim 8Enamide-acrylic acid) -Al3+An ionic hydrogel.
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