CN114395145A - Preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel - Google Patents
Preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel Download PDFInfo
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- 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
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- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention discloses a preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel, which comprises the following steps: firstly, modifying graphene oxide by tannic acid to prepare tannic acid functionalized reduced graphene oxide powder, doping the tannic acid functionalized reduced graphene oxide powder into polyvinyl alcohol by a blending method, and then obtaining the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel by a freeze-thaw method. The hydrogel prepared by the method enhances the dispersibility of the conductive filler in the gel matrix, and simultaneously improves the conductivity and mechanical properties of the hydrogel.
Description
Technical Field
The invention belongs to the technical field of polymer composite material preparation, and particularly relates to a preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel.
Background
The hydrogel is a flexible material with a three-dimensional network structure, which is formed by taking water as a medium and through the crosslinking action of intermolecular covalent bonds, hydrogen bonds and other bond positions of a high polymer material containing hydrophilic groups. Nanocomposite hydrogels are typically prepared by adding nanoscale fillers to immiscible soft or rigid components by physical blending or in situ growth methods. Compared with pure polymer hydrogel, the nano composite hydrogel has more abundant performance.
Graphene Oxide (GO) is an effective filler, is produced by oxidation stripping of graphite, has a large specific surface area, and can improve the electrical properties, mechanical properties, thermal properties and the like of the composite material. However, in the currently prepared graphene oxide nanocomposite hydrogel, due to poor conductivity of graphene oxide and insufficient compatibility and interface bonding strength between graphene oxide and hydrogel, the electrical property and mechanical property of the composite material cannot meet the requirements. Therefore, modifying graphene oxide to improve its electrical conductivity, compatibility with hydrogel, and interface bonding strength is a problem that needs to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of tannin modified GO/polyvinyl alcohol nano composite hydrogel, which enhances the dispersibility of graphene oxide in a gel matrix and simultaneously improves the conductivity and mechanical properties of the hydrogel.
The technical scheme adopted by the invention is that the preparation method of the tannin modified GO/polyvinyl alcohol nano composite hydrogel is implemented according to the following steps:
step 2, adding polyvinyl alcohol into deionized water, stirring to obtain a suspension, pouring the suspension into a round-bottom flask, and placing the round-bottom flask in an oil bath for stirring reaction to obtain a solution b;
and 3, adding the tannic acid functionalized reduced graphene oxide prepared in the step 1 into the solution b, placing the solution in an oil bath, stirring the solution to obtain a mixed solution a, pouring the mixed solution a into a polytetrafluoroethylene mold, and performing freeze-thaw cycling to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps:
adding graphene oxide into a tris solution, uniformly stirring, and performing ultrasonic treatment to obtain a solution a; and then adding tannic acid, adjusting the pH value of the solution a to 8-10 by using HCl, stirring for reaction, washing by using deionized water, performing suction filtration, and performing cold drying to obtain black powdery tannic acid functionalized reduced graphene oxide.
The concentration of the trihydroxymethyl aminomethane solution is 0.1-0.15 moL/L; the mass ratio of the tannic acid to the graphene oxide is 2-4: 1; the concentration of HCl is 0.1-0.3 moL/L.
The ultrasonic power is 120-150W, and the ultrasonic time is 20-30 min; stirring and reacting for 8-10 h; during cold drying, the mixture is frozen in a cold trap at the temperature of-55 to-65 ℃ for 3 to 6 hours and then dried for 24 to 48 hours.
In the step 2, the mass fraction of the polyvinyl alcohol suspension is 6-9%; the oil bath reaction temperature is 95 ℃, and the oil bath reaction time is 3-5 h.
In the step 3, the concentration of the tannic acid functionalized reduced graphene oxide added into the solution b is 0.5-5 moL/L; the oil bath temperature is 90 ℃, and the oil bath time is 1-3 h.
In the step 3, when freeze-thaw cycle is carried out, the freezing temperature is-20 to-30 ℃, the freezing time is 10 to 15 hours, the thawing time is 3 to 6 hours, and the number of freeze-thaw cycles is 2 to 5.
The invention has the beneficial effects that:
the tannin modified graphene oxide/polyvinyl alcohol nano composite hydrogel enhances the dispersibility of the conductive filler in the gel matrix, and simultaneously improves the conductive performance and the mechanical performance of the hydrogel. In addition, the modified material used by the method is green and natural, meets the requirement of green environmental protection, has simple preparation process, is easy to realize production environment, and achieves the production mode with low cost and high efficiency.
Drawings
FIG. 1 is an infrared spectrum of a tannic acid-modified graphene oxide and an unmodified graphene oxide according to the present invention;
figure 2 is a tensile stress-strain graph of an unmodified hydrogel versus a tannic acid modified GO/polyvinyl alcohol hydrogel of the invention.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The invention relates to a preparation method of tannin modified GO/polyvinyl alcohol nanocomposite hydrogel, which is characterized in that natural polyphenol compound tannin is adopted to modify graphene oxide, and the tannin modified graphene oxide is doped into polyvinyl alcohol by a blending method to prepare the nanocomposite hydrogel; the method is implemented according to the following steps:
adding graphene oxide into a Tris solution, uniformly stirring, and performing ultrasonic treatment to obtain a solution a; then adding tannic acid, adjusting the pH value of the solution a to 8-10 by using HCl, stirring at normal temperature for reaction, washing by using deionized water, performing suction filtration, and performing cold drying to obtain black powdery tannic acid functionalized reduced graphene oxide;
wherein the concentration of the tris solution is 0.1-0.15 moL/L; the mass ratio of the tannic acid to the graphene oxide is 2-4: 1; the ultrasonic power is 120-150W, and the ultrasonic time is 20-30 min; the HCl concentration is 0.1-0.3 moL/L; stirring and reacting for 8-10 h; during cold drying, freezing the mixture in a cold trap at the temperature of between 55 ℃ below zero and 65 ℃ below zero for 3 to 6 hours, and then drying the mixture for 24 to 48 hours;
step 2, preparing a polyvinyl alcohol solution;
adding polyvinyl alcohol into deionized water, magnetically stirring to obtain a suspension, pouring the suspension into a round-bottom flask, putting the round-bottom flask into an oil bath, and stirring for reaction to obtain a solution b;
the mass fraction of the polyvinyl alcohol suspension is 6-9%; the oil bath reaction temperature is 95 ℃, and the oil bath reaction time is 3-5 h;
step 3, adding the tannic acid functionalized reduced graphene oxide prepared in the step 1 into the solution b, placing the solution in an oil bath, stirring the solution to obtain a mixed solution a, pouring the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, and performing freeze-thaw cycle to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel with high conductivity and excellent mechanical property;
the concentration of the tannic acid functionalized reduced graphene oxide added into the solution b is 0.5-5 moL/L; the oil bath temperature is 90 ℃, and the oil bath time is 1-3 h;
and (3) performing freeze-thaw cycling at the freezing temperature of-20 to-30 ℃, for 10 to 15 hours, for 3 to 6 hours, and for 2 to 5 times.
According to the infrared spectrogram of the tannic acid modified graphene oxide and the unmodified graphene oxide, as shown in fig. 1, it can be seen that after GO is reduced by TA, epoxy functional groups, epoxy and alkoxy stretching vibration peaks in a graphene sample are obviously weakened or even disappear, namely that GO is successfully modified and reduced.
FIG. 2 is a tensile stress-strain plot of unmodified polyvinyl alcohol hydrogel and TA-GO/PVA conductive hydrogels of different conductive filler concentrations. From FIG. 2, it can be seen that the hydrogel without tannin modified GO filler (PVA Hydrogels) has a tensile strength of only 76.27kPa, while the nanocomposite hydrogel with 2mg/ml and 5mg/ml tannin modified GO (TA-GO)2mg/ml PVA Hydrogels、TA-GO5mg/mlPVA Hydrogels) have tensile strengths of 228.84kPa and 574.79kPa respectively, and compared with unmodified hydrogel, the tensile strength of the hydrogel prepared by the invention is improved by 3-7.5 times. Compared with unmodified hydrogel, the tensile strength of the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel is obviously improved. Namely, the nanocomposite hydrogel of the present invention has more excellent mechanical properties than unmodified one.
Example 1
The invention discloses a preparation method of tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel, which is implemented according to the following steps:
Step 2, 5.4g polyvinyl alcohol was added to 60mL deionized water, stirred magnetically for 1h, allowed to foam to give a suspension, which was poured into a round bottom flask, stirred mechanically at 1000r/min and placed in a 95 ℃ oil bath for 3h to give solution b.
And 3, adding 60mg of the tannic acid functionalized reduced graphene oxide prepared in the first step into the solution b, stirring at the speed of 1500r/min, placing in an oil bath at 90 ℃ for 2h to obtain a mixed solution a, injecting the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, placing in a refrigerator, freezing at-24 ℃ for 12h, unfreezing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel with high conductivity and excellent mechanical property.
Example 2
The invention discloses a preparation method of tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel, which is implemented according to the following steps:
Step 2, 5.4g polyvinyl alcohol was added to 60mL deionized water, stirred magnetically for 1h, allowed to foam to give a suspension, which was poured into a round bottom flask, stirred mechanically at 1000r/min and placed in a 95 ℃ oil bath for 3h to give solution b.
And 3, adding 120mg of the tannic acid functionalized reduced graphene oxide prepared in the first step into the solution b, stirring at the speed of 1500r/min, placing in an oil bath at 90 ℃ for 2h to obtain a mixed solution a, injecting the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, placing into a refrigerator, freezing at-24 ℃ for 12h, unfreezing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel with high conductivity and excellent mechanical property.
Example 3
The invention discloses a preparation method of tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel, which is implemented according to the following steps:
Step 2, 5.4g polyvinyl alcohol was added to 60mL deionized water, stirred magnetically for 1h, allowed to foam to give a suspension, which was poured into a round bottom flask, stirred mechanically at 1000r/min and placed in a 95 ℃ oil bath for 3h to give solution b.
And 3, adding 180mg of the tannic acid functionalized reduced graphene oxide prepared in the first step into the solution b, stirring at the speed of 1500r/min, placing in an oil bath at 90 ℃ for 2h to obtain a mixed solution a, injecting the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, placing in a refrigerator, freezing at-24 ℃ for 12h, unfreezing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel with high conductivity and excellent mechanical property.
Example 4
The invention discloses a preparation method of tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel, which is implemented according to the following steps:
Step 2, 5.4g polyvinyl alcohol was added to 60mL deionized water, stirred magnetically for 1h, allowed to foam to give a suspension, which was poured into a round bottom flask, stirred mechanically at 1000r/min and placed in a 95 ℃ oil bath for 3h to give solution b.
And 3, adding 240mg of the tannic acid functionalized reduced graphene oxide prepared in the first step into the solution b, stirring at the speed of 1500r/min, placing in an oil bath at 90 ℃ for 2h to obtain a mixed solution a, injecting the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, placing in a refrigerator, freezing at-24 ℃ for 12h, unfreezing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel with high conductivity and excellent mechanical property.
Example 5
The invention discloses a preparation method of tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel, which is implemented according to the following steps:
Step 2, 5.4g polyvinyl alcohol was added to 60mL deionized water, stirred magnetically for 1h, allowed to foam to give a suspension, which was poured into a round bottom flask, stirred mechanically at 1000r/min and placed in a 95 ℃ oil bath for 3h to give solution b.
And 3, adding 300mg of the tannic acid functionalized reduced graphene oxide prepared in the first step into the solution b, stirring at the speed of 1500r/min, placing in an oil bath at 90 ℃ for 2h to obtain a mixed solution a, injecting the mixed solution a into a Polytetrafluoroethylene (PTFE) mold, placing in a refrigerator, freezing at-24 ℃ for 12h, unfreezing at room temperature for 3h, and performing freeze-thaw cycle for 3 times to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel with high conductivity and excellent mechanical property.
The performance of the tannic acid modified graphene oxide/polyvinyl alcohol nanocomposite hydrogel prepared in the embodiment of the present invention is detected, and the results are shown in tables 1 and 2:
TABLE 1 comparison of results of electrical property measurements
| Sample name | Resistor (Qian Ou) |
| Example 1 | 376.00 |
| Example 2 | 110.00 |
| Example 3 | 86.20 |
| Example 4 | 68.55 |
| Example 5 | 55.00 |
| Unmodified polyvinyl alcohol hydrogels | 1570 |
TABLE 2 comparison of the results of the compressive Strength measurements
| Sample name | Compressive Strength (kPa) |
| Example 1 | 897.762 |
| Example 2 | 1213.940 |
| Example 3 | 1352.830 |
| Example 4 | 1523.451 |
| Example 5 | 1730.766 |
| Unmodified polyvinyl alcohol hydrogels | 800.712 |
As can be seen from the resistance test of the hydrogel in table 1, the resistance of the hydrogel gradually decreases with the doping of the conductive filler, namely, the hydrogel prepared shows more and more excellent conductivity with the doping of the conductive filler, namely, the tannic acid modified graphene oxide. Therefore, compared with the unmodified graphene oxide/polyvinyl alcohol nano composite hydrogel, the tannin modified graphene oxide/polyvinyl alcohol nano composite hydrogel prepared by the invention has excellent electrical properties.
As can be seen from the compression performance test of the hydrogel in table 2, the compressive strength of the hydrogel gradually increases with the increase of the doping concentration of the conductive filler, tannic acid modified graphene oxide. Compared with the unmodified graphene oxide/polyvinyl alcohol nano composite hydrogel, the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel prepared by the invention has more excellent mechanical properties.
The graphene oxide is subjected to non-covalent modification by using Tannic Acid (TA), and is used as a reducing agent and a stabilizing agent, so that the uniform distribution of reduced graphene oxide (rGO) in a polyvinyl alcohol polymer network is promoted. The tannin modified GO serves as a conductive component and a nano reinforcing agent in the hydrogel, so that the hydrogel is endowed with excellent conductivity, and the mechanical property of the hydrogel is improved.
The performance of the hydrogel is changed by adding the conductive filler, namely the tannic acid modified graphene oxide, and the reasons are as follows: the hydroxyl in TA reacts with the carbon atoms in GO to form ether bonds, and after suction filtration and washing, the formation of catechol and reduced graphene oxide in TA is caused along with the elimination of water. The tannic acid has a benzene ring structure, and when the tannic acid is used for reducing graphene oxide, the tannic acid also has an interaction with a conjugated n-type bond on a graphene sheet layer, and can be inserted between the graphene sheet layers, so that the stacking of the graphene sheet layers is effectively hindered. So that the TA modified GO can be uniformly distributed in the polyvinyl alcohol polymer network, and the conductivity of the hydrogel is increased. ② the Tannin (TA) modified GO and the hydroxyl on the molecular chain of the polyvinyl alcohol (PVA) form various hydrogen bond combinations, so that the interfacial bonding force between the TA-GO and the PVA is increased, and the mechanical property of the composite hydrogel is improved.
Claims (7)
1. The preparation method of the tannin modified GO/polyvinyl alcohol nano composite hydrogel is characterized by comprising the following steps:
step 1, preparing tannic acid functionalized reduced graphene oxide;
step 2, adding polyvinyl alcohol into deionized water, stirring to obtain a suspension, pouring the suspension into a round-bottom flask, and placing the round-bottom flask in an oil bath for stirring reaction to obtain a solution b;
and 3, adding the tannic acid functionalized reduced graphene oxide prepared in the step 1 into the solution b, placing the solution in an oil bath, stirring the solution to obtain a mixed solution a, pouring the mixed solution a into a polytetrafluoroethylene mold, and performing freeze-thaw cycling to obtain the tannic acid modified graphene oxide/polyvinyl alcohol nano composite hydrogel.
2. The method for preparing the tannin modified GO/polyvinyl alcohol nanocomposite hydrogel according to claim 1, wherein the step 1 specifically comprises:
adding graphene oxide into a tris solution, uniformly stirring, and performing ultrasonic treatment to obtain a solution a; and then adding tannic acid, adjusting the pH value of the solution a to 8-10 by using HCl, stirring for reaction, washing by using deionized water, performing suction filtration, and performing cold drying to obtain black powdery tannic acid functionalized reduced graphene oxide.
3. The method for preparing the tannin modified GO/polyvinyl alcohol nanocomposite hydrogel according to claim 2, wherein the concentration of the tris solution is 0.1-0.15 moL/L; the mass ratio of the tannic acid to the graphene oxide is 2-4: 1; the concentration of HCl is 0.1-0.3 moL/L.
4. The preparation method of the tannin modified GO/polyvinyl alcohol nanocomposite hydrogel according to claim 2, wherein the ultrasonic power is 120-150W, and the ultrasonic time is 20-30 min; stirring and reacting for 8-10 h; during cold drying, the mixture is frozen in a cold trap at the temperature of-55 to-65 ℃ for 3 to 6 hours and then dried for 24 to 48 hours.
5. The method for preparing the tannin modified GO/polyvinyl alcohol nanocomposite hydrogel according to claim 1, wherein in the step 2, the mass fraction of the polyvinyl alcohol suspension is 6-9%; the oil bath reaction temperature is 95 ℃, and the oil bath reaction time is 3-5 h.
6. The method for preparing the tannin modified GO/polyvinyl alcohol nanocomposite hydrogel according to claim 1, wherein in the step 3, the concentration of the tannin functionalized reduced graphene oxide added into the solution b is 0.5-5 moL/L; the oil bath temperature is 90 ℃, and the oil bath time is 1-3 h.
7. The preparation method of the tannin modified GO/polyvinyl alcohol nanocomposite hydrogel according to claim 1, wherein in the step 3, when freeze-thaw cycles are performed, the freezing temperature is-20 to-30 ℃, the freezing time is 10 to 15 hours, the thawing time is 3 to 6 hours, and the number of the freeze-thaw cycles is 2 to 5.
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