CN112679754B - Preparation method and application of photo-thermal conversion hydrogel - Google Patents
Preparation method and application of photo-thermal conversion hydrogel Download PDFInfo
- Publication number
- CN112679754B CN112679754B CN202110052047.2A CN202110052047A CN112679754B CN 112679754 B CN112679754 B CN 112679754B CN 202110052047 A CN202110052047 A CN 202110052047A CN 112679754 B CN112679754 B CN 112679754B
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- molybdenum dioxide
- hectorite
- isopropylacrylamide
- preparation
- 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.)
- Active
Links
Images
Landscapes
- Medicinal Preparation (AREA)
Abstract
The invention belongs to the field of polymer composite functional materials, and discloses a preparation method of photo-thermal conversion hydrogel, which comprises the following steps: (1) dispersing molybdenum dioxide in water to prepare a molybdenum dioxide dispersion liquid; (2) dissolving hectorite in water, adding the molybdenum dioxide dispersion liquid obtained in the step (1), and uniformly mixing to obtain a mixed solution; (3) dissolving N-isopropylacrylamide in the mixed solution obtained in the step (2) in an ice bath and in a nitrogen atmosphere, adding an initiator, a cross-linking agent and an auxiliary initiator, and uniformly mixing to obtain a mixed pre-polymerization solution; (4) and (4) injecting the mixed pre-polymerization liquid obtained in the step (3) into a mold, and reacting at room temperature for 24 hours to obtain the hydrogel. The hydrogel prepared by the invention has obvious photo-thermal conversion effect, good light transmittance and mechanical property, and excellent temperature rise and fall cycling stability, and has huge application potential in the fields of intelligent hydrogel drivers, remote light-operated micro-flow valves, photo-thermal physical therapy sheets and the like.
Description
Technical Field
The invention relates to the field of polymer composite functional materials, in particular to a preparation method and application of a photothermal conversion hydrogel.
Background
The photoresponse hydrogel is one of intelligent hydrogels, has controllable intelligence effect mainly under the action of light irradiation induction, and has no direct physical contact with external factors, so that the photoresponse hydrogel is widely researched in the fields of soft robots, sensors, micro devices, drug release and the like.
Near infrared light is considered an ideal light source for triggering the photoresponsive behavior of hydrogels, since the intensity, timing and location of the near infrared light irradiation can be easily controlled artificially. Composite hydrogel prepared by combining thermosensitive poly-N-isopropylacrylamide hydrogel with near-infrared photothermal conversion fillers such as graphene oxide, carbon nanotubes, ferroferric oxide nanoparticles, gold nanorods and molybdenum disulfide has been widely researched. However, the carbon-based nanomaterial has poor dispersibility in a hydrogel system, the noble metal nanomaterial has high preparation cost and certain cytotoxicity, and the transition metal double-halogenated photothermal material has poor chemical stability and is easily oxidized under the conditions of high temperature or repeated laser irradiation, thereby hindering the practical application of the transition metal double-halogenated photothermal material. In addition, the composite hydrogel prepared by doping the traditional photothermal filler has extremely poor transparency, is completely black or has too deep color and is completely light-proof, and cannot be applied to the field of visualization.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide a preparation method and application of a photothermal conversion hydrogel.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a method for preparing a photothermal conversion hydrogel, comprising the steps of:
(1) dispersing molybdenum dioxide in water to obtain molybdenum dioxide dispersion liquid;
(2) dispersing hectorite in water to obtain a hectorite solution, adding the molybdenum dioxide dispersion liquid obtained in the step (1) into the hectorite solution, and uniformly mixing to obtain a mixed solution;
(3) dissolving N-isopropyl acrylamide in the mixed solution obtained in the step (2) in an ice bath and an inert gas atmosphere, adding an initiator, a cross-linking agent and an auxiliary initiator, and uniformly mixing to obtain a mixed pre-polymerization solution;
(4) and (4) injecting the mixed pre-polymerization liquid obtained in the step (3) into a mold, and reacting for 24 hours at room temperature to obtain a hydrogel sample.
According to the preparation method, the mass ratio of the N-isopropylacrylamide to the molybdenum dioxide in the molybdenum dioxide dispersion liquid in the step (3) is preferably 1: (0.003-0.015).
According to the preparation method, the mass ratio of the N-isopropylacrylamide to the hectorite in the step (3) is preferably 1 (0.05-0.3); more preferably, the mass ratio of N-isopropylacrylamide to hectorite is 1: 0.2.
According to the above production method, preferably, the initiator in the step (3) is ammonium persulfate; the cross-linking agent is N, N' -methylene bisacrylamide; the coinitiator is N, N, N ', N' -tetramethyl ethylenediamine.
According to the preparation method, preferably, the mass ratio of the ammonium persulfate to the N-isopropylacrylamide in the step (3) is (0.01-0.04): 1; the mass ratio of the N, N' -methylene bisacrylamide to the N-isopropylacrylamide is (0.0005-0.004): 1; the dosage of the N, N, N ', N' -tetramethyl ethylenediamine is 10 mu L/1g N-isopropyl acrylamide; more preferably, the mass ratio of the ammonium persulfate to the N-isopropylacrylamide is 0.02: 1; the mass ratio of the N, N' -methylene bisacrylamide to the N-isopropyl acrylamide is 0.001: 1.
according to the above preparation method, preferably, the molybdenum dioxide is a commercially available reagent or prepared according to the following method: uniformly mixing molybdenum trioxide and zinc powder according to the weight ratio of 1:0.02, calcining for 4 hours at 400 ℃ under the protection of nitrogen to obtain a product, washing the product with hydrochloric acid solution, ammonia water solution and water in sequence to obtain a precipitate, and drying at 50 ℃ to obtain molybdenum dioxide.
In a second aspect, the present invention provides a photothermal conversion hydrogel, that is, a photothermal conversion hydrogel obtained according to the above-described production method.
In a third aspect, the invention provides an application of the photothermal conversion hydrogel in a light-operated micro-fluidic valve.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) according to the invention, molybdenum dioxide is added into a reaction system of hectorite and N-isopropylacrylamide to prepare the hydrogel, and the prepared hydrogel has a remarkable photo-thermal conversion effect and good recycling performance; and with the increase of the content of molybdenum dioxide in the hydrogel, the heating rate and the steady-state temperature of the hydrogel are increased; when the content of molybdenum dioxide in the hydrogel is 1.5mg/mL, the using wavelength is 808nm and the power is 0.8W/cm2The surface temperature of the hydrogel is raised by 30 ℃ after the laser irradiation for 15 s; meanwhile, the temperature of the hydrogel is continuously increased along with the prolonging of the illumination time, and after the illumination time reaches 90s, the surface temperature of the hydrogel basically reaches a steady-state temperature which is about 70 ℃; in addition, the heating rate and steady-state temperature of the hydrogel can be adjusted by the laser power, and the heating rate and steady-state temperature increase with increasing laser power.
(2) The hydrogel prepared by the invention has obvious photo-thermal conversion effect on near infrared light, also has photo-thermal conversion effect on light in other wavelength ranges, and has the power of 3.0W/cm2Under the irradiation of the fluorescent lamp, the steady-state temperature of the hydrogel reaches about 40 ℃, is increased by 18 ℃ compared with the initial temperature, and has excellent photo-thermal conversion effect.
(3) The composite hydrogel prepared by the invention has good light transmission, and when the content of molybdenum dioxide in the hydrogel is 1.5mg/mL, the light transmittance of the composite hydrogel at 600nm can still reach 27%. Compared with the traditional photo-thermal conversion hydrogel compounded by carbon nano tubes or graphene oxide, the hydrogel prepared by the invention has good photo-thermal conversion effect and good light transmittance, and is beneficial to the application in the field of intelligent visualization.
(4) The hydrogel prepared by the invention can be used for preparing a micro-fluidic valve device, and the prepared micro-fluidic valve device can control the circulation of a micro-fluidic channel through remote laser; the hydrogel has great application value in the fields of intelligent drive, miniature light control devices, photo-thermal physical therapy patches and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a photothermal conversion hydrogel and its response under near-infrared "On-Off" conditions according to an embodiment of the present invention;
FIG. 2 shows the hydrogel samples prepared in examples 1 to 6 under near infrared laser (808 nm, 0.8W/cm)2) Graph of temperature change under irradiation;
FIG. 3 is a graph showing transmittance profiles of hydrogel samples prepared in examples 1 to 6;
FIG. 4 is a stress-strain graph of hydrogel samples prepared in example 5 and examples 7-10;
FIG. 5 is a graph showing the temperature changes of hydrogel samples prepared in example 4 under irradiation of near infrared laser (808 nm) of different powers;
FIG. 6 is a graph of the change in temperature of the hydrogel sample prepared in example 5 after 30 cycles under the near-infrared laser "On-Off" condition;
FIG. 7 is a graph showing the temperature change of the hydrogel samples prepared in examples 5 and 6 under irradiation of a fluorescent lamp;
FIG. 8 is a graph showing the change of the hydrogel prepared according to the present invention as a micro flow valve under irradiation of near infrared laser; wherein a is the hydrogel prepared in example 6 and b is the hydrogel prepared in example 5.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
Discussion experiment of molybdenum dioxide
In order to investigate the influence of the amount of molybdenum dioxide on the hydrogel properties, examples 1 to 6 were carried out, and the details of examples 1 to 6 are as follows.
Example 1:
a preparation method of a photothermal conversion hydrogel is shown in a schematic flow chart of fig. 1, and specifically comprises the following steps:
(1) dispersing 30mg of molybdenum dioxide in 10mL of deionized water, carrying out ultrasonic treatment for 0.5h, and stirring for 3h to obtain a molybdenum dioxide dispersion liquid with the concentration of 3 mg/mL; the molybdenum dioxide is a commercial reagent or is prepared by the following method: uniformly mixing molybdenum trioxide and zinc powder according to the weight ratio of 1:0.02, calcining for 4 hours at 400 ℃ under the protection of nitrogen to obtain a black product, washing the black product with hydrochloric acid solution, ammonia water solution and water in sequence to obtain a precipitate, and drying at 50 ℃ to obtain molybdenum dioxide.
(2) Dispersing 200mg of hectorite in deionized water, performing ultrasonic treatment for 30min to obtain a clear and transparent hectorite solution, adding the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL obtained in the step (1) into the hectorite solution, and stirring and mixing uniformly to obtain a mixed solution; wherein the using amount of the deionized water is 9.0 mL; the dosage of the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL is 1.0mL, and the concentration of the molybdenum dioxide in the hydrogel is 0.3 mg/mL.
(3) Under ice bath and nitrogen atmosphere, dissolving 1.0g N-isopropyl acrylamide in the mixed solution obtained in the step (2), then adding 20mg of initiator ammonium persulfate, 1.0mg of cross-linking agent N, N ' -methylene bisacrylamide and 10 mu L of auxiliary initiator N, N, N ', N ' -tetramethyl ethylenediamine, and uniformly mixing to obtain a mixed pre-polymerization solution; wherein the mass ratio of the molybdenum dioxide to the N-isopropylacrylamide in the mixed pre-polymerization solution is 0.003: 1.
(4) And (4) injecting the mixed prepolymer solution obtained in the step (3) into a polytetrafluoroethylene mold, and reacting for 24 hours at room temperature to obtain a hydrogel sample.
Example 2:
the contents of example 2 are substantially the same as those of example 1, except that:
in the step (2), the using amount of the deionized water is 8.0 mL; the dosage of the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL is 2.0mL, and the concentration of the molybdenum dioxide in the hydrogel is 0.6 mg/mL; in the step (3), the mass ratio of the molybdenum dioxide to the N-isopropylacrylamide in the mixed pre-polymerization solution is 0.006: 1.
example 3:
the contents of example 3 are substantially the same as those of example 1, except that:
in the step (2), the using amount of the deionized water is 7.0 mL; the dosage of the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL is 3.0mL, and the concentration of the molybdenum dioxide in the hydrogel is 0.9 mg/mL; in the step (3), the mass ratio of the molybdenum dioxide to the N-isopropylacrylamide in the mixed pre-polymerization solution is 0.009: 1.
example 4:
the contents of example 4 are substantially the same as those of example 1, except that:
in the step (2), the using amount of the deionized water is 6.0 mL; the dosage of the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL is 4.0mL, and the concentration of the molybdenum dioxide in the hydrogel is 1.2 mg/mL; in the step (3), the mass ratio of the molybdenum dioxide to the N-isopropylacrylamide in the mixed pre-polymerization solution is 0.012: 1.
example 5:
the contents of example 5 are substantially the same as those of example 1, except that:
in the step (2), the using amount of the deionized water is 5.0 mL; the dosage of the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL is 5.0mL, and the concentration of the molybdenum dioxide in the hydrogel is 1.5 mg/mL; in the step (3), the mass ratio of the molybdenum dioxide to the N-isopropylacrylamide in the mixed pre-polymerization solution is 0.015: 1.
example 6:
the contents of example 6 are substantially the same as those of example 1, except that:
in the step (2), the using amount of the deionized water is 10.0 mL; the dosage of the molybdenum dioxide dispersion liquid with the concentration of 3mg/mL is 0mL, namely, molybdenum dioxide is not added.
In order to investigate the effect of molybdenum dioxide on the photothermal conversion effect of the hydrogel, the hydrogel samples prepared in examples 1 to 6 were cut into rectangular blocks of 2.0cm × 2.0cm × 0.2cm (length × width × thickness), respectively, and then placed in the center of a petri dish, and deionized water was injected around the center. Using a near-infrared laser (808 nm, 0.8W/cm)2) Irradiating the central position of the cuboid hydrogel, and simultaneously recording the surface temperature change process of the hydrogel by using a thermal imaging instrument. The test results are shown in fig. 2 and table 1.
TABLE 1 influence of the molybdenum dioxide content on the warming effect of the hydrogels
Note: t in the table represents temperature in units of; the lower right hand corner of T represents time in units of s; Δ T represents TMaxAnd T0The difference of (a).
As can be seen from FIG. 2 and Table 1, the temperature-raising effect of the hydrogel is in a positive correlation with the concentration of molybdenum dioxide in the hydrogel. The hydrogel with higher molybdenum dioxide concentration has more obvious photo-thermal conversion effect. The concentration of molybdenum dioxide in the hydrogel sample obtained in the embodiment 5 is 1.5mg/mL, under the irradiation of a light source, the molybdenum dioxide in the hydrogel matrix rapidly absorbs near infrared light energy and is converted into a large amount of heat energy, so that the surface temperature of the hydrogel rapidly exceeds the critical phase transition temperature point, the hydrogel generates response, and the volume changes; the hydrogel surface temperature increased from 20.0 ℃ to 48.1 ℃ in only about 15 seconds, and when the irradiation time continued to be extended, the hydrogel reached a maximum steady state temperature of 69.2 ℃ and the temperature increased by 49.2 ℃ compared to the initial temperature. In contrast, the maximum steady-state temperature of the hydrogel obtained in example 6, which did not contain molybdenum dioxide, was 29.6 ℃ under the same conditions, which only increased by 9.6 ℃ compared to the initial temperature. The result shows that the molybdenum dioxide is introduced into the hydrogel system, so that the hydrogel has an excellent photo-thermal conversion effect.
In order to investigate the influence of the amount of molybdenum dioxide on the light transmittance of the hydrogel, the hydrogel film samples prepared in examples 1 to 6 were cut into square films of 20mm × 20mm in thickness of 2mm, and the films were attached to a sample holder of an ultraviolet spectrophotometer to perform a transmittance test, with a wavelength measurement range of 300nm to 800 nm. The test results are shown in fig. 3 and table 2.
TABLE 2 influence of the amount of molybdenum dioxide on the light transmittance of the hydrogels
As can be seen from fig. 3 and table 2, the light transmittance of the hydrogel prepared without adding molybdenum dioxide at 600nm is as high as 67.9%, and after adding molybdenum dioxide, the light transmittance of the hydrogel in the wavelength range of 300nm to 800nm is reduced to a certain extent, and the light transmittance tends to be gradually reduced with the increase of the content of molybdenum dioxide. However, when the concentration of the molybdenum dioxide in the system is 1.5mg/mL, the light transmittance of the hydrogel film at 600nm can still reach 27%, and the hydrogel still has good light transmittance. Compared with the traditional photothermal conversion hydrogel added with carbon nanotubes or graphene oxide, when photothermal fillers with the same concentration are added, the hydrogel containing molybdenum dioxide prepared by the invention has better light transmittance, and is beneficial to the application in the field of intelligent transparent visualization.
Discussion experiment of (II) laponite dosage
In order to investigate the effect of the amount of hectorite on the hydrogel properties, the present inventors performed experiments in examples 7 to 10, and examples 7 to 10 were as follows.
Example 7: (1) dispersing 30mg of molybdenum dioxide in 10mL of deionized water, carrying out ultrasonic treatment for 0.5h, and stirring for 3h to obtain a molybdenum dioxide dispersion liquid with the concentration of 3 mg/mL; the molybdenum dioxide is a commercial reagent or is prepared by the following method: uniformly mixing molybdenum trioxide and zinc powder according to the weight ratio of 1:0.02, calcining for 4 hours at 400 ℃ under the protection of nitrogen to obtain a black product, washing the black product with hydrochloric acid solution, ammonia water solution and water in sequence to obtain a precipitate, and drying at 50 ℃ to obtain molybdenum dioxide.
(2) Dispersing hectorite in 5.0mL of deionized water, performing ultrasonic treatment for 30min to obtain a clear and transparent hectorite solution, adding 5.0mL of molybdenum dioxide dispersion liquid with the concentration of 3mg/mL obtained in the step (1) into the hectorite solution, and stirring and mixing uniformly to obtain a mixed solution; wherein the hectorite is 50 mg.
(3) Under ice bath and nitrogen atmosphere, dissolving 1.0g N-isopropyl acrylamide in the mixed solution obtained in the step (2), then adding 20mg of initiator ammonium persulfate, 1.0mg of cross-linking agent N, N ' -methylene bisacrylamide and 10 mu L of auxiliary initiator N, N, N ', N ' -tetramethyl ethylenediamine, and uniformly mixing to obtain a mixed pre-polymerization solution; wherein the mass ratio of the molybdenum dioxide to the N-isopropylacrylamide in the mixed pre-polymerization solution is 0.015: 1.
(4) And (4) injecting the mixed prepolymer solution obtained in the step (3) into a polytetrafluoroethylene mold, and reacting for 24 hours at room temperature to obtain a hydrogel sample.
Example 8:
the contents of example 8 are substantially the same as those of example 7, except that:
in the step (2), the dosage of the hectorite is 100 mg.
Example 9:
the contents of example 9 are substantially the same as those of example 7, except that:
in the step (2), the amount of the hectorite is 300 mg.
Example 10:
the contents of example 10 are substantially the same as those of example 7, except that:
in the step (2), the amount of the hectorite is 400 mg.
In order to investigate the influence of the amount of hectorite on the hydrogel properties, the hydrogels prepared in examples 7 to 10 and 5 were tested for mechanical properties and equilibrium swelling degree, wherein the mechanical properties were tested by the following specific steps: cutting the hydrogel sample film into rectangular sample strips with the length multiplied by 5mm multiplied by 2mm (length multiplied by width multiplied by thickness), carrying out uniaxial tension test by using an electronic universal stretcher at room temperature, wherein the tension speed is 50mm/min, taking five parallel samples from each group of samples, and calculating the elongation at break and the tensile strength according to the average value; the specific test steps for balancing swelling degree are as follows: the hydrogel sample films were cut into square specimens of 20 mm. times.20 mm. times.2 mm (length. times.width. times.thickness), dried and the dry weight W recordeddPutting the dry glue into a culture dish, and using deionized waterImmersing completely, placing in an oven at 20 deg.C for three days until swelling is balanced, and recording the balance weight WsThe swelling degree calculation formula is as follows: SR = (W)s-Wd）/WdFive replicates of each set were taken and their equilibrium swelling was calculated from the average. The test results are shown in fig. 4 and table 3.
TABLE 3 Effect of hectorite dosage on hydrogel Properties
As can be seen from fig. 4 and table 3, the mechanical properties of the hydrogel are significantly affected by the content of hectorite in the system, and the hydrogen bonding between the hectorite and the poly-N-isopropylacrylamide molecular chain can greatly improve the mechanical properties of the hydrogel. When no hectorite is added in the system, the mixed pre-polymerized liquid is difficult to form, and the mechanical strength of the hydrogel is extremely poor. The hectorite has good physical crosslinking effect in a hydrogel system, and when the addition amount of the hectorite in the hydrogel system is 200mg, the breaking elongation of the hydrogel is as high as 681%; the content of the hectorite is continuously increased, the tensile strength of the hydrogel is continuously increased, but the breaking elongation of the hydrogel is reduced, because the crosslinking effect of hydrogen bonds in the gel network is continuously enhanced, so that the hydrogel network becomes more compact; and with the increase of the content of the hectorite in the system, the equilibrium swelling degree of the hydrogel is gradually reduced, and the increase of the degree of hydrogen bond crosslinking in the hydrogel system is reflected from the side. Therefore, in order to ensure that the hydrogel has good toughness and simultaneously does not influence the LCST (lower temperature coefficient of thermal plasticity) point volume shrinkage effect of the temperature-sensitive hydrogel, the invention preferably selects 200mg of hectorite and 0.2:1 of mass ratio of the hectorite to N-isopropylacrylamide.
(III) hydrogel Property study
1. Analysis of hydrogel response to different laser powers
In order to investigate the influence of laser power on the temperature rising effect of the hydrogel, the wavelength used in the method is 808nm, and the power is 0.5W/cm respectively2、0.8 W/cm2And 1.3W/cm2For the hydrogel obtained in example 4The glue was tested and the results are shown in figure 5 and table 4.
TABLE 4 influence of different laser powers on the hydrogel heating effect
Note: t in the table denotes temperature in units of ℃; the lower right hand corner of T represents time in units of s; Δ T represents TMaxAnd T0The difference of (a).
As can be seen from FIG. 5 and Table 4, the temperature-raising effect of the hydrogel was in a positive correlation with the laser power, when the laser power was 0.5W/cm2When the temperature of the hydrogel is up to 40.8 ℃, and when the laser power is 1.3W/cm2The temperature of the hydrogel can reach 74.0 ℃ at most, which shows that the heating rate and the highest steady-state temperature of the hydrogel can be obviously improved by increasing the power of the irradiation laser.
Analysis of photo-thermal stability of hydrogel
In order to explore the photo-thermal stability and the heating repeatability of the hydrogel under the irradiation of near-infrared laser, the hydrogel obtained in example 5 is subjected to a 30-cycle heating and cooling test, and the specific process of the test is as follows: recording the onset temperature T0Then a laser lamp (808 nm, 0.8W/cm)2) The maximum temperature T was recorded after 15s of irradiationMaxTurning off the laser lamp until the hydrogel is gradually cooled to room temperature, and recording the temperature T0Then, the laser was irradiated for 15 seconds, and the test was repeated. The test results are shown in fig. 6 and table 5.
TABLE 5 hydrogel cycling warming Effect
As can be seen from FIG. 6 and Table 5, the hydrogel can be heated from 20 ℃ to about 50 ℃ in each cycle, and shows almost uniform heating law, indicating that the hydrogel has good photo-thermal stability and heating repeatability.
Analysis of hydrogel response to fluorescent lamp
In order to investigate the photothermal conversion ability of the hydrogels for light in wavelength ranges other than near infrared light, the hydrogels prepared in examples 5 and 6 were subjected to the fluorescent lamp irradiation temperature rise test according to the present invention, and the test procedure is as follows: two groups of samples were placed at a power of 3.0W/cm2The temperatures of the hydrogels were recorded at different times of irradiation, and the test results are shown in fig. 7 and table 6.
TABLE 6 temperatures of hydrogels under different daylight lamp irradiation times
Note: t in the table denotes temperature in units of ℃; the lower right hand corner of T indicates time in min; Δ T represents TMaxAnd T0The difference of (a).
As can be seen from FIG. 7 and Table 6, the sample prepared in example 6 without any molybdenum dioxide content increased in temperature by about 8.3 ℃ after being irradiated under a fluorescent lamp for 15min, whereas the sample prepared in example 5 with a molybdenum dioxide content of 1.5mg/mL increased in temperature by about 18.1 ℃ under the same conditions, indicating that the prepared hydrogel containing molybdenum dioxide had a good ability to convert sunlight into heat.
(IV) micro-fluidic valve near-infrared light response effect analysis based on hydrogel preparation
The hydrogels prepared in examples 5 and 6 were used to prepare a miniflow valve, and the near infrared light response effect of the prepared miniflow valve was studied.
The specific preparation process of the micro-fluidic valve is as follows: the mixed pre-polymerization solutions prepared in examples 5 and 6 were injected into the middle of a transparent quartz tube having an inner diameter of 5mm, respectively, and the quartz tube was placed in an N position2Standing at room temperature for 24h under atmosphere to complete polymerization, then injecting pink rhodamine B solution and deionized water into two ends of a quartz tube respectively, and using 808nm water with the concentration of 0.8W/cm2The laser of (2) is irradiated and a camera is used to record the whole process of the change of the micro valve and the liquid circulation. The test results are shown in fig. 8.
As can be seen from FIG. 8, when 808nm, 0.8W/cm was used2The color of the lower water of the micro flow valve device prepared in example 6 did not change substantially before and after the laser irradiation, whereas the color of the lower water of the micro flow valve device prepared in example 5 changed to pink, because the molybdenum dioxide in the hydrogel matrix rapidly absorbs the energy of near infrared light and converts into a large amount of heat, causing the hydrogel substrate to undergo phase transition and volume shrinkage, and at this time, the two liquids in the pipe flow up and down with each other, causing the color of the lower water to change to pink.
In addition, different power illumination experiments are carried out on the micro-flow valve device, and the experimental result shows that the time required for mixing the rhodamine B solution and the deionized water in the hydrogel micro-flow valve is obviously influenced by the laser power, and when the laser illumination power is increased to 1.3W/cm2The time required for the flow-through of the micro flow valve prepared in example 5 was about 60 seconds, and the laser power was 0.3W/cm2The time required for the microvalve to flow through is about 2.5 min.
In summary, the hydrogel containing molybdenum dioxide prepared by the application can be used for preparing a micro-fluidic valve device, the prepared micro-fluidic valve device can control the circulation of a micro-fluidic channel through remote laser, and the time for the micro-fluidic valve to circulate can be controlled by regulating and controlling the laser power, so that the flow controllability of the micro-fluidic valve is realized.
Claims (8)
1. A preparation method of the photothermal conversion hydrogel is characterized by comprising the following steps:
(1) dispersing molybdenum dioxide in water to obtain molybdenum dioxide dispersion liquid;
(2) dispersing hectorite in water to obtain a hectorite solution, adding the molybdenum dioxide dispersion liquid obtained in the step (1) into the hectorite solution, and uniformly mixing to obtain a mixed solution;
(3) dissolving N-isopropyl acrylamide in the mixed solution obtained in the step (2) in an ice bath and an inert gas atmosphere, adding an initiator, a cross-linking agent and an auxiliary initiator, and uniformly mixing to obtain a mixed pre-polymerization solution;
(4) and (4) injecting the mixed pre-polymerization liquid obtained in the step (3) into a mold, and reacting at room temperature for 22-24 hours to obtain a hydrogel sample.
2. The preparation method according to claim 1, wherein the mass ratio of the N-isopropylacrylamide to the molybdenum dioxide in the molybdenum dioxide dispersion liquid in the step (3) is 1: (0.003-0.015).
3. The preparation method according to claim 1, wherein the mass ratio of N-isopropylacrylamide to hectorite in the step (3) is 1 (0.05-0.3).
4. The method according to claim 3, wherein the initiator in the step (3) is ammonium persulfate; the cross-linking agent is N, N' -methylene-bisacrylamide; the coinitiator is N, N, N ', N' -tetramethyl ethylenediamine.
5. The preparation method according to claim 4, wherein the mass ratio of the ammonium persulfate to the N-isopropylacrylamide in the step (3) is (0.01-0.04): 1; the mass ratio of the N, N' -methylene bisacrylamide to the N-isopropyl acrylamide is (0.0005-0.004): 1; the dosage of the N, N, N ', N' -tetramethylethylenediamine is 10 mu L/1g N-isopropylacrylamide.
6. The preparation method according to claim 5, wherein the mass ratio of the ammonium persulfate to the N-isopropylacrylamide in the step (3) is 0.02: 1; the mass ratio of the N, N' -methylene bisacrylamide to the N-isopropyl acrylamide is 0.001: 1.
7. a photothermal conversion hydrogel obtained by the production method according to any one of claims 1 to 6.
8. Use of the photothermal conversion hydrogel of claim 7 in a light-operated micro flow valve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110052047.2A CN112679754B (en) | 2021-01-15 | 2021-01-15 | Preparation method and application of photo-thermal conversion hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110052047.2A CN112679754B (en) | 2021-01-15 | 2021-01-15 | Preparation method and application of photo-thermal conversion hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112679754A CN112679754A (en) | 2021-04-20 |
| CN112679754B true CN112679754B (en) | 2022-05-27 |
Family
ID=75458145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110052047.2A Active CN112679754B (en) | 2021-01-15 | 2021-01-15 | Preparation method and application of photo-thermal conversion hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112679754B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113568188B (en) * | 2021-07-16 | 2022-12-02 | 河南省人民医院 | Preparation method of intelligent contact lens for photothermal treatment and laser protection of eyes |
| CN114479127B (en) * | 2022-03-14 | 2023-04-21 | 北京石油化工学院 | Photochromic deformation hydrogel and preparation method and color-changing deformation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408683A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Preparation method of physical/chemical crosslinking photo-thermal response hydrogel |
| CN103408708A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Preparation method of near-infrared light response hydrogel |
| CN108219480A (en) * | 2017-12-07 | 2018-06-29 | 南京邮电大学 | Macromolecule based on thermal reversion Diels-Alder reactions-nano molybdenum disulfide piece composite hydrogel prepares and application |
| CN109294144A (en) * | 2018-09-25 | 2019-02-01 | 哈尔滨工业大学 | A kind of load MoO3The preparation method of the temperature sensitive composite microgel of PVCL base of quantum dot |
| KR20200065183A (en) * | 2018-11-29 | 2020-06-09 | 고려대학교 세종산학협력단 | Novel pan-based block copolymer for electrolyte gelator, electrolyte gelator including said block copolymer, and polymer gel electrolyte composition including said electrolyte gelator and inorganic nanoparticles |
| CN112126082A (en) * | 2020-08-18 | 2020-12-25 | 浙江大学衢州研究院 | Self-repairing multi-photoresponse double-layer supramolecular hydrogel and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180251649A1 (en) * | 2015-11-30 | 2018-09-06 | President And Fellows Of Harvard College | Hydrogel composite ink formulation and method of 4d printing a hydrogel composite structure |
-
2021
- 2021-01-15 CN CN202110052047.2A patent/CN112679754B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408683A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Preparation method of physical/chemical crosslinking photo-thermal response hydrogel |
| CN103408708A (en) * | 2013-07-15 | 2013-11-27 | 东华大学 | Preparation method of near-infrared light response hydrogel |
| CN108219480A (en) * | 2017-12-07 | 2018-06-29 | 南京邮电大学 | Macromolecule based on thermal reversion Diels-Alder reactions-nano molybdenum disulfide piece composite hydrogel prepares and application |
| CN109294144A (en) * | 2018-09-25 | 2019-02-01 | 哈尔滨工业大学 | A kind of load MoO3The preparation method of the temperature sensitive composite microgel of PVCL base of quantum dot |
| KR20200065183A (en) * | 2018-11-29 | 2020-06-09 | 고려대학교 세종산학협력단 | Novel pan-based block copolymer for electrolyte gelator, electrolyte gelator including said block copolymer, and polymer gel electrolyte composition including said electrolyte gelator and inorganic nanoparticles |
| CN112126082A (en) * | 2020-08-18 | 2020-12-25 | 浙江大学衢州研究院 | Self-repairing multi-photoresponse double-layer supramolecular hydrogel and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112679754A (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112679754B (en) | Preparation method and application of photo-thermal conversion hydrogel | |
| Zhang et al. | Energy-efficient smart window based on a thermochromic microgel with ultrahigh visible transparency and infrared transmittance modulation | |
| Ge et al. | Adjustable dual temperature-sensitive hydrogel based on a self-assembly cross-linking strategy with highly stretchable and healable properties | |
| CN106866993B (en) | Compound self-healing hydrogel of a kind of macromolecule based on nano thin-layer curing molybdenum sheet and preparation method thereof | |
| Wei et al. | Thermal-responsive PNIPAm-acrylic/Ag NRs hybrid hydrogel with atmospheric window full-wavelength thermal management for smart windows | |
| CN113881068B (en) | Preparation method and application of high-performance thermoelectric hydrogel based on ion conduction | |
| CN110982011B (en) | Light-directing bending material and preparation method thereof | |
| Shao et al. | Continuous synthesis of carbon dots with full spectrum fluorescence and the mechanism of their multiple color emission | |
| CN113999476B (en) | Dual-stimulation-responsive conductive composite hydrogel and preparation method and application thereof | |
| CN113024732B (en) | Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof | |
| CN104709894B (en) | Preparation method and applications of fluorescent carbon quantum dots | |
| CN108394885B (en) | Method for synthesizing solid carbon quantum dots by gas-phase detonation | |
| CN104448824A (en) | Polyimide-based composite film with optical limiting performance | |
| CN105866047A (en) | Biosensor for detecting divalent mercury ions, and making method thereof | |
| CN113419580A (en) | Intelligent temperature control device based on passive radiation cooling and solar heating and preparation method thereof | |
| CN106190101B (en) | Self-supporting film with micro-structure surface and preparation method thereof | |
| Breuer et al. | Light‐controllable polymeric material based on temperature‐sensitive hydrogels with incorporated graphene oxide | |
| Zhang et al. | Study on the room temperature synthesis of highly photoluminescent and temperature-sensitive CDs/PNIPAM hybrid hydrogels and their properties | |
| CN110845679A (en) | Modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material and preparation method thereof | |
| Gudadur et al. | Flexible reversible polymer nano-composite thin film patch for wearable temperature sensor | |
| WO2023197588A1 (en) | Rapid photoheating pcr apparatus using small-size micro-tube as container and method therefor | |
| CN110627975A (en) | Method for designing photothermal effect type self-healing hydrogel based on melanin chemistry | |
| CN112645406A (en) | Ultraviolet lamp disinfection water purification reactor and manufacturing method thereof | |
| CN112093794B (en) | Graphene optical drive material and preparation method thereof | |
| CN113856776B (en) | Preparation method and application of responsive structural color micro-pipeline |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |