CN113321770B - Preparation method of temperature-sensitive hydrogel - Google Patents
Preparation method of temperature-sensitive hydrogel Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The invention relates to a preparation method of a temperature-sensitive hydrogel, belonging to the technical field of high polymer materials. The invention utilizes a blending method to prepare the temperature-sensitive composite hydrogel from NIPPAM, PVA-SbQ, CNC and photoinitiator under the action of ultraviolet light. Compared with temperature-sensitive hydrogel prepared by thermal initiation, the preparation process is simpler and more efficient; temperature-sensitive hydrogel with different temperature sensitivities can be prepared by adjusting the difference of local light transmittance; meanwhile, due to the addition of CNC, compared with PNIPPAM hydrogel, the mechanical property of the hydrogel is more excellent.
Description
Technical Field
The invention relates to a preparation method of temperature-sensitive hydrogel, belonging to the technical field of high polymer materials.
Background
The hydrogel is a hydrophilic but water-insoluble high-molecular polymer having a three-dimensional network structure formed by physical or chemical action. The hydrogel may be classified into a natural hydrogel and a conventional hydrogel according to its origin; the hydrogel can be classified into a conventional hydrogel and an environmentally sensitive hydrogel according to the response of an external stimulus. Among them, the environmental sensitive hydrogels can be further classified into hydrogels sensitive to PH, light, electricity, temperature, and the like. Compared with the traditional hydrogel, the environment-sensitive hydrogel is sensitive to environmental changes, so that the corresponding physical structure and chemical property changes are generated, and the hydrogel has wide application prospects in various fields. The temperature-sensitive hydrogel is one of environment-sensitive hydrogels, and hydrophilic and hydrophobic groups exist in the temperature-sensitive hydrogel. The groups are influenced by temperature, and the hydrophilic and hydrophobic effects and the hydrogen bonding effects are changed, so that the structural change of molecular chains in the hydrogel is influenced, and the form of the hydrogel is influenced finally. Therefore, the temperature-sensitive hydrogel can generate stimulus response along with the change of the external temperature, and has wide application prospects in the aspects of temperature detection, material separation, drug release and the like.
The traditional poly N-isopropyl acrylamide (PNIPPAM) hydrogel has good temperature sensitivity and has potential application prospect in the aspect of temperature detection. Meanwhile, the low critical solution temperature is close to the human body temperature and has good biocompatibility. Therefore, the compound has great application prospect in the aspects of biomedicine such as drug release and the like. However, the PNIPPAM hydrogel has lower mechanical strength, and the development prospect is limited.
Disclosure of Invention
The technical problem is as follows:
in order to improve the mechanical strength of PNIPPAM hydrogel and obtain a composite hydrogel material with excellent mechanical property and temperature-sensitive property, the invention takes polyvinyl alcohol-styryl pyridinium condensate (PVA-SbQ), Cellulose Nanocrystalline (CNC) and N-isopropyl acrylamide (NIPPAM) as raw materials, prepares hydrogel with temperature-sensitive property by a photo-crosslinking strategy, and optimizes parameters of preparation conditions by a large number of experiments.
The invention has the technical concept that the photosensitive characteristic of PVA-SbQ is utilized, a network structure is formed by photo-crosslinking under the irradiation of ultraviolet light, and CNC is added on the basis, and can form hydrogen bonds with the PVA-SbQ, so that the mechanical strength of the hydrogel is enhanced. NIPPAM does not have photosensitive groups per se, direct photo-initiation polymerization cannot be carried out, and after the photoinitiator is added, the NIPPAM is polymerized under the irradiation of ultraviolet light to form PNIPPAM with temperature-sensitive characteristics and a long-chain structure. The PNIPPAM endows hydrogel with temperature-sensitive property on one hand, and can be combined with PVA-SbQ and CNC together through chain entanglement and hydrogen bond action on the other hand, so that the mechanical strength of the hydrogel is further enhanced.
The technical scheme is as follows:
the first purpose of the invention is to provide a preparation method of temperature-sensitive hydrogel, which comprises the steps of uniformly mixing polyvinyl alcohol-styryl pyridinium condensate PVA-SbQ, cellulose nanocrystalline CNC, N-isopropyl acrylamide NIPPAM and a photoinitiator under the condition of keeping out of the sun, defoaming to obtain a mixed solution, and then placing the mixed solution under an ultraviolet lamp for exposure reaction to obtain the temperature-sensitive hydrogel; wherein the mass ratio of PVA-SbQ, CNC, NIPPAM and photoinitiator is 8: (0.08-0.32): 3: (0.09 or 0.15).
In one embodiment of the present invention, the photoinitiator is any one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1-phenylpropanone and 1-hydroxycyclohexyl phenyl methanone.
In one embodiment of the invention, the power of the ultraviolet lamp is 40-50W/cm2(ii) a The exposure time of the ultraviolet lamp is 5-8 min.
In one embodiment of the present invention, the mass fraction of PVA-SbQ relative to the mixed system is 5 to 10%. Preferably 8%.
In one embodiment of the invention, the mass fraction of the NIPPAM relative to the mixed system is 2.67-3%. Preferably 2.85%.
In one embodiment of the present invention, the mass fraction of the CNC relative to the mixed system is 0.08-0.3%. Preferably 0.08%.
In one embodiment of the present invention, the photoinitiator has a mass fraction of 0.08% to 0.015% with respect to the mixed system. Preferably 0.09 to 0.015, for example 0.085%.
In one embodiment of the present invention, the mass ratio of PVA-SbQ, CNC, NIPPAM and photoinitiator is 8:0.08:3: 0.09.
in one embodiment of the present invention, the method specifically includes the following steps:
dissolving NIPPAM and a photoinitiator in deionized water, stirring in the dark, and after completely dissolving, adding a PVA-SbQ solution and a CNC suspension, wherein the mass ratio of PVA-SbQ, CNC, NIPPAM and the photoinitiator is 8: (0.08-0.32): 3: (0.09 or 0.15); stirring for 1 hour, standing for defoaming, after bubbles are completely eliminated, filling the mixed solution into a transparent container with different local light transmittance, and exposing and reacting under an ultraviolet lamp to obtain the temperature-sensitive hydrogel. The transparent containers with different local light transmittances include, but are not limited to, surface dishes with different local light transmittances, and the surface dishes with different local light transmittances can be obtained by coating a dark pigment (forming a specific pattern) on a part of the surface of a conventional surface dish.
The second purpose of the invention is to provide the temperature-sensitive hydrogel prepared by the method.
The third purpose of the invention is to provide the application of the temperature-sensitive hydrogel in the preparation of a temperature-sensitive color-changing water cup.
The invention has the beneficial effects that:
(1) the PVA-SbQ/NIPPAM/CNC composite hydrogel is prepared by blending a polyvinyl alcohol-styryl pyridinium condensate (PVA-SbQ), Cellulose Nanocrystal (CNC), N-isopropyl acrylamide (NIPPAM) and a photoinitiator and carrying out photocrosslinking reaction under the action of ultraviolet rays. Compared with the traditional poly N-isopropylacrylamide (PNIPPAM) hydrogel, the composite hydrogel disclosed by the invention is obtained by matching PVA-SbQ serving as a hydrogel substrate with NIPPAM and CNC under a specific condition, has good temperature sensitivity, has a potential application prospect in the aspect of temperature detection, has low critical dissolution temperature close to the temperature of a human body, good biocompatibility and excellent mechanical strength, and is particularly shown in that the tensile strength of the composite hydrogel disclosed by the invention is 2.7 times that of the traditional N-isopropylacrylamide (NIPPAM) hydrogel.
(2) According to the temperature-sensitive hydrogel obtained by the invention, by adding CNC and PVA-SbQ, compared with the traditional PNIPPAM temperature-sensitive hydrogel, the mechanical property of the hydrogel is greatly enhanced by NIPPAM photopolymerization, and the effects of endowing the hydrogel with temperature sensitivity and enhancing the mechanical property of the hydrogel are equivalently achieved.
(3) Compared with the traditional N-isopropyl acrylamide (NIPPAM) hydrogel prepared by adopting a thermal initiation method, the preparation method of the temperature-sensitive hydrogel is simpler and more efficient in preparation process; meanwhile, the temperature-sensitive hydrogel with obvious regional difference on temperature sensitivity can be prepared in one step by designing the simple operation step of carrying out photoinitiated reaction on the local light transmittance of a container for containing the mixed solution, namely the prepared temperature-sensitive hydrogel can show specific pattern change before and after temperature-sensitive color change.
(4) In the prior art, the temperature-sensitive hydrogel with the pattern is prepared by cutting the hydrogel with the temperature-sensitive characteristic into a specific shape and then bonding the hydrogel with another high-strength hydrogel to prepare the temperature-sensitive hydrogel capable of displaying the pattern. The method is complicated and easy to damage the hydrogel in the operation process, thereby affecting the mechanical property of the final product. In comparison, the temperature-sensitive hydrogel prepared by the invention is prepared into a whole block of hydrogel with a pattern change in a mode of changing the light transmittance, the preparation method is simple, and the temperature-sensitive hydrogel with the pattern is prepared on the basis of ensuring the mechanical property of the hydrogel.
Drawings
FIG. 1 is a graph comparing the results of tensile strength tests for different materials.
FIG. 2 is a graph showing the results of temperature-sensitive tests of the PVA-SbQ/NIPPAM/CNC composite hydrogel of the present invention.
Detailed Description
The PVA-SbQ materials in the examples and comparative examples of the present invention were purchased from Shanghai photopoiticida printing apparatus science and technology Co.
And (3) testing tensile strength: the sample hydrogel was cut into dumbbell-shaped sample strips with a length of 12mm, a width of 2mm and a thickness of 0.5. + -. 0.4mm, and the tensile strength and elongation at break of the hydrogel were measured by a universal tester at a tensile speed of 50 mm/min. The results of tensile strength testing of the different materials are compared and shown in figure 1.
And (3) temperature-sensitive test: adhering the prepared temperature-sensitive hydrogel on the surface of a beaker, pouring hot water with a pigment dissolved therein at the temperature of 80 ℃ into the beaker, and observing the temperature-sensitive discoloration phenomenon. The temperature-sensitive test result of the PVA-SbQ/CNC/NIPPAM composite hydrogel prepared in the example 1 of the invention is shown in a figure 2.
Example 1
10g of an 8% PVA-SbQ solution are taken, 0.23g of a 3.45% CNC suspension, 0.3g of NIPPAM and 0.009g of a photoinitiator are added thereto, stirred for 1 hour, left to stand for 0.5 hour, poured into a watch glass (for example, a glass plate with a "youth of material" written by a dark pigment on a conventional watch glass) with different local transmittances after complete elimination of air bubbles, and placed at 40W/cm2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC temperature-sensitive hydrogel, and recording the PVA-SbQ/NIPPAM/CNC-1 as the tensile strength test result shown in figure 1.
Through temperature-sensitive test, the temperature-sensitive test result of the PVA-SbQ/NIPPAM/CNC composite hydrogel prepared in the embodiment 1 of the invention is shown in a figure 2. Before hot water is added, the surface of the beaker adhered with the temperature-sensitive hydrogel is colorless and transparent; after hot water is added, the beaker surface adhered with the temperature-sensitive hydrogel presents a pattern like the youth material due to the color change of the temperature-sensitive hydrogel.
Example 2
10g of 8% PVA-SbQ solution was added with 0.46g of 3.45% CNC suspension, 0.3g of NIPPAM and 0.009g of photoinitiator, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC temperature-sensitive hydrogel which is recorded as PVA-SbQ/NIPPAM/CNC-2.
Example 3
10g of 8% PVA-SbQ solution was added with 0.69g of 3.45% CNC suspension, 0.3g of NIPPAM and 0.009g of photoinitiator, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC temperature-sensitive hydrogel which is recorded as PVA-SbQ/NIPPAM/CNC-3.
Example 4
10g of an 8% PVA-SbQ solution were taken, and 0.92g of a 3.45% CNC suspension was added,0.3g of NIPPAM and 0.009g of photoinitiator, stirring for 1 hour, standing for 0.5 hour, pouring into a watch glass with different local light transmittance after bubbles are completely eliminated, and placing in a 40W/cm2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC temperature-sensitive hydrogel which is recorded as PVA-SbQ/NIPPAM/CNC-4.
Example 5
Taking 10g of 8% PVA-SbQ solution, adding 0.23g of 3.45% CNC suspension, 0.3g of NIPPAM and 0.015g of photoinitiator, stirring for 1 hour, standing for 0.5 hour, pouring the mixture into a surface dish with different local light transmittances after bubbles are completely eliminated, and placing the surface dish in a place with 40W/cm2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC temperature-sensitive hydrogel which is recorded as PVA-SbQ/NIPPAM/CNC.
Comparative example 1(PVA-SbQ, CNC of 0% (w/w))
10g of 8% PVA-SbQ solution was poured into a petri dish with different local transmittances and placed at 40W/cm2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ hydrogel which is marked as PVA-SbQ, and testing the tensile strength of the PVA-SbQ hydrogel is shown in figure 1.
Through temperature sensitive test, the PVA-SbQ hydrogel prepared in the comparative example 1 has no temperature sensitive characteristic.
Comparative example 2(PVA-SbQ, 1% (w/w) CNC)
10g of 8% PVA-SbQ solution was added with 0.23g of 3.45% CNC suspension, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/CNC hydrogel. The tensile strength test results are shown in FIG. 1, which is recorded as PVA-SbQ/CNC-1.
Through temperature sensitive test, the PVA-SbQ/CNC hydrogel prepared in the comparative example 2 has no temperature sensitive characteristic.
Comparative example 3(PVA-SbQ, 2% (w/w) CNC)
10g of 8% PVA-SbQ solution was added with 0.46g of 3.45% CNC suspension, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under ultraviolet lamp for 6min to obtain PVA-SbQ/CNC hydrogel, recording as PVA-SbQ/CNC-2, and its tensile strengthThe test results are shown in FIG. 1.
Through temperature-sensitive test, the PVA-SbQ/CNC hydrogel prepared in the comparative example 3 has no temperature-sensitive characteristic.
Comparative example 4(PVA-SbQ, CNC of 3% (w/w))
10g of 8% PVA-SbQ solution was added with 0.69g of 3.45% CNC suspension, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/CNC hydrogel, recording as PVA-SbQ/CNC-3, and testing the tensile strength of the hydrogel as shown in figure 1.
Through temperature-sensitive test, the PVA-SbQ/CNC hydrogel prepared in the comparative example 4 has no temperature-sensitive characteristic.
Comparative example 5(PVA-SbQ, 4% (w/w) CNC)
10g of 8% PVA-SbQ solution was added with 0.92g of 3.45% CNC suspension, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under an ultraviolet lamp for 6min to obtain PVA-SbQ/CNC hydrogel which is marked as PVA-SbQ/CNC-4, and the tensile strength test result is shown in figure 1.
Through temperature sensitive test, the PVA-SbQ/CNC hydrogel prepared in the comparative example 5 has no temperature sensitive characteristic.
Comparative example 6 (thermal initiation method for preparing conventional NIPPAM hydrogel)
Dissolving NIPAM 1.64g and N, N' -Methylene Bisacrylamide (MBA) 0.02g in deionized water 18.82g, stirring at 50 deg.C to dissolve, cooling to room temperature, adding 20 μ LTEMED, introducing N2And (3) 30min, finally adding 100 mu L of 10 wt% Ammonium Persulfate (APS) solution, uniformly mixing, pouring into a watch glass, and standing for 2 hours to obtain the PNIPPAM temperature-sensitive hydrogel.
Comparative example 7
10g of 8% PVA-SbQ solution was added with 1.84g of 3.45% CNC suspension, 0.3g of NIPPAM and 0.09g of photoinitiator, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC temperatureThe pressure sensitive hydrogel is named as PVA-SbQ/NIPPAM/CNC-7.
Comparative example 8 (without initiator)
10g of 8% PVA-SbQ solution was added with 0.23g of 3.45% CNC suspension and 0.3g of NIPPAM, stirred for 1 hour, left to stand for 0.5 hour, poured into a petri dish with different local transmittances after bubbles were completely eliminated, and placed in a 40W/cm petri dish2Irradiating under ultraviolet lamp for 6min to obtain PVA-SbQ/NIPPAM/CNC hydrogel, and recording as PVA-SbQ/NIPPAM/CNC hydrogel’。
The properties of the materials of examples and comparative examples were measured and the results are shown in Table 1 and FIG. 1
TABLE 1 tensile Strength test results for different materials
| Material | Tensile Strength/kPa | Whether or not it has temperature sensitive characteristics |
| Example 1 | 108.61±4.99 | Is that |
| Example 2 | 100.45±6.38 | Is that |
| Example 3 | 93.59±8.51 | Is that |
| Example 4 | 86.12±4.68 | Is that |
| Example 5 | 84.56±6.77 | Is that |
| Comparative example 1 | 42.86±7.06 | Whether or not |
| Comparative example 2 | 70.62±9.56 | Whether or not |
| Comparative example 3 | 61.16±7.86 | Whether or not |
| Comparative example 4 | 54.90±7.74 | Whether or not |
| Comparative example 5 | 54.79±8.98 | Whether or not |
| Comparative example 6 | 39.69±5.33 | Is that |
| Comparative example 7 | 60.16±5.83 | Is that |
| Comparative example 8 | 68.33±3.22 | Whether or not |
As can be seen from Table 1, comparative example 2 is a hydrogel to which 1% (w/w) of CNC was added, and comparative examples 1, 3 to 5 are hydrogels to which CNC was not added and which were added at different contents, respectively, indicating that a proper amount of CNC was advantageous for enhancing the mechanical properties of the PVA-SbQ/CNC hydrogel.
Example 1 is a temperature-sensitive hydrogel to which NIPPAM was added, which has temperature-sensitive characteristics, compared to comparative examples 1 to 5 to which no NIPPAM was added. Comparative example 6 is a conventional PNIPPAM hydrogel with temperature sensitive properties, but too low mechanical strength (tensile strength of only 39.69 ± 5.33kPa under the same test conditions).
During the course of the present study, the applicant found that only the specific ratios of the components PVA-SbQ, cellulose nanocrystalline CNC, N-isopropylacrylamide NIPPAM and photoinitiator were used, i.e. the mass ratio of PVA-SbQ, CNC, NIPPAM and photoinitiator was 8: (0.08-0.32): 3: (0.09 or 0.15), the prepared PVA-SbQ/NIPPAM/CNC temperature-sensitive hydrogel has good temperature-sensitive performance and mechanical performance (the tensile strength is more than 80kPa and is obviously higher than that of the PVA-SbQ hydrogel, the PNIPPAM hydrogel and the PVA-SbQ/CNC hydrogel). In particular, when the mass ratio of PVA-SbQ, CNC, NIPPAM and photoinitiator was 8:0.08:3:0.09, the tensile strength reached 108.61. + -. 4.99 kPa. The mechanical properties of the hydrogel prepared in the compounding ratio range are sharply reduced, as shown in comparative examples 7-8, the mechanical properties are only 60.16 +/-5.83 kPa and 68.33 +/-3.22 kPa, and the hydrogel prepared in comparative example 8 (without adding an initiator) has no temperature-sensitive property.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of temperature-sensitive hydrogel is characterized by comprising the following steps: uniformly mixing polyvinyl alcohol-styryl pyridinium condensate PVA-SbQ, cellulose nanocrystalline CNC, N-isopropyl acrylamide NIPPAM and a photoinitiator under a light-proof condition, defoaming to obtain a mixed solution, and then placing the mixed solution under an ultraviolet lamp for exposure reaction to obtain temperature-sensitive hydrogel;
wherein the mass ratio of PVA-SbQ, CNC, NIPPAM and photoinitiator is 8: (0.08-0.32): 3: (0.09 or 0.15).
2. The method for preparing temperature-sensitive hydrogel according to claim 1, wherein the photoinitiator is any one or more of 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1-phenylacetone and 1-hydroxycyclohexyl phenyl ketone.
3. The preparation method of the temperature-sensitive hydrogel according to claim 1, wherein the power of the ultraviolet lamp is 40-50W/cm2(ii) a The exposure time of the ultraviolet lamp is 5-8 min.
4. The preparation method of the temperature-sensitive hydrogel according to claim 1, wherein the mass fraction of PVA-SbQ relative to the mixed system is 5-10%.
5. The preparation method of the temperature-sensitive hydrogel according to claim 1, wherein the mass fraction of the NIPPAM relative to the mixed system is 2.67-3%.
6. The preparation method of the temperature-sensitive hydrogel according to claim 1, wherein the mass fraction of the CNC relative to the mixed system is 0.08-0.3%.
7. The preparation method of the temperature-sensitive hydrogel according to claim 1 or 2, wherein the mass fraction of the photoinitiator relative to the mixed system is 0.08% to 0.015%.
8. The method for preparing a temperature-sensitive hydrogel according to claim 1, wherein the mixed solution is contained in a light-transmitting container having a different partial light transmittance in the step of exposing the mixed solution to an ultraviolet lamp.
9. Temperature-sensitive hydrogel prepared by the method of any one of claims 1 to 8.
10. The use of the temperature-sensitive hydrogel of claim 9 in the preparation of a temperature-sensitive color-changing cup.
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