CN114058033A - Preparation method of temperature-sensitive hydrogel and temperature-sensitive hydrogel product prepared by same - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 83
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 83
- 229940074391 gallic acid Drugs 0.000 claims abstract description 54
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 54
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
Abstract
The invention relates to the field of new materials, in particular to a preparation method of temperature-sensitive hydrogel and a temperature-sensitive hydrogel product prepared by the same. The preparation method comprises the following steps: and (3) placing the chemically crosslinked polyvinyl alcohol hydrogel into a gallic acid solution for dipping treatment, and obtaining the temperature-sensitive polyvinyl alcohol hydrogel after dipping. The invention soaks the polyvinyl alcohol hydrogel in gallic acid solution to carry on the dipping treatment, has got a hydrogel with temperature sensitivity, the mechanical strength of this hydrogel will change with the temperature under certain temperature stimulation, and, the mechanical strength of the temperature-sensitive hydrogel of the invention is obviously higher than ordinary polyvinyl alcohol hydrogel; in addition, when the external temperature reaches the phase transition temperature of the hydrogel, the transparency of the hydrogel is changed suddenly, namely, the hydrogel is converted into a transparent state from opaque milky white, and the hydrogel can still restore to the initial state after the temperature is reduced, so that the change process is reversible.
Description
Technical Field
The invention belongs to the field of novel intelligent materials, and particularly relates to a preparation method of temperature-sensitive hydrogel and a temperature-sensitive hydrogel product prepared by the same.
Background
The hydrogel is a high molecular material containing a large amount of water and having a three-dimensional network structure, and has important application prospects in the fields of joint lubrication, biological tissue engineering, drug controlled release carriers and the like. The intelligent hydrogel with the temperature sensitive characteristic can change the physical state after the external environment temperature reaches the phase transition temperature of the hydrogel, and can return to the original state after the temperature is recovered, and the process is completely reversible. The non-contact remote control can be realized by changing the environmental temperature, and the method has potential application in the field of injectable and bionic intelligent materials. At present, the most common temperature-sensitive hydrogel is chemically crosslinked polyisopropylacrylamide and copolymer hydrogel thereof, the phase transition temperature of the hydrogel can be regulated and controlled by changing the molar ratio of the polyisopropylacrylamide to the copolymer, when the temperature exceeds the phase transition temperature, the dehydration phenomenon occurs inside the hydrogel, the hydrogel suddenly changes in volume, swelling degree and transmittance, and when the temperature returns to be below the phase transition temperature, the hydrogel returns to the initial state.
The polyvinyl alcohol is a water-soluble polymer, has excellent biocompatibility and no toxicity, meets the requirement of current environmental protection in production and use, and is a green chemical material, so that the polyvinyl alcohol hydrogel is widely applied to the fields of agriculture and forestry, industry, medicine and health and the like. The polyvinyl alcohol hydrogel is usually prepared by a chemical method, a physical method, a radiation method and the like. The chemical method needs to introduce a cross-linking agent, but the cross-linking agent is difficult to eliminate and has cytotoxicity; the freeze-thaw method is the most common physical method for preparing polyvinyl alcohol hydrogel, and the hydrogel prepared by the method has the advantage of good elasticity, but can be converted into a solution at a higher temperature, and has the defects of long time consumption, small swelling degree, opacity and the like; the radiation method is a green method for synthesizing polyvinyl alcohol hydrogel, has high synthesis efficiency and good gel transparency, but has the problems of poor toughness and easy breakage. So far, there have been few reports based on the development of temperature-sensitive polyvinyl alcohol-based hydrogels with good mechanical properties.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a temperature-sensitive hydrogel and a temperature-sensitive hydrogel product prepared by the same.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of temperature-sensitive hydrogel, which comprises the following steps: and (3) putting the polyvinyl alcohol hydrogel into gallic acid solution for dipping treatment, and obtaining the temperature-sensitive polyvinyl alcohol hydrogel after dipping.
According to the above preparation method, preferably, the gallic acid solution is prepared by dissolving gallic acid in water, and the mass fraction of gallic acid in the gallic acid solution is 0.1-1.2%.
According to the preparation method, the soaking treatment time is preferably 2-48 h.
According to the above preparation method, preferably, the preparation method of the polyvinyl alcohol hydrogel comprises: and (3) carrying out irradiation treatment on the polyvinyl alcohol aqueous solution to obtain the polyvinyl alcohol hydrogel.
According to the above preparation method, preferably, the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol aqueous solution is 10% to 15%.
According to the preparation method, the irradiation dose of the irradiation treatment is preferably 10-30 kGy.
According to the above production method, preferably, the irradiation treatment is carried out by60Co gamma rays or electron beams are subjected to irradiation treatment.
In a second aspect, the present invention provides a temperature-sensitive hydrogel product produced by the method of the first aspect.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention soaks the polyvinyl alcohol hydrogel in gallic acid solution to carry on the dipping treatment, has got a hydrogel with temperature sensitivity, the mechanical strength of this hydrogel will change with the temperature under certain temperature stimulation, and, the mechanical strength of the temperature-sensitive hydrogel of the invention is obviously higher than ordinary polyvinyl alcohol hydrogel; in addition, when the external temperature reaches the phase transition temperature of the hydrogel, the transparency of the hydrogel is changed suddenly, namely, the hydrogel is converted into a transparent state from opaque milky white, and the hydrogel can still restore to the initial state after the temperature is reduced, so that the change process is reversible.
(2) The temperature sensitive hydrogel of the invention is directly prepared by60The polyvinyl alcohol hydrogel is prepared by treating a polyvinyl alcohol aqueous solution by Co gamma-ray or high-energy electron beam irradiation and then soaking the polyvinyl alcohol hydrogel in gallic acid solution, and the whole preparation process does not adopt any cross-linking agent or initiator, is environment-friendly and pollution-free, and the prepared temperature-sensitive hydrogel does not contain harmful components and has no cytotoxicity.
(3) The preparation method of the temperature-sensitive hydrogel is simple and easy to implement, does not need expensive equipment, has wide raw material sources and low cost, and is beneficial to realizing industrial transformation of the technology.
Drawings
FIG. 1 is a photograph of the change in transparency with temperature of the temperature-sensitive hydrogel according to the present invention;
FIG. 2 is a graph showing the change in storage modulus (G ') and loss modulus (G') with temperature during temperature increase of the temperature-sensitive hydrogel according to the present invention;
FIG. 3 is a graph showing the compressive strength of the temperature sensitive hydrogel of the present invention at the same temperature under different strains.
Detailed Description
Example 1:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 20g of polyvinyl alcohol (PVA) into 180g of water, stirring and heating to 90 ℃ until a homogeneous transparent polyvinyl alcohol solution with the mass fraction of 10% is obtained;
(2) transferring the polyvinyl alcohol solution to a mold, using60Carrying out irradiation treatment on Co gamma rays with the irradiation dose of 30kGy to obtain polyvinyl alcohol hydrogel with the thickness of 2 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 24h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 0.1%.
Example 2:
example 2 is substantially the same as example 1 except that the content of gallic acid in the aqueous solution of gallic acid in step (3) is 0.2% by mass.
Example 3:
example 3 is substantially the same as example 1 except that the content of gallic acid in the aqueous solution of gallic acid in step (3) is 0.5% by mass.
Example 4:
example 4 is substantially the same as example 1 except that the mass fraction of gallic acid in the aqueous solution of gallic acid in step (3) is 0.8%.
Example 5:
example 5 is substantially the same as example 1 except that the mass fraction of gallic acid in the aqueous solution of gallic acid in step (3) is 1.0%.
Example 6:
example 6 is substantially the same as example 1 except that the content of gallic acid in the aqueous solution of gallic acid in step (3) is 1.2% by mass.
Example 7:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 30g of polyvinyl alcohol (PVA) into 170g of water, stirring and heating to 90 ℃ until a homogeneous transparent 15 mass percent polyvinyl alcohol solution is obtained;
(2) transferring the polyvinyl alcohol solution to a mold, using60Carrying out irradiation treatment on Co gamma rays with the irradiation dose of 30kGy to obtain polyvinyl alcohol hydrogel with the thickness of 1 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 24h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 0.3%.
Example 8:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 30g of polyvinyl alcohol (PVA) into 170g of water, stirring and heating to 90 ℃ until a homogeneous transparent 15 mass percent polyvinyl alcohol solution is obtained;
(2) transferring the polyvinyl alcohol solution to a mold, using60Carrying out irradiation treatment on Co gamma rays with the irradiation dose of 10kGy to obtain polyvinyl alcohol hydrogel with the thickness of 1 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 24h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 0.3%.
Example 9:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 30g of polyvinyl alcohol (PVA) into 170g of water, stirring and heating to 90 ℃ until a homogeneous transparent 15 mass percent polyvinyl alcohol solution is obtained;
(2) transferring the polyvinyl alcohol solution to a mold, using60Carrying out irradiation treatment on Co gamma rays with the irradiation dose of 30kGy to obtain polyvinyl alcohol hydrogel with the thickness of 2 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 4h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 0.3%.
Example 10:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 20g of polyvinyl alcohol (PVA) into 180g of water, stirring and heating to 90 ℃ until a homogeneous transparent polyvinyl alcohol solution with the mass fraction of 10% is obtained;
(2) transferring the polyvinyl alcohol solution into a mould, and performing irradiation treatment by adopting an electron beam with the irradiation dose of 30kGy to obtain polyvinyl alcohol hydrogel, wherein the thickness of the polyvinyl alcohol hydrogel is 2 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 4h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 0.5%.
Example 11:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 20g of polyvinyl alcohol (PVA) into 180g of water, stirring and heating to 90 ℃ until a homogeneous transparent polyvinyl alcohol solution with the mass fraction of 10% is obtained;
(2) transferring the polyvinyl alcohol solution into a mould, and performing irradiation treatment by adopting an electron beam, wherein the irradiation dose is 15kGy, so as to obtain polyvinyl alcohol hydrogel, and the thickness of the polyvinyl alcohol hydrogel is 1 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 12h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 1.0%.
Example 12:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 20g of polyvinyl alcohol (PVA) into 180g of water, stirring and heating to 90 ℃ until a homogeneous transparent polyvinyl alcohol solution with the mass fraction of 10% is obtained;
(2) transferring the polyvinyl alcohol solution into a mould, and performing irradiation treatment by adopting an electron beam with the irradiation dose of 20kGy to obtain polyvinyl alcohol hydrogel, wherein the thickness of the polyvinyl alcohol hydrogel is 1 mm;
(3) putting the polyvinyl alcohol hydrogel prepared in the step (2) into a gallic acid aqueous solution, soaking for 12h, and taking out after soaking to obtain a temperature-sensitive hydrogel; wherein the mass fraction of gallic acid in the gallic acid aqueous solution is 0.8%.
Example 13:
example 13 is substantially the same as example 1 except that the irradiation dose in step (2) was 20 kGy.
Comparative example 1:
a preparation method of temperature-sensitive hydrogel comprises the following specific steps:
(1) adding 20g of polyvinyl alcohol (PVA) into 180g of water, stirring and heating to 90 ℃ until a homogeneous transparent polyvinyl alcohol solution with the mass fraction of 10% is obtained;
(2) transferring the polyvinyl alcohol solution into a mould, and performing irradiation treatment by adopting electron beams60Carrying out irradiation treatment on Co gamma rays with the irradiation dose of 30kGy to obtain polyvinyl alcohol hydrogel with the thickness of 2 mm;
(3) and (3) soaking the polyvinyl alcohol hydrogel prepared in the step (2) in pure water for 24 hours.
The temperature-sensitive hydrogel prepared by the invention has the following performance test experiments:
1. hydrogel phase transition temperature detection
The phase transition temperature of the temperature-sensitive hydrogels prepared in examples 1 to 6 and the hydrogel prepared in comparative example 1 were measured, and the results are shown in Table 1.
TABLE 1 detection of phase transition temperature of hydrogels
| Example numbering | Gallic acid solution concentration | Phase transition temperature |
| Comparative example | 0 | Is free of |
| Example 1 | 0.1％ | 47±2℃ |
| Example 2 | 0.2％ | 53±1℃ |
| Example 3 | 0.5％ | 57±2℃ |
| Example 4 | 0.8％ | 62±1℃ |
| Example 5 | 1.0％ | 65±1℃ |
| Example 6 | 1.2％ | 66±1℃ |
As can be seen from table 1, the phase transition temperature of the temperature-sensitive hydrogel gradually increases with the increase of the concentration of the gallic acid solution, and when the concentration of the gallic acid solution is 1.0%, the phase transition temperature of the temperature-sensitive hydrogel reaches 65 ± 1 ℃, so that the concentration of the gallic acid solution is further increased, and the phase transition temperature of the temperature-sensitive hydrogel does not change significantly. The result shows that the concentration of the gallic acid solution has an important influence on the phase transition temperature of the temperature-sensitive hydrogel, and the phase transition temperature of the prepared temperature-sensitive hydrogel can be changed by adjusting the concentration of the gallic acid solution.
2. Hydrogel transparency change with temperature detection
The temperature-sensitive hydrogel prepared in example 4 was used as an example for transparency change detection, while the hydrogel prepared in comparative example was used as a comparison. The concrete operation of the hydrogel transparency change detection experiment is as follows: the prepared hydrogel is packaged and then placed in a heating table or an oven for heating, and the change of the transparent state of the hydrogel is observed and photographed and recorded, and the result is shown in figure 1.
In FIG. 1, A is a photograph of the initial transparency of the hydrogel without heating (left side is the hydrogel prepared by comparison, right side is the hydrogel prepared by example 4 of the present invention), B is a photograph of the transparency of the hydrogel heated to 61 ℃ (left side is the hydrogel prepared by comparison, right side is the hydrogel prepared by example 4 of the present invention), and C is a photograph of the transparency of the gel heated to 65 ℃ (left side is the hydrogel prepared by comparison, right side is the hydrogel prepared by example 4 of the present invention). As can be seen from FIG. 1, the transparency of the hydrogel prepared in comparative example hardly changed with increasing temperature; the temperature-sensitive hydrogel prepared in the embodiment 4 of the invention gradually changes from opaque milky white to transparent state along with the rise of temperature, and when the temperature of the hydrogel is restored to the initial temperature, the temperature-sensitive hydrogel can still be restored to the initial opaque milky white state; and repeating the processes of initial temperature-heating to final temperature-cooling to initial temperature for many times, the transparency of the temperature sensitive hydrogel can be changed along with the temperature.
3. Hydrogel mechanical property detection
(1) Storage modulus and loss modulus measurements
Storage modulus (G ') and loss modulus (G') were measured using the temperature-sensitive hydrogel prepared in example 4 as an example, while the hydrogel prepared in comparative example was used as a comparative example. The results of the storage modulus and the loss modulus are shown in fig. 2, and the results of the compressive strength are shown in fig. 3.
As can be seen from FIG. 2, the hydrogel prepared in comparative example has a storage modulus G 'during the temperature range from room temperature to 75 deg.C'Almost remains stable (10)3Pa), no significant change occurred; the storage modulus G' (10) of the hydrogel prepared in inventive example 44Pa) is much higher than the comparative example; moreover, at the stage that the temperature is lower than the phase transition temperature, the storage modulus G 'and the loss modulus G' of the temperature-sensitive hydrogel are basically kept unchanged, which is consistent with the comparison example, and when the temperature is close to the phase transition temperature, the G 'and the G' are obviously reduced, which shows that part of the hydrogel system is damaged by polyvinyl alcohol and a hydrogen bond network, so that the strength is suddenly changed, and meanwhile, due to the existence of chemical cross-linking bonds, the temperature-sensitive hydrogel prepared in the embodiment 4 of the invention does not have the state transition of gel-sol, and can keep the original shape unchanged. Thus, the temperature-sensitive type prepared by the present invention has significantly improved mechanical strength compared to the comparative example.
(2) Measurement of hydrogel compressive Strength
The temperature-sensitive hydrogels prepared in examples 2, 3, 4, 5 and 6 according to the present invention were tested for compressive strength, while the hydrogels prepared in comparative examples were used as a comparison. The results of the compression strength test are shown in fig. 3.
As can be seen from FIG. 3, the compressive strength of the hydrogel prepared in the comparative example was 0.055MPa and the compressive strengths of the temperature-sensitive hydrogels prepared in examples 2, 3, 4, 5 and 6 according to the present invention were 0.337MPa, 1.338MPa, 1.632MPa, 1.922Ma and 1.884MPa, respectively, under the same strain (25.6%), wherein the compressive strength of the temperature-sensitive hydrogel prepared in example 5 was increased by 3391% as compared to that of the comparative example, thus indicating that the compressive strength of the temperature-sensitive hydrogel prepared according to the present invention was significantly higher than that of the conventional polyvinyl alcohol hydrogel.
Furthermore, as can be seen from fig. 3, the compressive strength of the temperature-sensitive hydrogel of the present invention increases with the concentration of gallic acid solution, and when the mass fraction of the gallic acid solution is greater than 1%, the compressive strength remains substantially unchanged because the absorption of gallic acid by the polyvinyl alcohol hydrogel approaches saturation.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of temperature-sensitive hydrogel is characterized by comprising the following steps: and (3) putting the polyvinyl alcohol hydrogel into gallic acid solution for dipping treatment, and obtaining the temperature-sensitive polyvinyl alcohol hydrogel after dipping.
2. The method according to claim 1, wherein the gallic acid solution is prepared by dissolving gallic acid in water, and the mass fraction of gallic acid in the gallic acid solution is 0.1-1.2%.
3. The method according to claim 2, wherein the immersion treatment time is 2 to 48 hours.
4. The method according to claim 2, wherein the polyvinyl alcohol hydrogel is prepared by: and (3) carrying out irradiation treatment on the polyvinyl alcohol aqueous solution to obtain the polyvinyl alcohol hydrogel.
5. The method according to claim 4, wherein the mass fraction of the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is 10% to 15%.
6. The production method according to claim 5, wherein the irradiation treatment is performed at an irradiation dose of 10 to 30 kGy.
7. The method according to claim 6, wherein the irradiation treatment is performed by60Irradiation with Co gamma rays or electron beamsAnd (6) irradiating.
8. A temperature-sensitive hydrogel product produced by the production method according to any one of claims 1 to 7.
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