CN114507314A - Hydrogel sensitive to temperature and solvent concentration and preparation method thereof - Google Patents
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 110
- 239000002904 solvent Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 50
- 230000035945 sensitivity Effects 0.000 claims abstract description 42
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 22
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 22
- 239000001639 calcium acetate Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000010382 chemical cross-linking Methods 0.000 claims abstract description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 238000002791 soaking Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical group OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 claims description 22
- 239000011229 interlayer Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 16
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 claims description 11
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002985 plastic film Substances 0.000 claims description 9
- 229920006255 plastic film Polymers 0.000 claims description 9
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 9
- 239000004800 polyvinyl chloride Substances 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
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- 239000000499 gel Substances 0.000 abstract description 17
- 231100000956 nontoxicity Toxicity 0.000 abstract description 6
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- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 28
- 238000002834 transmittance Methods 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- -1 carboxylate radical ions Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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Abstract
The invention discloses a hydrogel sensitive to temperature and solvent concentration and a preparation method thereof, wherein the preparation method comprises the following steps: adding a hydrophilic monomer methacrylic acid, a chemical cross-linking agent and a photoinitiator into deionized water, and mixing until the monomers are completely dissolved to obtain a pre-polymerization solution; injecting the pre-polymerization liquid into a mold, and irradiating under an ultraviolet spotlight to obtain precursor hydrogel; and (3) soaking the precursor hydrogel in a calcium acetate solution for at least 30 days to prepare the hydrogel which is sensitive to both temperature and solvent concentration. The invention can prepare the sensitive intelligent hydrogel with temperature sensitivity and solvent concentration sensitivity, solves the problem of single sensitivity of the traditional sensitive intelligent gel material, improves the sensitivity range of the hydrogel, and has the advantages of simple preparation process, easily obtained raw materials, low cost and no toxicity or harm to the environment.
Description
Technical Field
The invention relates to the technical field of intelligent gel materials, in particular to a hydrogel sensitive to temperature and solvent concentration and a preparation method thereof.
Background
Hydrogels are water-based and have a unique internal structure and crosslinked network. Different hydrogels can be obtained by different preparation methods or preparation formulas during the preparation of the hydrogels, and the properties and functions of the hydrogels can be different.
The sensitive intelligent gel material is a novel material which can respond to external stimuli correspondingly. The traditional sensitive intelligent gel material can only respond correspondingly (such as phase separation, shape, mechanical strength and the like) to external single stimuli (such as physical stimuli and chemical stimuli), and the gel has good adaptability in application. The sensitive intelligent gel can be divided into a biosensing hydrogel, a shape self-adaptive hydrogel actuator, a nano-composite hydrogel strain and pressure sensor and the like according to different application layers.
At present, the main problem of the traditional sensitive intelligent gel material is that the sensitivity is relatively single, and the sensitive intelligent gel material cannot cope with various external changing environments, which greatly limits the application range of the sensitive intelligent gel, so that the sensitive intelligent gel material which responds to two or more external stimuli at the same time is urgently needed to be developed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a hydrogel which is sensitive to both temperature and solvent concentration and a preparation method thereof, so as to solve the technical problems in the prior art. The invention can prepare the sensitive intelligent hydrogel with temperature sensitivity and solvent concentration sensitivity, solves the problem of single sensitivity of the traditional sensitive intelligent gel material, improves the sensitivity range of the hydrogel, can cope with more external environmental stimuli, and has simple preparation process, easily obtained raw materials, low cost and no toxicity or harm to the environment.
The purpose of the invention is realized by the following technical scheme:
a method for preparing hydrogel which is sensitive to temperature and solvent concentration, comprising the following steps:
step 1, adding a hydrophilic monomer methacrylic acid, a chemical cross-linking agent and a photoinitiator into deionized water, and mixing until the monomers are completely dissolved to obtain a pre-polymerization solution;
step 2, injecting the pre-polymerization solution into a mold, and placing the mold under an ultraviolet spotlight for irradiation, thereby obtaining precursor hydrogel;
and 3, soaking the precursor hydrogel in a calcium acetate solution for at least 30 days to prepare the hydrogel which is sensitive to both temperature and solvent concentration.
Preferably, in the step 1, the chemical crosslinking agent is N-N 'methylene bisacrylamide, the photoinitiator is alpha-ketoglutaric acid, and the mass ratio of the hydrophilic monomer methacrylic acid to the N-N' methylene bisacrylamide to the alpha-ketoglutaric acid is 0.8609-6.0623: 0.015-0.108: 0.0014-0.0103.
Preferably, in the step 3, the concentration of the calcium acetate solution is 100-500 mmol/L.
Preferably, in the step 2, the irradiation under the ultraviolet spotlight is performed for 6 to 8 hours under the ultraviolet spotlight with the power of 36 w.
Preferably, in the step 2, the method for preparing the mold comprises: cutting the interlayer material into a square shape, hollowing the interlayer material, clamping the interlayer material by using two glass sheets with the same size, and clamping by using a long-tail clamp to obtain the mold.
Preferably, the interlayer material is a polyvinyl chloride plastic film material, the side lengths of the glass sheet and the interlayer material are both 10cm, and the side length of the hollowed area of the interlayer material is 8 cm.
Preferably, in the step 1, the mixing manner is at least one of ultrasound, shaking and magnetic stirring.
The hydrogel sensitive to both temperature and solvent concentration is prepared by the preparation method of the hydrogel sensitive to both temperature and solvent concentration.
Compared with the prior art, the method comprises the steps of firstly forming a crosslinking network by chemically crosslinking and photoinitiating a prepolymerization solution mixed by a hydrophilic monomer methacrylic acid, a chemical crosslinking agent and a photoinitiator under the irradiation of ultraviolet light with specific power, forming a precursor hydrogel of which the main component is polymethacrylic acid in a three-dimensional network shape by free radical polymerization, and then soaking the precursor hydrogel in a calcium acetate solution for a certain time so as to introduce calcium ions into the precursor hydrogel with LCST (lower critical solution temperature), wherein the calcium ions in the calcium acetate solution carry divalent positive ions and can be simultaneously combined with two chain segments of carboxylate radical ions carried in the precursor hydrogel, so that the internal combination of the hydrogel is tighter, the mechanical property is greatly improved, and the hydrogel has stronger sensitivity in response to the change of an external environment, can have double sensitivity of temperature sensitivity and solvent concentration sensitivity: when the external calcium ion concentration of the hydrogel changes, the concentration difference can cause the calcium ion concentration in the hydrogel to change, so that the hydrogel is subjected to concentration sensitivity to whiten, and when the external temperature of the hydrogel reaches a value above an LCST value, the hydrogel is subjected to phase change, so that the hydrogel has excellent temperature sensitivity; the method solves the problems of single sensitivity and high preparation difficulty of the traditional sensitive intelligent gel material, improves the sensitivity range of the hydrogel, can respond to more external environmental stimuli, and has the advantages of strong sensitivity, simple preparation process, easy acquisition of used raw materials, low cost and no toxicity or harm to the environment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a graph of the transmittance of temperature and solvent concentration sensitive hydrogels prepared in example 1 of the present invention in different concentrations of calcium acetate over time.
FIG. 2 is a graph showing the transmittance of a temperature-and solvent-concentration-sensitive hydrogel prepared in example 1 of the present invention as a function of temperature.
FIG. 3 is a graph showing the stress-strain curves at different temperatures for the hydrogel with dual sensitivity to temperature and solvent concentration prepared in example 1 of the present invention.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below by combining the attached drawings in the embodiment of the invention; it is to be understood that the described embodiments are merely exemplary of the invention, and are not intended to limit the invention to the particular forms disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The terms that may be used herein are first described as follows:
the terms "comprising," "including," "containing," "having," or other similar terms of meaning should be construed as non-exclusive inclusions. For example: including a feature (e.g., material, component, ingredient, carrier, formulation, material, dimension, part, component, mechanism, device, process, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product, or article of manufacture), is to be construed as including not only the particular feature explicitly listed but also other features not explicitly listed as such which are known in the art.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as ranges of values, the ranges of values should be understood to specifically disclose all ranges formed by any pair of upper values, lower values, or preferred values within the range, regardless of whether the ranges are explicitly recited; for example, if a numerical range of "2 ~ 8" is recited, then the numerical range should be interpreted to include ranges of "2 ~ 7", "2 ~ 6", "5 ~ 7", "3 ~ 4 and 6 ~ 7", "3 ~ 5 and 7", "2 and 5 ~ 7", and the like. Unless otherwise indicated, the numerical ranges recited herein include both the endpoints thereof and all integers and fractions within the numerical range.
The hydrogel sensitive to both temperature and solvent concentration and the preparation method thereof provided by the present invention are described in detail below. Details not described in the present invention are well known to those skilled in the art. Those not specifically mentioned in the examples of the present invention were carried out according to the conventional conditions in the art or conditions suggested by the manufacturer. The reagents or instruments used in the examples of the present invention are not specified by manufacturers, and are all conventional products available by commercial purchase.
The invention provides a preparation method of hydrogel which is double sensitive to temperature and solvent concentration, which is used for preparing hydrogel which is double sensitive to temperature and solvent concentration and comprises the following steps:
step 1, adding a hydrophilic monomer methacrylic acid, a chemical cross-linking agent and a photoinitiator into deionized water, and fully and uniformly mixing until the monomers are completely dissolved to obtain a pre-polymerization solution.
And 2, injecting the pre-polymerization solution into a mold, and placing the mold under a 36w ultraviolet spotlight for irradiating for 6-8 hours to obtain the precursor hydrogel.
And 3, completely soaking the precursor hydrogel in a calcium acetate solution, wherein the concentration of the calcium acetate solution is 100-500 mmol/L, and the soaking time is at least 30 days, so that the hydrogel sensitive to both temperature and solvent concentration is prepared.
Specifically, the preparation method of the hydrogel which is dual sensitive to temperature and solvent concentration may include the following embodiments:
(1) in the step 1, N-N 'methylene bisacrylamide is preferably adopted as the chemical crosslinking agent, alpha-ketoglutaric acid is preferably adopted as the photoinitiator, and the mass ratio of the hydrophilic monomer methacrylic acid to the N-N' methylene bisacrylamide to the alpha-ketoglutaric acid is 0.8609-6.0623: 0.015-0.108: 0.0014-0.0103.
(2) In the step 1, the mixing mode is at least one of ultrasonic, vibration and magnetic stirring.
(3) In the step 2, the method for preparing the mold includes: cutting the interlayer material into a square shape, hollowing the interlayer material, clamping the interlayer material by two glass sheets with the same size, and clamping by a certain number of long-tail clamps to obtain the mold. The glass plate is characterized in that the interlayer material is a polyvinyl chloride plastic film material, the side lengths of the glass plate and the interlayer material are both 10cm, and the side length of a hollowed area of the interlayer material is 8 cm. In practice, the pre-polymerization solution may be injected into the mold by means of a syringe.
(4) In the step 3, the calcium acetate solution is preferably made of calcium acetate with the content of at least 99.7%, and the concentration of the calcium acetate solution is preferably 500 mmol/L.
Compared with the prior art, the hydrogel which is sensitive to both temperature and solvent concentration and the preparation method thereof provided by the invention have the following advantages:
(1) the invention firstly carries out chemical crosslinking and photoinitiation under the irradiation of ultraviolet light with specific power on pre-polymerized liquid mixed by hydrophilic monomer methacrylic acid, chemical crosslinking agent and photoinitiator to form a crosslinked network, and forms precursor hydrogel with a three-dimensional network shape and the main component of polymethacrylic acid through free radical polymerization, and then the precursor hydrogel is soaked in calcium acetate solution with specific concentration for a certain time, thereby calcium ions are introduced into the precursor hydrogel with LCST, because the calcium ions in the calcium acetate solution carry divalent positive ions and can be simultaneously combined with two chain segments of carboxylate radical ions carried in the precursor hydrogel, the internal combination of the hydrogel is tighter, the mechanical property is greatly improved, and the hydrogel has stronger sensitivity when dealing with the change of external environment, can have double sensitivity of temperature sensitivity and solvent concentration sensitivity: when the external calcium ion concentration of the hydrogel changes, the concentration difference can cause the calcium ion concentration in the hydrogel to change, so that the hydrogel is subjected to concentration sensitivity to whiten, and when the external temperature of the hydrogel reaches a value above an LCST value, the hydrogel is subjected to phase change, so that the hydrogel has excellent temperature sensitivity; the method solves the problems of single sensitivity and high preparation difficulty of the traditional sensitive intelligent gel material, improves the sensitivity range of the hydrogel, and has the advantages of strong sensitivity, simple preparation process, easily obtained raw materials, low cost and no toxicity or harm to the environment.
(2) The hydrogel which is sensitive to both temperature and solvent concentration and prepared by the invention has good mechanical property, and particularly, when the hydrogel is heated to a certain temperature, the strength of the hydrogel is improved by nearly one order of magnitude, so that the sensitive intelligent hydrogel which responds to two external stimuli, namely temperature and solvent concentration, prepared by the invention solves the problem that the strength of the traditional sensitive intelligent gel material is not high enough, and has great application value in the fields of physics, engineering and the like.
(3) The hydrogel prepared by the invention is a sensitive intelligent hydrogel which can respond to two external stimuli of temperature and solvent concentration at the same time, and the development way of the hydrogel in the aspects of optical devices, medical fields, information storage and the like is expanded.
In conclusion, the embodiment of the invention can prepare the sensitive intelligent hydrogel with temperature sensitivity and solvent concentration sensitivity, solves the problem of single sensitivity of the traditional sensitive intelligent gel material, improves the sensitivity range of the hydrogel, can respond to more external environmental stimuli, and has the advantages of simple preparation process, easily obtained raw materials, low cost, no toxicity and no harm to the environment.
In order to more clearly show the technical solutions and the technical effects provided by the present invention, the hydrogel sensitive to both temperature and solvent concentration and the preparation method thereof provided by the embodiments of the present invention are described in detail with specific examples.
Example 1
A hydrogel which is sensitive to both temperature and solvent concentration can be prepared by the following steps:
a1, cutting a polyvinyl chloride plastic film material into squares, hollowing the squares, clamping the polyvinyl chloride plastic film material by two glass sheets with the same size, clamping the glass sheets by a certain number of long tail clamps, wherein the side lengths of the glass sheets and the interlayer material are both 10cm, and the side length of the hollowed area of the interlayer material is 8cm, so that the mold is manufactured.
Step A2, adding 2.5827g of hydrophilic monomer methacrylic acid, 46.251mg of chemical cross-linking agent N-N' methylene bisacrylamide and 4.383mg of photoinitiator alpha-ketoglutaric acid into 10g of deionized water, and then placing the mixture on a magnetic stirrer to stir for 15min until the components are completely dissolved and uniformly mixed, thereby obtaining the pre-polymerization solution.
Step A3, injecting the pre-polymerized liquid obtained in the step A2 into the mold obtained in the step A1 through a disposable plastic drop, and placing the mold under a 36w ultraviolet spotlight for irradiating for 8 hours, thereby obtaining the precursor hydrogel.
And A4, completely soaking the precursor hydrogel in a calcium acetate solution, wherein the concentration of the calcium acetate solution is 500mmol/L, and the soaking time is at least 30 days, so that the hydrogel sensitive to both temperature and solvent concentration is prepared.
Example 2
A hydrogel which is sensitive to both temperature and solvent concentration can be prepared by the following steps:
and step B1, cutting the polyvinyl chloride plastic film material into a square shape, hollowing the middle of the square shape, clamping the polyvinyl chloride plastic film material by two glass sheets with the same size, clamping the glass sheets by a certain number of long tail clamps, wherein the side length of each glass sheet and the interlayer material is 10cm, and the side length of the hollowed area of the interlayer material is 8cm, so that the mold is manufactured.
And step B2, adding 4.3045g of hydrophilic monomer methacrylic acid, 77.085mg of chemical cross-linking agent N-N 'methylene bisacrylamide and 7.305mg of photoinitiator alpha-ketoglutaric acid into 10g of deionized water, and then stirring for 15min on a magnetic stirrer until the hydrophilic monomer methacrylic acid, the chemical cross-linking agent N-N' methylene bisacrylamide and the photoinitiator alpha-ketoglutaric acid are completely dissolved and uniformly mixed, thereby obtaining a pre-polymerization liquid.
And step B3, injecting the pre-polymerization solution obtained in the step B2 into the mold obtained in the step B1 through a disposable plastic drop, and placing the mold under a 36w ultraviolet spotlight for irradiating for 7 hours to obtain the precursor hydrogel.
And step B4, completely soaking the precursor hydrogel in a calcium acetate solution, wherein the concentration of the calcium acetate solution is 250mmol/L, and the soaking time is at least 30 days, so that the hydrogel sensitive to both temperature and solvent concentration is prepared.
Example 3
A hydrogel which is sensitive to both temperature and solvent concentration can be prepared by the following steps:
and step C1, cutting the polyvinyl chloride plastic film material into a square shape, hollowing the middle of the square shape, clamping the polyvinyl chloride plastic film material by two glass sheets with the same size, clamping the glass sheets by a certain number of long tail clamps, wherein the side length of each glass sheet and the interlayer material is 10cm, and the side length of the hollowed area of the interlayer material is 8cm, so that the mold is manufactured.
And step C2, adding 6.0263g of hydrophilic monomer methacrylic acid, 107.919mg of chemical cross-linking agent N-N 'methylene bisacrylamide and 10.227mg of photoinitiator alpha-ketoglutaric acid into 10g of deionized water, and then stirring for 15min on a magnetic stirrer until the hydrophilic monomer methacrylic acid, the chemical cross-linking agent N-N' methylene bisacrylamide and the photoinitiator alpha-ketoglutaric acid are completely dissolved and uniformly mixed, thereby obtaining the pre-polymerization liquid.
And C3, injecting the pre-polymerization solution obtained in the step C2 into the mold obtained in the step C1 through a disposable plastic drop, and placing the mold under a 36w ultraviolet spotlight for 6 hours to obtain the precursor hydrogel.
And step C4, completely soaking the precursor hydrogel in a calcium acetate solution, wherein the concentration of the calcium acetate solution is 100mmol/L, and the soaking time is at least 30 days, so that the hydrogel sensitive to both temperature and solvent concentration is prepared.
Performance detection
The hydrogel prepared in example 1 of the present invention, which is sensitive to both temperature and solvent concentration, was tested for the following properties:
(1) the time-dependent transmittance of the hydrogel sensitive to both temperature and solvent concentration prepared in example 1 of the present invention was measured in different concentrations of calcium acetate solution, so as to obtain the time-dependent transmittance curve shown in fig. 1. As can be seen from fig. 1: when the solvent concentration was decreased, the transmittance of the hydrogel was significantly decreased with the lapse of time, and the larger the difference in the solvent concentration was, the larger the transmittance decrease was, which indicates that the hydrogel having double sensitivity to temperature and solvent concentration prepared in example 1 of the present invention had good sensitivity to the solvent concentration.
(2) The temperature-dependent transmittance of the hydrogel prepared in example 1 was measured to obtain a transmittance curve as shown in FIG. 2. As can be seen from fig. 2: when the external temperature is increased, the transmittance of the hydrogel is obviously reduced, and the hydrogel is whitened in whole, which shows that the hydrogel which is sensitive to both temperature and solvent concentration and prepared in the example 1 of the invention has extremely strong sensitivity to temperature.
(3) Stress-strain conditions of the hydrogel which is prepared in example 1 and is sensitive to both temperature and solvent concentration at different temperatures are detected, so as to obtain a stress-strain curve diagram shown in fig. 3. As can be seen from fig. 3: when the external temperature rises, the strength of the hydrogel is increased, and when the temperature rises to 95 ℃, the strength of the hydrogel is increased by nearly one order of magnitude, which further illustrates that the hydrogel which is prepared in the embodiment 1 and is sensitive to both temperature and solvent concentration has extremely strong sensitivity to temperature, and the problem that the strength of the traditional sensitive intelligent gel material is not high enough can be solved.
In conclusion, the embodiment of the invention can prepare the sensitive intelligent hydrogel with temperature sensitivity and solvent concentration sensitivity, solves the problem of single sensitivity of the traditional sensitive intelligent gel material, improves the sensitivity range of the hydrogel, can respond to more external environmental stimuli, and has the advantages of simple preparation process, easily obtained raw materials, low cost, no toxicity and no harm to the environment.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (8)
1. A method for preparing hydrogel which is sensitive to temperature and solvent concentration, which is characterized by comprising the following steps:
step 1, adding a hydrophilic monomer methacrylic acid, a chemical cross-linking agent and a photoinitiator into deionized water, and mixing until the monomers are completely dissolved to obtain a pre-polymerization solution;
step 2, injecting the pre-polymerization solution into a mold, and placing the mold under an ultraviolet spotlight for irradiation, thereby obtaining precursor hydrogel;
and 3, soaking the precursor hydrogel in a calcium acetate solution for at least 30 days to prepare the hydrogel which is sensitive to both temperature and solvent concentration.
2. The method for preparing a hydrogel which is dual sensitive to temperature and solvent concentration according to claim 1, wherein in the step 1, the chemical cross-linking agent is N-N 'methylene bisacrylamide, the photoinitiator is alpha-ketoglutaric acid, and the mass ratio of the hydrophilic monomer methacrylic acid to the N-N' methylene bisacrylamide and the alpha-ketoglutaric acid is 0.8609-6.0623: 0.015-0.108: 0.0014-0.0103.
3. The method for preparing hydrogel which is sensitive to both temperature and solvent concentration according to claim 1 or 2, wherein in the step 3, the concentration of the calcium acetate solution is 100-500 mmol/L.
4. The method for preparing hydrogel which is sensitive to both temperature and solvent concentration according to claim 1 or 2, wherein in the step 2, the irradiation under the UV spotlight is performed for 6-8 hours under the UV spotlight with power of 36 w.
5. The method for preparing hydrogel which is sensitive to both temperature and solvent concentration according to claim 1 or 2, wherein in the step 2, the method for preparing the mold comprises: cutting the interlayer material into a square shape, hollowing the interlayer material, clamping the interlayer material by two glass sheets with the same size, and clamping by a long-tail clamp to obtain the mold.
6. The method for preparing hydrogel with dual sensitivity to temperature and solvent concentration according to claim 5, wherein the barrier material is polyvinyl chloride plastic film material, the side length of the glass sheet and the barrier material is 10cm, and the side length of the hollow area of the barrier material is 8 cm.
7. The method for preparing hydrogel with dual sensitivity to temperature and solvent concentration according to claim 1 or 2, wherein in the step 1, the mixing manner is at least one of ultrasound, shaking and magnetic stirring.
8. A hydrogel which is sensitive to both temperature and solvent concentration, which is prepared by the method for preparing the hydrogel according to any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210247689.2A CN114507314A (en) | 2022-03-14 | 2022-03-14 | Hydrogel sensitive to temperature and solvent concentration and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651218A (en) * | 2022-08-25 | 2023-01-31 | 四川大学 | Method for preparing injectable polyphenol-macromolecule adhesive hydrogel |
| CN117582900A (en) * | 2024-01-18 | 2024-02-23 | 广州贝龙环保产业科技股份有限公司 | Intelligent production system of hydrogel phase change cold storage material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177636A (en) * | 2013-05-22 | 2014-12-03 | 天津科技大学 | In-situ mineralized reinforced composite hydrogel and preparation method thereof |
| CN104610495A (en) * | 2015-02-05 | 2015-05-13 | 中国科学院兰州化学物理研究所 | Preparation method of bi-crosslinked hydrogel |
| CN113648455A (en) * | 2021-08-10 | 2021-11-16 | 太原理工大学 | Double-slow-release drug-loaded hydrogel dressing with double-layer microspheres encapsulated in semi-interpenetrating network, and preparation method and application thereof |
| CN113943430A (en) * | 2021-10-27 | 2022-01-18 | 中国科学院长春应用化学研究所 | In-situ mineralized hydrogel and preparation method and application thereof |
-
2022
- 2022-03-14 CN CN202210247689.2A patent/CN114507314A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177636A (en) * | 2013-05-22 | 2014-12-03 | 天津科技大学 | In-situ mineralized reinforced composite hydrogel and preparation method thereof |
| CN104610495A (en) * | 2015-02-05 | 2015-05-13 | 中国科学院兰州化学物理研究所 | Preparation method of bi-crosslinked hydrogel |
| CN113648455A (en) * | 2021-08-10 | 2021-11-16 | 太原理工大学 | Double-slow-release drug-loaded hydrogel dressing with double-layer microspheres encapsulated in semi-interpenetrating network, and preparation method and application thereof |
| CN113943430A (en) * | 2021-10-27 | 2022-01-18 | 中国科学院长春应用化学研究所 | In-situ mineralized hydrogel and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LUQIN HUA ET AL.: "Cold-induced shape memory hydrogels for strong and programmable", 《SCIENCE CHINA MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115651218A (en) * | 2022-08-25 | 2023-01-31 | 四川大学 | Method for preparing injectable polyphenol-macromolecule adhesive hydrogel |
| CN115651218B (en) * | 2022-08-25 | 2024-05-17 | 四川大学 | Method for preparing injectable polyphenol-macromolecule adhesive hydrogel |
| CN117582900A (en) * | 2024-01-18 | 2024-02-23 | 广州贝龙环保产业科技股份有限公司 | Intelligent production system of hydrogel phase change cold storage material |
| CN117582900B (en) * | 2024-01-18 | 2024-04-05 | 广州贝龙环保产业科技股份有限公司 | Intelligent production system of hydrogel phase change cold storage material |
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