CN116376060A - Hydrogel phase-change material suitable for cold chain transportation and preparation method and application thereof - Google Patents
Hydrogel phase-change material suitable for cold chain transportation and preparation method and application thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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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- 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
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract
The invention discloses a hydrogel phase-change material suitable for cold chain transportation, and a preparation method and application thereof. The preparation method comprises the following steps: mixing acrylamide, salt, N' -methylene-bis-acrylamide, a photoinitiator and water, and heating to fully dissolve to obtain a gel solution; the salt is at least one of sodium chloride and potassium chloride; adding N, N-dimethylformamide solution of fluorescent molecules into the gel solution, and irradiating with ultraviolet light to obtain a hydrogel phase-change material; the fluorescent molecule is at least one of tetraphenyl ethylene, tetra [4- (3, 5-dicarboxyphenyl ] tetraphenyl ethylene, 4'- (1, 2-diphenyl-1, 2-ethylenediynyl) dibenzoic acid and 4,4' - (1, 2-diphenylethylene-1, 2-diyl) diphenylamine.
Description
Technical Field
The invention relates to the field of cold chain transportation, in particular to a hydrogel phase-change material suitable for cold chain transportation, and a preparation method and application thereof.
Background
Cold chain transportation is an important link of cold chain logistics, and how to reduce the cold chain transportation cost has important significance for the development of the cold chain logistics.
The cold-storage ice bag is an important cold-storage product for cold chain transportation, has the characteristics of no toxicity, no harm and repeated use, and is widely used in the fields of aquatic product preservation, milk product preservation, fruit beverage cold storage, biological reagent, plasma and vaccine cold preservation, physical cooling such as bruise, fever and the like.
Compared with dry ice with low-temperature fresh-keeping effect, the ice bag is not limited by transportation modes such as aviation, trains and the like. Even if the ice bag is recovered, the mass volume of the ice bag does not change obviously before and after normal-temperature thawing, so that the recovery cost is about equal to the cost of transporting again. Research in the field of refrigerating materials is increasingly developed, for example, a patent with publication number CN115505064A discloses a preparation method of a low-soluble substance super absorbent resin and application of the low-soluble substance super absorbent resin in preparation of ice bags, and a patent with publication number CN113444200A discloses an anti-freezing hydrogel and a preparation method and application of the anti-freezing hydrogel.
However, most of the refrigeration ice bags widely used at present are specially prepared compounds, the refrigeration ice bags are in a liquid state after thawing, and when the packaging bags are damaged, liquid leakage is caused, so that environmental pollution is caused, and meanwhile, the problems of difficult recovery and the like are faced. In addition, the freezing degree of the ice bag cannot be monitored in the freezing process of the ice bag, and the ice bag is not frozen or is frozen but is frozen continuously because the freezing degree is not monitored, so that resource waste is caused.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a preparation method of a hydrogel phase-change material suitable for cold chain transportation, the prepared hydrogel phase-change material is in a gel state under the general condition, the problem of liquid leakage after the package bag of the conventional refrigeration ice bag is damaged is solved, the hydrogel phase-change material can be reused, the quality and the volume of the water absorption and dehydration process are greatly changed, the recovery is convenient, and the practical application is facilitated. In addition, the hydrogel phase-change material can also show different fluorescence properties in different states, for example, the hydrogel phase-change material is transparent in fluorescence in a common gel state, and the hydrogel phase-change material is opaque in a low-temperature freezing state, and the fluorescence intensity is obviously stronger than that in the common gel state. The characteristic enables the freezing process to be timely and accurately adjusted according to the fluorescence result feedback, so that the transition waste of refrigeration energy consumption is avoided, and the energy is saved.
The specific technical scheme is as follows:
a preparation method of hydrogel phase-change material suitable for cold chain transportation comprises the following steps:
(1) Mixing acrylamide, salt, N' -methylene-bis-acrylamide, a photoinitiator and water, and heating to fully dissolve to obtain a gel solution; the salt is at least one of sodium chloride and potassium chloride;
(2) Adding N, N-dimethylformamide solution of fluorescent molecules into the gel solution, and irradiating with ultraviolet light to obtain the hydrogel phase-change material; the fluorescent molecule is at least one of tetraphenyl ethylene, tetra [4- (3, 5-dicarboxyphenyl ] tetraphenyl ethylene, 4'- (1, 2-diphenyl-1, 2-ethylenediynyl) dibenzoic acid and 4,4' - (1, 2-diphenylethylene-1, 2-diyl) diphenylamine.
According to the preparation method provided by the invention, acrylamide is used as a crosslinking monomer, N' -methylene-bis-acrylamide is used as a crosslinking agent, salt (namely sodium chloride, potassium chloride or a mixture of the sodium chloride and the potassium chloride) and a photoinitiator are added to prepare a gel solution, and in the step (2), the freezing phase change process of the hydrogel phase change material is easy to monitor by adding specific fluorescent molecules.
The hydrogel phase-change material can achieve high salt content, and further obtain a lower solidifying point. In a preferred embodiment, in the preparation method, in the step (1), the mass ratio of the acrylamide to the salt to the water is 1-2:1.5-3:10.
The increased amount of the cross-linking agent N, N' -methylene-bis-acrylamide can improve the toughness and the forming capability of the hydrogel phase-change material. In a preferred embodiment, in the preparation method, in the step (1), the mass ratio of the acrylamide to the N, N' -methylene-bis-acrylamide to the photoinitiator is 100:0.01-0.5:2-4.
In a preferred embodiment, in the preparation method, in the step (1), the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone (Irgacure 2959).
In one embodiment, in the preparation method, in step (1), the gel solution further contains agar. The amount of agar can be adjusted according to the target toughness of the hydrogel phase-change material. Optionally, the mass ratio of agar to water is 0.1-0.3:10.
In a preferred embodiment, in the preparation method, in the step (1), the heating temperature is 80-90 ℃.
In the preparation method, in the step (2), the dosage ratio of fluorescent molecules, N-dimethylformamide and water in the gel solution is preferably 4-6 mg:0.3-0.5 mL:20g, and more preferably 5mg:0.4mL:20g.
In a preferred embodiment, in the preparation method, in the step (2), the wavelength of the ultraviolet light is 365nm.
In the above preparation method, in the step (2), the irradiation time is preferably not less than 1h, and more preferably 2 to 2.5h.
The invention also provides the hydrogel phase-change material prepared by the preparation method.
The hydrogel phase-change material which has the advantages of low freezing point, easy monitoring of the phase-change process, reusability, excellent water absorption and retention properties, safety and low cost recovery and is particularly suitable for cold chain transportation is successfully prepared by the preparation method with simple operation process and low cost.
The invention also provides application of the hydrogel phase-change material in cold chain transportation as a general inventive concept.
The hydrogel phase-change material prepared by the preparation method provided by the invention can be soaked in water for continuous water absorption, and according to the test result, when the mass of the prepared hydrogel phase-change material is 9 g, the mass of the hydrogel phase-change material after being soaked in water can reach 28 g at most, and the mass is about 3 times more than the initial mass; the hydrogel obtained is dried, the weight of the hydrogel can reach 3 g at the minimum after the moisture is removed, and the calculation shows that the water absorption capacity of the hydrogel phase-change material can reach more than 8 times of the dry weight of the hydrogel phase-change material. And meanwhile, after the xerogel with water removed is recovered, the high-salt water gel phase-change material is soaked in water again for repeated use.
Based on the characteristics of repeated water absorption and dehydration, large quality change, xerogel state instead of flowing liquid state after removing water and the like, the hydrogel phase-change material can be well recycled when being used for cold chain transportation, and has low recycling difficulty and large recycling amount, and a large amount of recycling can be realized only by dehydrating the hydrogel phase-change material into xerogel, so that the recycling efficiency is high and the transportation cost is low.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method provided by the invention has simple operation process, and can be prepared by only heating to dissolve the raw materials and then using ultraviolet irradiation; the raw material salt (namely sodium chloride, potassium chloride or a mixture of the sodium chloride and the potassium chloride) and the raw material acrylamide used in the preparation method are low in cost and easy to obtain; the preparation method is flexible, and the concentration ratio of each raw material and whether agar is added or not can be adjusted according to actual requirements, so that the hydrogel phase-change material with different softness and toughness is prepared.
2. The preparation method provided by the invention can prepare the hydrogel phase-change material with low freezing point, the hydrogel phase-change material is in a gel state after thawing, and the hydrogel phase-change material cannot flow out and leak due to package breakage, so that the safety and convenience in the cold chain transportation and refrigeration process are improved; in addition, the hydrogel phase-change material can contain high-concentration salt, so that the solidifying point of the hydrogel phase-change material is greatly reduced, and the hydrogel phase-change material still presents a soft gel state at minus 20 ℃ and is not frozen.
3. The hydrogel phase-change material provided by the invention has excellent water absorption and water retention properties, and the water absorption capacity can reach more than 8 times of the dry weight of the hydrogel phase-change material. After the use, the water can be removed to become xerogel, the weight and the volume are greatly reduced, and the recycling cost can be greatly reduced by recycling and transporting in the xerogel form.
4. The hydrogel phase-change material provided by the invention can be repeatedly used, is environment-friendly, is not easy to deform and has strong toughness.
5. The phase change process of the hydrogel phase change material provided by the invention is easy to monitor, and different fluorescent characteristics are shown in different phase states by introducing specific fluorescent molecules, so that accurate feedback and regulation and control of the phase state of the hydrogel phase change material are facilitated, manual direct touch sensing is not needed, the labor cost is reduced, and the damage of low temperature to human bodies is avoided.
Drawings
FIG. 1 is a photograph of a high brine gel phase change material prepared in example 1.
Fig. 2 is a photograph of a stretched high-salt hydrogel phase-change material prepared in example 1.
Fig. 3 is a photograph of the high salt hydrogel phase-change material prepared in example 1 after stretching and self-reduction.
Fig. 4 is a photograph of the high brine gel phase change material prepared in example 2.
Fig. 5 is a photograph of the high brine gel phase change material prepared in example 3.
FIG. 6 is a graph showing the results of a flash Differential Scanning Calorimetry (DSC) test of the high-salt hydrogel phase-change material prepared in example 3.
FIG. 7 is a fluorescence photograph of the hydrogel phase-change material prepared in example 3 in the gel state (left panel) and frozen state (right panel), respectively.
Fig. 8 is a photograph of the hydrogel phase-change material prepared in example 3 dried with moisture (left panel) and soaked for 1 day after drying (right panel).
Fig. 9 is a graph showing the change in mass with the soaking time after drying the hydrogel phase-change material prepared in example 3.
Detailed Description
The invention will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
The preparation method of the high-salt hydrogel phase-change material which is difficult to deform, has stronger toughness and can restore the original shape and is suitable for cold chain transportation comprises the following steps:
(1) Acrylamide 4 g, sodium chloride 4 g, N, N '-methylene-bis-acrylamide 2.6 mg, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionne (Irgacure 2959) 0.12 g, agar 0.32 g were mixed and added to 20 ml of water;
(2) Heating the solution obtained in the step (1) at 90 ℃ for 5 minutes to accelerate dissolution of raw materials, obtaining a gel solution, dissolving 5mg of fluorescent molecule tetra [4- (3, 5-dicarboxyphenyl ] tetraphenyl ethylene in 400 microliters of N, N-dimethylformamide, obtaining a fluorescent molecule N, N-dimethylformamide solution, and adding the fluorescent molecule N, N-dimethylformamide solution into the gel solution;
(3) And (3) pouring the mixed solution obtained in the step (2) into a required mould, and irradiating with 365nm ultraviolet light for 2 hours to obtain the required high-salt hydrogel phase-change material.
The obtained high-salt hydrogel phase-change material has strong shape retention capacity (see figure 1), and can recover to the original shape by self-reduction after being stretched (see figure 2) (see figure 3). The solidifying point of the obtained high-salt water gel phase-change material is-41 ℃.
Example 2
A preparation method of a high-salt hydrogel phase-change material suitable for cold chain transportation comprises the following steps:
(1) 2 g of acrylamide, 4 g of sodium chloride, 2 mg of N, N '-methylene-bis-acrylamide, 60 mg of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionne (Irgacure 2959) were taken and added to 20 ml of water;
(2) Heating the solution obtained in the step (1) at 90 ℃ for 5 minutes to accelerate dissolution of raw materials, obtaining a gel solution, dissolving 5mg of fluorescent molecule tetra [4- (3, 5-dicarboxyphenyl ] tetraphenyl ethylene in 400 microliters of N, N-dimethylformamide, obtaining a fluorescent molecule N, N-dimethylformamide solution, and adding the fluorescent molecule N, N-dimethylformamide solution into the gel solution;
(3) Pouring the mixed solution obtained in the step (2) into a required mould, and irradiating with 365nm ultraviolet light for 2 hours to obtain the required high-salt hydrogel phase-change material, wherein the appearance is shown in figure 4, and the solidifying point is similar to that of the embodiment 1.
Example 3
A preparation method of a high-salt hydrogel phase-change material suitable for cold chain transportation comprises the following steps:
(1) 2 g of acrylamide, 4 g of sodium chloride, 3 mg of N, N '-methylene-bis-acrylamide, 60 mg of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionne (Irgacure 2959) were taken and added to 20 ml of water;
(2) Heating the solution obtained in the step (1) at 90 ℃ for 5 minutes to accelerate dissolution of raw materials, obtaining a gel solution, dissolving 5mg of fluorescent molecule tetra [4- (3, 5-dicarboxyphenyl ] tetraphenyl ethylene in 400 microliters of N, N-dimethylformamide, obtaining a fluorescent molecule N, N-dimethylformamide solution, and adding the fluorescent molecule N, N-dimethylformamide solution into the gel solution;
(3) Pouring the mixed solution obtained in the step (2) into a required mould, and irradiating with 365nm ultraviolet light for 2 hours to obtain the required high-salt hydrogel phase-change material, wherein the appearance is shown in figure 5, and the solidifying point is similar to that of the embodiment 1.
FIG. 6 is a flash Differential Scanning Calorimetry (DSC) test result of the high-salt aqueous gel phase change material prepared in example 3, showing a freezing point of-41.36℃according to the test result.
With the high-brine gel phase-change material prepared in example 3, the high-brine gel phase-change material was irradiated with 365nm ultraviolet light, and fig. 7 is a fluorescence photograph of the high-brine gel phase-change material in a gel state (left diagram in fig. 7) and frozen state (right diagram in fig. 7), respectively. The high-salt water gel phase-change material has transparent fluorescence and lighter color in a gel state, and has opaque fluorescence and darker color in a low-temperature freezing state, and the fluorescence intensity in the freezing state is obviously stronger than that in the gel state. The difference of fluorescence characteristics under different phase states can be used for reflecting the phase states in time, so that the phase change process of the high-salt hydrogel phase change material is easy to monitor.
Water absorption and retention performance and repeatability experiments of the high-salt hydrogel phase-change material:
the high-salt hydrogel phase-change material prepared in example 3 was dried in an oven at 110 ℃ for 1 hour, the water in the obtained hydrogel was removed (see left diagram in fig. 8), and when the hydrogel phase-change material was used again, it was immersed in water for 1 hour, and if more water was required to be absorbed, the immersion time was prolonged to 1 day (see right diagram in fig. 8).
Fig. 9 is a graph showing the change in mass with soaking time after drying the high-salt aqueous gel phase-change material prepared in example 3.
The high-salt water gel phase-change material disclosed by the invention has good water absorption and water retention performances after repeated dehydration and water absorption for many times.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (10)
1. The preparation method of the hydrogel phase-change material suitable for cold chain transportation is characterized by comprising the following steps:
(1) Mixing acrylamide, salt, N' -methylene-bis-acrylamide, a photoinitiator and water, and heating to fully dissolve to obtain a gel solution; the salt is at least one of sodium chloride and potassium chloride;
(2) Adding N, N-dimethylformamide solution of fluorescent molecules into the gel solution, and irradiating with ultraviolet light to obtain the hydrogel phase-change material; the fluorescent molecule is at least one of tetraphenyl ethylene, tetra [4- (3, 5-dicarboxyphenyl ] tetraphenyl ethylene, 4'- (1, 2-diphenyl-1, 2-ethylenediynyl) dibenzoic acid and 4,4' - (1, 2-diphenylethylene-1, 2-diyl) diphenylamine.
2. The method according to claim 1, wherein in step (1):
the mass ratio of the acrylamide to the salt to the water is 1-2:1.5-3:10;
the mass ratio of the acrylamide to the N, N' -methylene-bis-acrylamide to the photoinitiator is 100:0.01-0.5:2-4.
3. The method of claim 1, wherein in step (1), the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone.
4. The method according to claim 1, wherein in the step (1), the gel solution further contains agar, and the mass ratio of the agar to the water is 0.1-0.3:10.
5. The method according to claim 1, wherein in the step (1), the heating temperature is 80 to 90 ℃.
6. The method according to claim 1, wherein in the step (2), the fluorescent molecule, N-dimethylformamide and water in the gel solution are used in a ratio of 4 to 6mg:0.3 to 0.5mL:20g.
7. The method according to claim 1, wherein in the step (2), the ultraviolet light has a wavelength of 365nm.
8. The method according to claim 1, wherein in the step (2), the irradiation time is not less than 1h.
9. The hydrogel phase-change material prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the hydrogel phase-change material of claim 9 in cold chain transportation.
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