CN115232329A - Lipoic acid hydrogel and preparation method and application thereof - Google Patents

Lipoic acid hydrogel and preparation method and application thereof Download PDF

Info

Publication number
CN115232329A
CN115232329A CN202210943867.5A CN202210943867A CN115232329A CN 115232329 A CN115232329 A CN 115232329A CN 202210943867 A CN202210943867 A CN 202210943867A CN 115232329 A CN115232329 A CN 115232329A
Authority
CN
China
Prior art keywords
lipoic acid
acid hydrogel
hydrogel
preparation
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210943867.5A
Other languages
Chinese (zh)
Inventor
朱东雨
蓝明辉
唐楚玲
蒋开祥
江嘉馨
陈至鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202210943867.5A priority Critical patent/CN115232329A/en
Publication of CN115232329A publication Critical patent/CN115232329A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/0066—Medicaments; Biocides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/008—Hydrogels or hydrocolloids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/02—Polythioethers; Polythioether-ethers
    • 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
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a lipoic acid hydrogel as well as a preparation method and application thereof, and relates to the technical field of high polymer hydrogels. The preparation method of the lipoic acid hydrogel realizes the self-assembly of the lipoic acid in the water by controlling the temperature and the molar ratio of the lipoic acid to the sodium lipoate, the prepared lipoic acid hydrogel does not depolymerize with the change of time or temperature, contains abundant disulfide bonds, and can realize high-efficiency self-healing. The lipoic acid hydrogel has simple preparation process and strong stability, has cohesiveness, injectability, high-efficiency self-healing property and temperature sensitivity, and can be applied to adhesives, dressings and anti-counterfeiting materials.

Description

Lipoic acid hydrogel and preparation method and application thereof
Technical Field
The invention relates to the technical field of high-molecular hydrogel, and particularly relates to lipoic acid hydrogel and a preparation method and application thereof.
Background
Lipoic acid is a disulfide compound of a vitamin, is an important coenzyme in organisms, has the effects of oxidation resistance, saccharification resistance, inflammation resistance and the like, and has a molecular structure mainly existing in the form of five-membered rings containing disulfide bonds and active carboxyl groups. Nowadays, lipoic acid is increasingly used to prepare supramolecular polymer hydrogels by ring-opening self-polymerization (ROP) of five-membered disulfide rings caused by dynamic disulfide exchange, and is widely applied to the fields of recyclable high molecular materials, bio-antibacterial materials, viscous materials, etc. Because the active terminal disulfide free radical of the polythiooctanoic acid can initiate reverse closed-loop depolymerization, the polythiooctanoic acid is in a metastable state, and the application of the polythiooctanoic acid material is greatly limited. At present, researches report that a vinyl monomer (1, 3-diisopropenyl benzene, acrylic acid, itaconic acid and the like) is added to participate in a polymerization process of lipoic acid or an ionic liquid and the like are introduced to stabilize disulfide bonds in the lipoic acid and prevent the closed-loop depolymerization behavior of the lipoic acid, but the disulfide bonds involve the use of volatile toxic substances or the leakage of the ionic liquid, easily cause pollution to the environment, require multi-step organic synthesis, and have a complex preparation process.
The preparation process is simple, can be applied to skin wound repair, spinal nerve injury repair and ultraviolet shielding, but the poly lipoic acid can depolymerize in concentrated alkali, the concentration of the alkali liquor needs to be strictly controlled in the preparation process, the depolymerization behavior of the poly lipoic acid cannot be solved, the prepared hydrogel has instability, and the subsequent use can be influenced by the alkali residue in the alkali liquor, such as stimulation to skin.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides the preparation method of the lipoic acid hydrogel, strong alkali is not needed, the obtained lipoic acid hydrogel is not depolymerized along with the change of time or temperature, disulfide bonds are formed by the sufficient ring-opening reaction of disulfide rings in the preparation process, and hydrogen bonds, ionic bonds and disulfide bonds exist in the gel, so that efficient self-healing can be realized.
Another object of the present invention is to provide a lipoic acid hydrogel.
The invention also aims to provide the application of the lipoic acid hydrogel in the adhesive.
The invention also aims to provide application of the lipoic acid hydrogel in the dressing.
The invention also aims to provide application of the lipoic acid hydrogel in anti-counterfeiting materials.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of lipoic acid hydrogel comprises the following steps:
s1, dissolving a lipoic acid and sodium lipoate mixed monomer with a molar ratio of 10-10;
s2, heating the mixed solution at 45-80 ℃, uniformly mixing and reacting for more than 1h, and then keeping the temperature at 40-60 ℃ until hydrogel is formed, wherein the obtained hydrogel is lipoic acid hydrogel.
The inventors have found that when the molar ratio of lipoic acid to sodium lipoate is lower than 10; when the molar ratio of lipoic acid to sodium lipoate is higher than 10.
The ring-opening polymerization reaction of the lipoic acid and the sodium lipoate and the gelation of the solution can also be influenced by the addition amount of water in the S1, when the addition amount of the water is less than 2 times of the mass of the mixed monomer in the S1, the lipoic acid and the sodium lipoate cannot be uniformly mixed, so that the polymerization reaction cannot be smoothly carried out, and when the addition amount of the water is too high, the gelation of a reaction product after the polymerization reaction is difficult to realize, so that a hydrogel product cannot be obtained.
The reaction temperature in the S2 is to induce the lipoic acid and the sodium lipoate to self-assemble in water to form the polythiooctanoic acid, when the temperature is too low, the ring-opening polymerization of disulfide rings in the lipoic acid and the sodium lipoate is not sufficiently induced, and when the reaction temperature is too high, the evaporation of water is too fast, the water content of the lipoic acid hydrogel is influenced, a stable hydrogel cannot be formed, and the excessive temperature can make a reaction product in a sol state, so that the gelation process is difficult to perform. The reaction time in S2 also influences the occurrence of polymerization reaction due to the time required for the ring-opening polymerization of disulfide rings, and when the reaction time is too short, lipoic acid and sodium lipoate cannot react sufficiently, so that the ring-opening reaction of disulfide rings cannot be completed, and the polymerization degree of the final lipoic acid hydrogel is influenced.
In addition, the lipoic acid hydrogel needs to be kept at a constant temperature for a period of time after the ring-opening polymerization reaction is performed, as described in S2, because a viscous substance is obtained after the ring-opening polymerization reaction, gelation is not achieved, and bonds are also formed and stabilized during the gelation process, such as hydrogen bonds between carboxyl groups, hydrogen bonds between carboxyl groups and carboxyl anions, and ionic bonds between carboxyl anions and sodium ions, and the formation of the chemical bonds all needs energy, so that the lipoic acid hydrogel needs to be performed under a constant temperature condition, and when the constant temperature is too low, sufficient energy cannot be provided for various chemical bonds inside the gel during the gelation process, which is not beneficial to the formation and stabilization of the chemical bonds, and further affects the stability of the lipoic acid hydrogel; when the temperature is too high, the stability of the formation of chemical bonds is not further promoted, and the progress of the gelation process is not facilitated.
Preferably, the molar ratio of the thioctic acid to the sodium thioctate in S1 is 10.
Preferably, the reaction time in S2 is 1-2 h.
When the disulfide rings are subjected to ring-opening polymerization, too long reaction time cannot bring better effect to the lipoic acid hydrogel, but the preparation efficiency is reduced.
Preferably, the constant temperature time in the S2 is 6-12 h.
The constant temperature time is too short, chemical bonds in the gel are not completely formed and stabilized, and the stability of the final lipoic acid hydrogel is influenced, but the constant temperature time is too long and cannot bring better effect to the lipoic acid hydrogel, so the constant temperature time needs to be controlled.
The lipoic acid hydrogel is simple in preparation method, the used raw materials cannot pollute the environment, uniform liquid can be formed after heating in water by controlling the molar ratio of the lipoic acid to the sodium lipoate, the lipoic acid hydrogel is induced by temperature to generate a polymerization reaction of the lipoic acid and the sodium lipoate, and the obtained lipoic acid hydrogel is high in stability and cannot generate depolymerization behaviors along with the change of time and temperature.
The invention particularly provides the lipoic acid hydrogel prepared by the lipoic acid hydrogel preparation method.
The disulfide bonds in the lipoic acid hydrogel are dynamic disulfide bonds, and can be re-crosslinked through exchange among the disulfide bonds after being damaged and recovered, and the lipoic acid hydrogel prepared by the invention also contains hydrogen bonds among carboxyl groups, hydrogen bonds among the carboxyl groups and carboxyl anions and ionic bonds among the carboxyl anions and sodium ions, and the self-healing speed of the lipoic acid hydrogel is higher due to the action of the chemical bonds. In addition, the lipoic acid hydrogel prepared by the invention has injectability, and provides a good implementation mode for the application of various lipoic acid hydrogels.
The invention particularly relates to the application of lipoic acid hydrogel in the adhesive.
Preferably, the binder acts as a binder for wood or metal bonding.
The lipoic acid hydrogel has cohesiveness, can realize the adhesion of dried wood or metal by coating the lipoic acid hydrogel on the surface of the dried wood or metal, and also has adhesive effect on the surfaces of polytetrafluoroethylene, rubber, wood boards, stones, metal, plastic, glass, leaves and pigskin. The lipoic acid hydrogel prepared by the invention has injectability and can be adhered by being injected to the surface of an object. In addition, the disulfide bond in the poly lipoic acid can be decomposed by the enzyme of the organism, degraded into the small-molecule lipoic acid and further absorbed and utilized by the organism. Therefore, the lipoic acid hydrogel can be degraded by microorganisms as a binder, and the pollution of the binder to the environment is reduced.
More preferably, the lipoic acid hydrogel as a binder has a molar ratio of lipoic acid to sodium lipoate of 10.
When the molar ratio of the lipoic acid to the sodium lipoate is 10.
A further object of the invention is to protect the use of a lipoic acid hydrogel in dressings.
The lipoic acid hydrogel has the characteristic of high efficiency self-healing, and can be quickly restored to the original state after being damaged by the outside, so that when the lipoic acid hydrogel is used as a wound dressing, the gel can be injected to a wound in a needle tube injection mode, and the wound healing is promoted. In addition, disulfide bonds in the lipoic acid can generate sulfur free radicals to react with the surface of bacteria to inactivate the bacteria, so that the lipoic acid hydrogel can be used as a biological anti-inflammatory agent, and no additional anti-inflammatory agent is needed.
The invention also aims to protect the application of the lipoic acid hydrogel in the anti-counterfeiting material, wherein the lipoic acid hydrogel is prepared by the preparation method provided by the invention, and the molar ratio of lipoic acid to sodium lipoate in S1 is 10.
When the molar ratio of the lipoic acid to the sodium lipoate is 10.
Compared with the prior art, the invention has the beneficial effects that:
the lipoic acid hydrogel is prepared by the self-assembly of the lipoic acid and the sodium lipoate in water and the ring-opening polymerization, and because sufficient reaction time is given, the reverse ring-closing depolymerization behavior cannot occur, the lipoic acid hydrogel has rich disulfide bonds, and the lipoic acid and the sodium lipoate are used as raw materials, and the obtained gel also contains hydrogen bonds and ionic bonds, so that the gel can be self-healed within 30min after being damaged, and is restored to the original state. Because stable hydrogen bonds among carboxyl groups, hydrogen bonds among carboxyl groups and carboxyl anions and ionic bonds among the carboxyl anions and sodium ions can be formed in the gel in the gelation process, the lipoic acid hydrogel prepared by the invention has high stability, and can not be depolymerized after being placed at room temperature for 60 days.
The lipoic acid hydrogel prepared by the invention has cohesiveness, injectability, temperature sensitivity and high-efficiency self-healing performance, is suitable for the adhesion of a bonder, particularly dry wood and metal, and has the shear strength of 1.927MPa when being adhered to the dry wood and the peel strength of 329N/m when being adhered to metal zinc. In addition, the lipoic acid hydrogel is also suitable for dressings and anti-counterfeiting materials, when the lipoic acid hydrogel is used as the dressings, the wound healing can be promoted, the dressings can be quickly restored to the original shape after being damaged by the external environment, and the anti-inflammatory effect of the gel can be better played; when the anti-counterfeiting material is used as an anti-counterfeiting material, the visibility of information can be controlled through temperature change.
Drawings
FIG. 1 is a graph of the UV absorption spectra of lipoic acid hydrogel with a molar ratio of 10;
fig. 2 is an infrared spectrum of the lipoic acid hydrogel of example 1, example 2 and example 3;
FIG. 3 is an XRD spectrum of lipoic acid, sodium lipoate, and the lipoic acid hydrogel of example 2;
fig. 4 is a graph comparing the appearance of the lipoic acid hydrogels of example 1 and example 2 as a function of temperature;
FIG. 5 is a diagram showing the adhesion of the hydrogel prepared by the present invention as an adhesive on the surface of various materials;
fig. 6 is a presentation showing injectability of the lipoic acid hydrogel of example 2;
fig. 7 is a picture of the self-healing of the lipoic acid hydrogel of example 2 at various times.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the embodiments in any way. The starting reagents used in the examples of the present invention are those conventionally purchased, unless otherwise specified.
Example 1
A preparation method of lipoic acid hydrogel comprises the following steps:
s1, dissolving lipoic acid and sodium lipoate in deionized water according to a molar ratio of 10 (mass ratio is 1.29g;
s2, heating the mixed solution in the S1 at 60 ℃, stirring and reacting for 1.5h, stopping stirring, keeping the temperature at 50 ℃ for 6h, and cooling to room temperature to obtain the lipoic acid hydrogel.
Examples 2 to 14 and comparative examples 1 to 8
The preparation method of the lipoic acid hydrogel is the same as that of example 1, and the difference is shown in Table 1.
TABLE 1 lipoic acid hydrogel preparation parameters of examples 1-14 and comparative examples 1-8
Figure BDA0003783029440000051
Figure BDA0003783029440000061
Comparative example 9
A thioctic acid-based hydrogel is prepared by the following steps:
1mmol of lipoic acid and 1mL0.4M sodium bicarbonate solution are evenly mixed under the heating condition of 45 ℃, stirred to be dissolved, and then the lipoic acid high-molecular hydrogel material is obtained after reaction in water bath at 60 ℃ for 6 hours.
Performance testing
The infrared spectrum test method of the lipoic acid hydrogel comprises the following steps:
testing by using a Fourier infrared spectrometer iS50R, analyzing a lipoic acid hydrogel sample by using a total reflection mode of the infrared spectrometer, and testing lipoic acid and sodium lipoate by using a potassium bromide tabletting method, wherein the wave number range iS 4000-400cm -1 The scanning times are 32 times, and the infrared spectrum data of the lipoic acid, the sodium lipoate and lipoic acid hydrogel samples with various proportions can be obtained.
The ultraviolet spectrum test method of the lipoic acid hydrogel comprises the following steps:
the measurement was carried out using an ultraviolet Spectrophotometer (UV-Vis Spectrophotometer), wavelength accuracy: plus or minus 0.3nm; resolution ratio: 0.1nm; the testing wavelength range is 230-500nm, and the ultraviolet absorption spectra of the lipoic acid hydrogel under the same solubility and different reaction times are respectively tested.
The healing speed of the lipoic acid hydrogel was tested as follows:
the gel surface was cross-hatched with a razor blade to a depth of 3mm and left in a room temperature environment to record the time required to observe complete healing.
The depolymerization behavior of the lipoic acid hydrogel is tested as follows:
XRD characterization is carried out on the lipoic acid hydrogel which is placed at room temperature for different time, and whether reverse closed-loop depolymerization occurs or not is judged by testing whether the lipoic acid hydrogel has a diffraction peak of lipoic acid or sodium lipoate crystals or not.
When the lipoic acid hydrogel is used in a binder, the shear strength of the lipoic acid hydrogel is measured as follows:
uniformly coating the prepared gel on 100 × 25 × 2mm rectangular pine boards, coating the size of 25 × 25mm, coating two boards, adhering the front surfaces of the boards with the gel surface, placing the boards on a press machine, pressing for 12 hours at 80 ℃ and 8Mpa to dry and solidify the boards, testing the shear strength by using a universal tensile machine, testing the tensile speed of 5mm/min, paralleling five samples in each group, and averaging. The test results are shown in table 2.
TABLE 2 shear strength of lipoic acid hydrogel adhesive dried Wood of example 1, example 2 and example 3
Shear strength (MPa)
Example 1 1.25878
Example 2 1.19843
Example 3 1.92725
The peel strength of the adhesive with the metal surface is tested in the following way:
uniformly coating the gel on different metal surfaces by using a film coating machine, wherein the coating thickness is 0.15mm, drying in a 60 ℃ oven for 12 hours, adhering the gel on the metal surface containing a sample by using a 3M adhesive tape, tightly adhering the gel by using a roller for rolling, testing the peel strength by using a universal tensile machine, wherein the speed is 100mm/min, the peel distance is 100mm, the width of the adhesive tape is 20mm, and each group of three parallel samples are tested and averaged. The test results are shown in table 3.
TABLE 3 peel Strength of lipoic acid hydrogels of example 1, example 2, and example 3 at different metals
Example 1 Peel Strength Example 2 Peel Strength Example 3 Peel Strength
Aluminium 105N/m 79.3 N/m 144N/m
Copper (Cu) 199N/m 182N/m 215N/m
Zinc 265N/m 251N/m 329N/m
TABLE 4 lipoic acid hydrogel test results of examples 1 to 14 and comparative examples 1 to 9
Figure BDA0003783029440000081
Figure BDA0003783029440000091
As can be seen from the test results of table 4, when the molar ratio of lipoic acid to sodium lipoate is less than 10. At a constant temperature of less than 40 ℃, gelation does not proceed completely due to insufficient energy supplied to the gelation process, and the final reaction product exists in a sol state. The lipoic acid hydrogel obtained in comparative example 4 has a high healing rate, but is very susceptible to depolymerization because the reaction time is too short and the lipoic acid and sodium lipoate are not sufficiently subjected to ring-opening polymerization. In addition, the healing rate in comparative example 9 is significantly lower than that of the lipoic acid hydrogels prepared in examples 1 to 12, because the type and content of chemical bonds in the hydrogel of comparative example 9 are not as abundant as those in examples 1 to 14, and the preparation conditions are alkaline again, and ring-closure depolymerization easily occurs, since there are fewer stable chemical bonds in the gel.
Fig. 1 is an ultraviolet absorption spectrum diagram of thioctic acid and sodium lipoate in a molar ratio of 10, at different reaction times, when the reaction time is too short, an obvious ultraviolet absorption peak of disulfide bonds in five-membered disulfide rings exists at 330nm, and as the reaction time increases, the five-membered disulfide rings in thioctic acid and sodium lipoate gradually undergo ring-opening polymerization, and after the reaction time is 1h, the ultraviolet absorption peak almost completely disappears, which corresponds to the results of example 11 and comparative example 4, further explaining that when the reaction time is too short, the ring-opening polymerization reaction of five-membered disulfide rings in thioctic acid and sodium lipoate cannot sufficiently occur, and the obtained product has a low content of disulfide bonds after ring-opening and a slow self-healing speed.
FIG. 2 shows the preparation of examples 1, 2 and 3The lipoic acid hydrogel has an infrared spectrum, wherein PTA 1 、PTA 2 、PTA 3 Corresponding to the lipoic acid hydrogels of example 2, example 1 and example 3, respectively, it can be seen from the figure that the lipoic acid product is 1702cm -1 、1590cm -1 And the stretching vibration peak of carboxyl and carboxyl negative ions appears, which indicates that the carboxyl and carboxyl negative ions exist in the product, and further proves that the lipoic acid hydrogel contains various chemical bonds, thereby enhancing the stability of the lipoic acid hydrogel and preventing the lipoic acid hydrogel from being depolymerized along with the change of time.
The XRD patterns of lipoic acid, sodium lipoate and the lipoic acid hydrogel prepared in example 2 at 1 day, 3 days, 7 days and 15 days after being left standing are shown in fig. 3; wherein TA is lipoic acid, TA-Na is sodium lipoate, PTA 1 As can be seen from the results of the lipoic acid hydrogel prepared in example 2, no diffraction peaks of lipoic acid and sodium lipoate crystals appear after the lipoic acid hydrogel is left for 15 days, which indicates that the lipoic acid hydrogel does not undergo depolymerization with time and has stable properties.
FIG. 4 is a comparison of the appearance of the lipoic acid hydrogels of examples 1 and 2 as a function of temperature, PTA at 25 ℃ 1 PTA in opaque state due to lower temperature 2 Is transparent and, with increasing temperature, at 45 ℃ PTA 1 And PTA 2 The occluded information can be observed. And the above variations are for PTA 1 Is reversible, and this occurs because: when the environment temperature is lower, the lipoic acid content is higher, and the solubility of a chain segment formed by ring-opening polymerization of the lipoic acid is lower, so that the lipoic acid hydrogel prepared by the invention can be applied to anti-counterfeiting materials by utilizing the property.
Figure 5 is lipoic acid hydrogel PTA 2 The adhesion condition of polytetrafluoroethylene, rubber, wood boards, stones, metal, plastic, glass, leaf surfaces, pigskin and finger surfaces shows that the lipoic acid hydrogel prepared by the invention can be used as a binder to adhere various materials. The shear strength was 1.198MPa minimum and 1.927MPa maximum when dried wood was adhered (Table 2); when metal zinc is adhered, the peel strength is 2 at least51N/m and 329N/m at the maximum (Table 3), and has a peel strength of 182N/m at the minimum and 215N/m at the maximum (Table 3) when metal copper is adhered, and has a peel strength of 79.3N/m at the minimum and 144N/m at the maximum (Table 3) when metal aluminum is adhered.
Fig. 6 is an illustration of an injectable image showing the hydrogel prepared by the present invention as an injectable material, illustrating that the present invention can be injected to a corresponding substrate surface by a syringe at the time of use.
Fig. 7 is a self-healing picture of the lipoic acid hydrogel of example 2 at different times, and further demonstrates that the lipoic acid hydrogel prepared by the method can realize high-efficiency self-healing, can better play an anti-inflammatory role when being used as a wound dressing, and can further protect a wound.
It should be noted that, although the ultraviolet absorption spectrum, the infrared spectrum, the adhesion picture and the injectability picture are not provided in the other examples, the properties of the other examples are also equivalent to the results shown in the figures.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The preparation method of the lipoic acid hydrogel is characterized by comprising the following steps of:
s1, dissolving a lipoic acid and sodium lipoate mixed monomer with a molar ratio of 10-10;
s2, heating the mixed solution at 45-80 ℃, uniformly mixing and reacting for more than 1h, and then keeping the temperature at 40-60 ℃ until hydrogel is formed, wherein the obtained hydrogel is lipoic acid hydrogel.
2. The method for preparing the lipoic acid hydrogel according to claim 1, wherein the molar ratio of lipoic acid to sodium lipoate in S1 is 10.
3. The method for preparing the lipoic acid hydrogel according to claim 1, wherein the reaction time in S2 is 1 to 2 hours.
4. The method for preparing the lipoic acid hydrogel of claim 1, wherein the constant temperature time in the S2 is 6-12 h.
5. The lipoic acid hydrogel prepared by the lipoic acid hydrogel preparation method of any one of claims 1 to 4.
6. Use of the lipoic acid hydrogel of claim 5 as a binder.
7. Use according to claim 6, wherein the adhesive is an adhesive for wood or metal bonding.
8. The use of claim 6, wherein the lipoic acid hydrogel has a molar ratio of lipoic acid to sodium lipoate of 10.
9. Use of the lipoic acid hydrogel of claim 5 as a dressing.
10. The application of the lipoic acid hydrogel as an anti-counterfeiting material is characterized in that the lipoic acid hydrogel is prepared by the preparation method of claim 1, and the molar ratio of lipoic acid to sodium lipoate in S1 is 10.
CN202210943867.5A 2022-08-04 2022-08-04 Lipoic acid hydrogel and preparation method and application thereof Pending CN115232329A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210943867.5A CN115232329A (en) 2022-08-04 2022-08-04 Lipoic acid hydrogel and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210943867.5A CN115232329A (en) 2022-08-04 2022-08-04 Lipoic acid hydrogel and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115232329A true CN115232329A (en) 2022-10-25

Family

ID=83679871

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210943867.5A Pending CN115232329A (en) 2022-08-04 2022-08-04 Lipoic acid hydrogel and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115232329A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115779130A (en) * 2022-12-19 2023-03-14 绍兴百立盛新材料科技有限公司 Self-adhesive hydrogel film type wound dressing, preparation method and application
WO2023155753A1 (en) * 2022-02-15 2023-08-24 四川大学 Composite hydrosol, preparation method therefor and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023155753A1 (en) * 2022-02-15 2023-08-24 四川大学 Composite hydrosol, preparation method therefor and application thereof
CN115779130A (en) * 2022-12-19 2023-03-14 绍兴百立盛新材料科技有限公司 Self-adhesive hydrogel film type wound dressing, preparation method and application

Similar Documents

Publication Publication Date Title
CN115232329A (en) Lipoic acid hydrogel and preparation method and application thereof
CN110655651B (en) Lipoic acid-silver nano self-repairing material as well as preparation method and application thereof
CN113292671B (en) High molecular cross-linking agent containing phenylboronic acid group, biological adhesive prepared from high molecular cross-linking agent, preparation method and application of biological adhesive
Afroz et al. Synthesis and characterization of polyethylene oxide (PEO)—N, N-dimethylacrylamide (DMA) hydrogel by gamma radiation
Ma et al. Hydrogen bond detachment in polymer complexes
CN102766248B (en) Method for preparing liquid urethane acrylate resin by recovered solid polyurethane
US4306955A (en) Photopolymerized acrylic polymer essentially devoid of residual monomer(s)
KR20220044536A (en) Self-curing redox donor/acceptor adhesive composition
Gao et al. Preparation of UV curing crosslinked polyviologen film and its photochromic and electrochromic performances
Fabregat et al. An electroactive and biologically responsive hybrid conjugate based on chemical similarity
CN105482140A (en) Preparation method of polylactic acid/starch surface grafted sulfuric acid aminated chitosan composite thin film
CN105061733A (en) Synthesis method of cellulose grafted polycaprolactone
Sionkowska Photochemical stability of collagen/poly (ethylene oxide) blends
CN108503839A (en) Multifunctional mesh shaped polymer and the application of film, preparation method and the film in terms of electrochromism or automatically controlled fluorescence
JPS6253328A (en) N,n'-diphenylbenzidine polymer
CN114752210B (en) Ultraviolet curing electrolyte, preparation method of electrolyte membrane and electrochromic device
Sun et al. Electrosynthesis and characterization of aminomethyl functionalized PEDOT with electrochromic property
Hinokuma et al. Electrochromism of spin-coated MoO3· nH2O thin films from peroxo-polymolybdate
CN113754903B (en) Preparation method of double-crosslinked hyaluronic acid/chitosan composite hydrogel for skin repair
CN110003377A (en) Polymer and preparation method and application
EP4214263A1 (en) Biodegradable adhesive composition
Zhang et al. Cationic ring-opening polymerization of natural thioctic acid to chemically recyclable and self-healable poly (thioctic acid) supramolecular material
Wang et al. Preparation and properties of UV cation-initiated self-crosslinking acrylate pressure-sensitive adhesive without reactive diluent
CN101050334A (en) Water paint solidified by ultraviolet light, preparation method and application
CN116970204B (en) TPU high-low temperature film with optical color effect and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination