Anti-freezing, antibacterial and sensing multifunctional hydrogel and preparation method thereof
By introducing 1,3-propanesulfolide, glycerol and sodium ions into the hydrogel, it imparts antifreeze, antibacterial and sensing functions, solving the problems of easy freezing and single function of existing hydrogels at low temperatures, and achieving widespread application of multifunctional hydrogels.
Patent Information
- Application Number
- CN202510125900.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-27
- Publication Date
- 2025-05-06
AI Technical Summary
Existing hydrogels are prone to freezing at low temperatures, have a single function and are prone to bacterial growth, limiting their widespread use in anti-freeze, antibacterial and sensing applications.
The introduction of 1,3-propanesulfolactone produces antibacterial functional quaternary ammonium salt and sensory functional sulfobetaine structure, and the addition of glycerol to improve frost resistance, while the introduction of sodium ions to form coordination bonds with the hydrogel polymer network, improving mechanical properties and electrical conductivity.
The hydrogel maintains soft elasticity and conductivity at -50 to -10°C, significantly improves its antibacterial effect, and has the sensing function of shape changes and humidity changes.
Smart Images
Figure CN119930976A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the application field of multifunctional hydrogels, and relates to a type of antifreeze, antibacterial and sensing multifunctional hydrogels and a preparation method thereof. Background Art
[0002] Hydrogel is a new type of polymer material with water as the dispersion medium. It has the advantages of high water content, non-toxicity, good biocompatibility, and adjustable physical and chemical properties. It is an excellent soft material. By combining the functionality of functional groups and inorganic particles with network morphology design, multifunctional hydrogels with three-dimensional polymer networks show excellent properties, including conductivity, biocompatibility, and responsiveness to various stimuli. They have received increasing attention in the fields of flexible electronic devices, pollution control, and biomedicine.
[0003] There are many methods for preparing hydrogels at present, but there are still various defects. For example, problems such as easy dehydration and drying, easy freezing at low temperature, and single function limit the wide application of hydrogels. For example, the recently reported hydrogels based on chitosan, glycine and antimicrobial peptides have excellent antibacterial functions, but they are limited by environmental influences during use, such as easy freezing at sub-zero temperatures, which makes the antibacterial dressing ineffective. The reported antifreeze conductive hydrogel flexible sensor can maintain long-term environmental stability and antifreeze properties. When used as a flexible sensor, the soft elasticity and conductivity of the hydrogel can be maintained for a long time, but it is easy to breed bacteria when in contact with the human body during use, which is unhealthy for the human body. Therefore, it is very necessary to develop a new type of hydrogel that can meet multiple needs such as antifreeze, antibacterial, and sensing. Summary of the invention
[0004] In view of the problems existing in the prior art, the present invention provides a type of antifreeze, antibacterial, and sensing multifunctional hydrogel and a preparation method thereof. The present invention introduces 1,3-propane sultone to produce an antibacterial functional quaternary ammonium salt and a sensing functional sulfobetaine structure, thereby giving the hydrogel antibacterial and sensing functions. Glycerol with a high boiling point, strong hygroscopicity and antifreeze properties is further introduced into the hydrogel to give the hydrogel long-term environmental stability and antifreeze properties. Sodium ions are further introduced to form coordination bonds with the hydrogel polymer network to improve the mechanical properties, and the conductivity of the hydrogel is improved due to the conductive properties of the ions. The sodium ions and sulfobetaine synergistically exert the sensing function.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:
[0006] A type of antifreeze, antibacterial, and sensing multifunctional hydrogel, wherein the multifunctional hydrogel is a hydrogel with multiple functions after being grafted with 1,3-propane sultone and modified by the introduction of glycerol and sodium ions. The structural formula of the 1,3-propane sultone is as follows:
[0007] The antifreeze function is provided by introducing glycerol with high boiling point, high hygroscopicity and antifreeze function into the hydrogel. The structural formula of the glycerol is as follows:
[0008] The antibacterial effect is provided by the quaternary ammonium salt structure generated by the reaction of 1,3-propane sultone with the tertiary amine in the hydrogel. The sensing effect is provided by the synergistic effect of the sulfobetaine structure generated by the reaction of 1,3-propane sultone with the tertiary amine in the hydrogel and the sodium ion. The reaction formula of 1,3-propane sultone and tertiary amine is as follows:
[0009] A method for preparing a multifunctional hydrogel with antifreeze, antibacterial and sensing properties, comprising the following steps:
[0010] (1) Dissolve bisphenol A diglycidyl ether and polyethylene glycol glycidyl ether (Mn=500 g / mol) and 3-amino-1-propanol in 10-20 ml of an organic solvent to obtain a mixture, and react at 60-140° C. for 6-14 h to obtain a linear prepolymer PBAPEG solution.
[0011] Furthermore, the molar ratio of bisphenol A diglycidyl ether to polyethylene glycol glycidyl ether is 1:(0.25-4), wherein the concentration of bisphenol A diglycidyl ether in the mixed solution is 0.133-0.533 mol / L; the amount of the amino monomer is 0.75-0.95 times the total molar amount of bisphenol A diglycidyl ether and polyethylene glycol glycidyl ether epoxy monomer.
[0012] Furthermore, the organic solvent includes N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).
[0013] (2) Add 1,3-propane sultone to the PBAPEG prepolymer solution, turn off the heating while adding and let the temperature drop naturally, and obtain the PBAPEG-PS solution after 10-14 hours.
[0014] Furthermore, the molar ratio of 1,3-propane sultone to 3-amino-1-propanol is (0.5-1.5):1.
[0015] (3) Add the chemical crosslinking agent diluted with 2-4 ml of organic solvent to the PBAPEG-PS solution, stir for 5-10 minutes and transfer to a 40-70° C. oven to obtain an elastomeric crosslinked polymer PBAPEGPU-PS after 36-48 hours.
[0016] Furthermore, the molar ratio of the chemical crosslinking agent to the amino monomer is (0.3-0.75):1.
[0017] Furthermore, the chemical cross-linking agent includes hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), and dicyclohexylmethane diisocyanate (HMDI).
[0018] (4) At room temperature, immerse PBAPEGPU-PS in a mixed solution of water, glycerol, and sodium chloride for 6-24 hours to obtain the multifunctional hydrogel WPBAPEGPU-PS.
[0019] Furthermore, in the mixed solution, the mass concentration of glycerol is 33-67%, the mass concentration of sodium chloride is 5-15%, and the rest is water.
[0020] Experimental tests of the present invention:
[0021] (1) WPBAPEGPU-PS antifreeze test: The hydrogel material was placed in a freezer at -50 to -10°C for 12-24 hours, the state of the hydrogel before and after freezing was observed, and a simple bending deformation test was performed to determine the antifreeze function of the hydrogel.
[0022] (2) WPBAPEGPU-PS antibacterial test and characterization: The antibacterial function was evaluated by comparing the number of bacterial colonies cultivated. Escherichia coli was used as the experimental bacteria and was cultivated in the experimental materials and control materials for 2-5 days.
[0023] (3) WPBAPEGPU-PS sensor test: The test was completed by using a CHI760F electrochemical workstation. A hydrogel strip with a size of 5mm*30mm*1mm was selected, and both ends were connected to the electrochemical workstation. A fixed voltage of 0.5-2V was applied to stretch the hydrogel strip. The resistance changed with the shape change, and the output current also changed accordingly. The stretching operation was cyclically performed to obtain the stretching sensing curve of the hydrogel. The bending sensing curve, compression sensing curve and humidity change sensing curve can be obtained in the same way.
[0024] The beneficial effects of the present invention are:
[0025] The present invention endows the hydrogel with antifreeze, antibacterial and sensing functions by introducing 1,3-propane sultone, glycerol and sodium ions. The multifunctional hydrogel WPBAPEGPU-PS can still maintain the soft elasticity of the gel material when stored at -50 to -10°C for 12-24 hours. After culturing E. coli for 2-5 days, the number of E. coli colonies on WPBAPEGPU-PS was 78.4-89.9% less than that of the blank control group, showing a significant antibacterial effect. WPBAPEGPU-PS can respond to shape changes such as stretching, bending, and compression at a fixed voltage of 0.5-2V, as well as humidity changes caused by blowing air into the hydrogel, proving that the hydrogel has a sensing function. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 This is the tensile behavior sensing curve of the hydrogel WPBAPEGPU-PS obtained in Example 2;
[0027] Figure 2 This is the bending behavior sensing curve of the hydrogel WPBAPEGPU-PS obtained in Example 2;
[0028] Figure 3 This is the compression behavior sensing curve of the hydrogel WPBAPEGPU-PS obtained in Example 2;
[0029] Figure 4 This is the humidity change sensing curve of the hydrogel WPBAPEGPU-PS obtained in Example 2. DETAILED DESCRIPTION
[0030] The present invention is further described below in conjunction with specific embodiments.
[0031] Example 1
[0032] (1) Dissolve bisphenol A diglycidyl ether (0.002 mol, 0.68 g) and polyethylene glycol glycidyl ether (0.008 mol, 4 g) and 3-amino-1-propanol (0.0075 mol, 0.56 g) in 20 ml of DMSO to obtain a mixture, and react at 140° C. for 14 h to obtain a linear prepolymer PBAPEG solution.
[0033] (2) 1,3-Propane sultone (0.00375 mol, 0.46 g) was added to the PBAPEG prepolymer solution. At the same time, the heating was turned off and the temperature was naturally lowered to obtain a PBAPEG-PS solution after 10 hours.
[0034] (3) MDI (0.00225 mol, 0.56 g) was added to the PBAPEG-PS solution via 2 ml of DMSO. After stirring for 15 min, the solution was transferred to a 70°C oven. After 48 h, an elastomeric cross-linked polymer PBAPEGPU-PS was obtained.
[0035] (4) At room temperature, PBAPEGPU-PS was immersed in a water / glycerol / sodium chloride mixed solution with a glycerol mass fraction of 67% and a sodium chloride mass fraction of 15% for 24 hours to obtain the multifunctional hydrogel WPBAPEGPU-PS.
[0036] From the freezing test of the WPBAPEGPU-PS of this embodiment at -50°C for 24h, it can be seen that it will not break when bent at -20°C and remains soft, thus having anti-freeze properties.
[0037] From the comparison of the E. coli colonies cultured for 5 days on the WPBAPEGPU-PS of this embodiment and the control group, it can be seen that the number of E. coli colonies on the WPBAPEGPU-PS is about 61, and the number of E. coli colonies on the control group is about 282. The number of E. coli colonies on the hydrogel is 78.4% less than that of the blank control group.
[0038] From the stretching, bending, compression, and humidity change sensing curves of WPBAPEGPU-PS in this embodiment at a fixed voltage of 2V, it can be seen that the hydrogel can stably output a cyclic current change curve for stretching, bending, compression shape changes and humidity changes caused by hydrogel blowing, proving that the hydrogel has a sensing function.
[0039] Example 2
[0040] (1) Bisphenol A diglycidyl ether (0.005 mol, 1.7 g) and polyethylene glycol glycidyl ether (0.005 mol, 2.5 g) were dissolved with 3-amino-1-propanol (0.0085 mol, 0.64 g) in 15 ml of DMF to obtain a mixture, which was reacted at 120° C. for 12 h to obtain a linear prepolymer PBAPEG solution.
[0041] (2) 1,3-Propane sultone (0.0085 mol, 1.04 g) was added to the PBAPEG prepolymer solution. At the same time, the heating was turned off and the temperature was naturally lowered to obtain the PBAPEG-PS solution after 12 hours.
[0042] (3) HDI (0.003825 mol, 0.64 g) was added to the PBAPEG-PS solution via 2 ml of DMF. After stirring for 10 min, the solution was transferred to a 70 °C oven. After 48 h, an elastomeric cross-linked polymer PBAPEGPU-PS was obtained.
[0043] (4) At room temperature, PBAPEGPU-PS was immersed in a water / glycerol / sodium chloride mixed solution with a glycerol mass fraction of 67% and a sodium chloride mass fraction of 10% for 12 hours to obtain the multifunctional hydrogel WPBAPEGPU-PS.
[0044] From the freezing test of the WPBAPEGPU-PS of this embodiment at -20°C for 18h, it can be seen that the WPBAPEGPU-PS will not break when bent at -20°C and remains soft, thus having anti-freeze properties.
[0045] From the comparison of the E. coli colonies cultured for 3 days between the WPBAPEGPU-PS of this embodiment and the control group, it can be seen that the number of E. coli colonies on the WPBAPEGPU-PS is about 32, and the number of E. coli colonies on the control group is about 277. The number of E. coli colonies on the hydrogel is 88.4% less than that of the blank control group.
[0046] Depend on Figure 1-Figure 4 From the stretching, bending, compression and humidity change sensing curves of the hydrogel WPBAPEGPU-PS at a fixed voltage of 0.5V, it can be seen that the hydrogel can stably output the cyclic current change curve for the stretching, bending, compression shape changes and the humidity changes caused by blowing air into the hydrogel, proving that the hydrogel has a sensing function.
[0047] Example 3
[0048] (1) Bisphenol A diglycidyl ether (0.004 mol, 1.36 g) and polyethylene glycol glycidyl ether (0.006 mol, 3.0 g) were dissolved with 3-amino-1-propanol (0.008 mol, 0.60 g) in 15 ml of DMF to obtain a mixture, which was reacted at 110° C. for 13 h to obtain a linear prepolymer PBAPEG solution.
[0049] (2) 1,3-Propane sultone (0.008 mol, 0.98 g) was added to the PBAPEG prepolymer solution. At the same time, the heating was turned off and the temperature was naturally lowered. After 13 hours, the PBAPEG-PS solution was obtained.
[0050] (3) HDI (0.003825 mol, 0.64 g) was added to the PBAPEG-PS solution via 3 ml of DMF. After stirring for 10 min, the solution was transferred to a 60 °C oven. After 42 h, an elastomeric cross-linked polymer PBAPEGPU-PS was obtained.
[0051] (4) At room temperature, PBAPEGPU-PS was immersed in a water / glycerol / sodium chloride mixed solution with a glycerol mass fraction of 50% and a sodium chloride mass fraction of 10% for 10 h to obtain the multifunctional hydrogel WPBAPEGPU-PS.
[0052] From the freezing test of the WPBAPEGPU-PS of this embodiment at -30°C for 15h, it can be seen that it will not break when bent at -30°C and remains soft, thus having anti-freeze properties.
[0053] From the comparison of the E. coli colonies cultured for 4 days between the WPBAPEGPU-PS of this embodiment and the control group, it can be seen that the number of E. coli colonies on the WPBAPEGPU-PS is about 36, and the number of E. coli colonies on the control group is about 279. The number of E. coli colonies on the hydrogel is 87.1% less than that of the blank control group.
[0054] From the stretching, bending, compression, and humidity change sensing curves of WPBAPEGPU-PS in this embodiment at a fixed voltage of 1V, it can be seen that the hydrogel can stably output a cyclic current change curve for stretching, bending, compression shape changes and humidity changes caused by hydrogel blowing, proving that the hydrogel has a sensing function.
[0055] Example 4
[0056] (1) Dissolve bisphenol A diglycidyl ether (0.008 mol, 2.72 g) and polyethylene glycol glycidyl ether (0.002 mol, 1 g) and 3-amino-1-propanol (0.0095 mol, 0.72 g) in 10 ml of THF to obtain a mixture, and react at 60° C. for 6 h to obtain a linear prepolymer PBAPEG solution.
[0057] (2) 1,3-Propane sultone (0.01425 mol, 1.74 g) was added to the PBAPEG prepolymer solution. At the same time, the heating was turned off and the temperature was naturally lowered to obtain the PBAPEG-PS solution after 14 hours.
[0058] (3) HMDI (0.007125 mol, 1.20 g) was added to the PBAPEG-PS solution via 4 ml of THF. After stirring for 5 min, the solution was transferred to a 40°C oven. After 36 h, an elastomeric cross-linked polymer PBAPEGPU-PS was obtained.
[0059] (4) At room temperature, PBAPEGPU-PS was immersed in a water / glycerol / sodium chloride mixed solution with a glycerol mass fraction of 33% and a sodium chloride mass fraction of 5% for 6 h to obtain the multifunctional hydrogel WPBAPEGPU-PS.
[0060] From the freezing test of the WPBAPEGPU-PS of this embodiment at -10°C for 12h, it can be seen that it will not break when bent at -10°C and remains soft, thus having anti-freeze properties.
[0061] From the comparison of the E. coli colonies cultured for 2 days on the WPBAPEGPU-PS of this embodiment and the control group, it can be seen that the number of E. coli colonies on the WPBAPEGPU-PS is about 28, and the number of E. coli colonies on the control group is about 277. The number of E. coli colonies on the hydrogel is 89.9% less than that of the blank control group.
[0062] From the stretching, bending, compression, and humidity change sensing curves of WPBAPEGPU-PS in this embodiment at a fixed voltage of 0.5V, it can be seen that the hydrogel can stably output a cyclic current change curve for stretching, bending, compression shape changes and humidity changes caused by hydrogel blowing, proving that the hydrogel has a sensing function.
[0063] The above-described embodiments merely express the implementation methods of the present invention, but they cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.
Claims
1. A multifunctional hydrogel with antifreeze, antibacterial and sensing properties, characterized in that: The multifunctional hydrogel is a hydrogel with multiple functions after being grafted with 1,3-propane sultone and modified by the introduction of glycerol and sodium ions; the structural formula of the 1,3-propane sultone is as follows:
2. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 1, characterized in that: The antifreeze property is provided by introducing glycerol into the hydrogel; The antibacterial property is provided by the quaternary ammonium salt structure generated by the reaction of 1,3-propane sultone with the tertiary amine in the hydrogel; the sensing property is provided by the synergistic effect of the sulfobetaine structure generated by the reaction of 1,3-propane sultone with the tertiary amine in the hydrogel and the sodium ion.
3. The antifreeze, antibacterial and sensing multifunctional hydrogel according to claim 1, characterized in that: The following steps are involved: The first step is to dissolve bisphenol A diglycidyl ether and polyethylene glycol glycidyl ether with 3-amino-1-propanol in an organic solvent to obtain a mixed solution, and react at 60-140° C. for 6-14 hours to obtain a linear prepolymer PBAPEG solution; The second step is to add 1,3-propane sultone to the PBAPEG prepolymer solution, turn off the heating and cool it naturally, and obtain the PBAPEG-PS solution after 10-14 hours; The third step is to add the chemical crosslinking agent diluted with 2-4 ml of organic solvent to the PBAPEG-PS solution, stir for 5-10 minutes and then transfer to a 40-70°C oven to obtain an elastomeric crosslinked polymer PBAPEGPU-PS after 36-48 hours; The fourth step is to immerse PBAPEGPU-PS in a mixed solution of water, glycerol and sodium chloride for 6-24 hours to obtain the multifunctional hydrogel WPBAPEGPU-PS.
4. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 3, characterized in that: In the first step, the molar ratio of bisphenol A diglycidyl ether to polyethylene glycol glycidyl ether is 1:(0.25-4), wherein the concentration of bisphenol A diglycidyl ether in the mixed solution is 0.133-0.533 mol / L.
5. The antifreeze, antibacterial and sensing multifunctional hydrogel according to claim 3, characterized in that: In the first step, the feeding amount of the 3-amino-1-propanol is 0.75-0.95 times the total molar amount of the bisphenol A diglycidyl ether and the polyethylene glycol glycidyl ether epoxy monomer.
6. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 3, characterized in that: In the first step, the organic solvent includes N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).
7. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 3, characterized in that: In the second step, the molar ratio of 1,3-propane sultone to 3-amino-1-propanol is (0.5-1.5):
1.
8. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 3, characterized in that: In the third step, the molar ratio of the chemical crosslinking agent to the amino monomer is (0.3-0.75):
1.
9. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 3, characterized in that: In the third step, the chemical cross-linking agent includes hexamethylene diisocyanate HDI, diphenylmethane diisocyanate MDI, and dicyclohexylmethane diisocyanate HMDI.
10. The multifunctional hydrogel for antifreeze, antibacterial and sensing according to claim 3, characterized in that: In the third step and the fourth step, in the mixed solution, the mass concentration of glycerol is 33-67%, the mass concentration of sodium chloride is 5-15%, and the rest is water.