Composite hydrogel material with buffering protection function as well as preparation method and application of composite hydrogel material
The micro-phase region is formed by polymerizing charged hydrogel monomers with polymer polymer radicals, which solves the problem of fragility of traditional hydrogels and achieves high elastic modulus and buffer protection functions.
Patent Information
- Application Number
- CN202510278565.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-10
- Publication Date
- 2025-07-04
AI Technical Summary
Traditional hydrogel materials have poor mechanical properties, are prone to breakage, have low toughness, and cannot effectively buffer and protect.
By radically polymerizing charged hydrogel monomers with oppositely charged polymer polymers, a microphase region is formed to increase the elastic modulus of the gel.
The elastic modulus of the hydrogel is significantly improved, and it can maintain integrity under large compressive stress, avoid breakage, and provide effective buffering protection.
Smart Images
Figure CN120248221A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of functional polymer hydrogels, and particularly relates to a composite hydrogel material with a buffering and protective function, a preparation method thereof, and an application thereof. Background Art
[0002] In recent years, as a new type of material, hydrogels have received a great deal of attention from researchers. As a three-dimensional structure material with water as the base, hydrogels have excellent stretchability and elasticity. However, traditional hydrogel materials have disadvantages such as poor mechanical properties, easy fragmentation, and low toughness. To improve the above defects, currently, mainly by adding cross-linking agents (divinylbenzene, diisocyanate, N,N-methylenebisacrylamide, etc.), hydrophilic substances (such as glucose, glycerol, PEG, etc.) or adjusting the preparation process (such as changing the reaction temperature, pressure, or pH value of the reaction system, etc.) to increase the elasticity of the hydrogel. However, the hydrogels prepared by the above methods have problems such as poor mechanical properties and easy fragmentation under external forces. Summary of the Invention
[0003] In order to improve the deficiencies of the prior art, the present invention provides a composite hydrogel material with a buffering and protective function, a preparation method thereof, and an application thereof. The elastic modulus range of the composite hydrogel material is 6.51 - 406440 Pa.
[0004] In the first aspect, the present invention provides a preparation method of a composite hydrogel material with a buffering and protective function, and the method includes the following steps:
[0005] Performing a free radical polymerization reaction on a hydrogel monomer and a polymer macromolecule to obtain a composite hydrogel material, at least a part of the hydrogel monomer being charged, and the polymer macromolecule having a charge opposite to that of the hydrogel monomer on its polymer chain.
[0006] According to an embodiment of the present invention, the hydrogel monomer includes at least one of acrylamide, N-isopropylacrylamide, polyethylene glycol diacrylate, hydroxyethyl methacrylate, and polypropylene glycol diacrylate.
[0007] According to an embodiment of the present invention, the hydrogel monomer at least includes one charged hydrogel monomer, and the charged hydrogel monomer is selected from at least one of acryloyloxyethyl trimethyl ammonium chloride, dimethyldiallyl ammonium chloride, 2-(acryloyloxy)ethyl trimethyl ammonium bromide, and [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride.
[0008] As an example, the hydrogel monomer is acrylamide, [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride, and sodium polystyrene sulfonate.
[0009] According to an embodiment of the present invention, the polymeric macromolecule is selected from at least one of sodium polyvinyl sulfonate, sodium polyacrylate, and sodium polystyrene sulfonate, and is, for example, PSSNa.
[0010] According to an embodiment of the present invention, the molecular weight of the PSSNa is 1 to 4000 kDa, preferably the molecular weight of the PSSNa is 2 to 2242 kDa, and is, for example, 1.6 kDa, 70 kDa, 200 kDa, 1000 kDa, 2000 kDa.
[0011] According to an embodiment of the present invention, the method comprises the following steps:
[0012] S1. Mix a hydrogel monomer, a crosslinking agent, and a polymeric macromolecule in a reaction vessel, and then add a co-initiator and water and mix to obtain a pre-gel solution;
[0013] S2. Add an initiator to the pre-gel solution and react in an anaerobic environment to obtain a composite hydrogel material.
[0014] According to an embodiment of the present invention, the crosslinking agent is selected from at least one of ethylene glycol, trimethylolpropane, polyoxypropylene ether triol, and N,N′-methylenebisacrylamide, and is, for example, N,N′-methylenebisacrylamide.
[0015] According to an embodiment of the present invention, the co-initiator is selected from at least one of potassium persulfate, ammonium persulfate, polyvinylpyrrolidone (PVP), and a photoinitiator, and is, for example, tetramethylethylenediamine, and the photoinitiator is selected from photoinitiators known in the art, and is, for example, dimethyl 2,2′-azobis(2-methylpropionate).
[0016] According to an embodiment of the present invention, the initiator is selected from ammonium persulfate.
[0017] According to an embodiment of the present invention, the step S1 comprises the following steps:
[0018] Mix acrylamide with a concentration of 32% - 41%, [2-(methacryloyloxy)ethyl]trimethylammonium chloride with a concentration of 60% - 85%, and N,N′-methylenebisacrylamide with a concentration of 1% - 4%, then add sodium polystyrene sulfonate with a concentration of 18% - 45% and mix, and then add TEMED and water and mix to obtain a pre-gel solution.
[0019] According to an embodiment of the present invention, the volume ratio of acrylamide, [2-(methacryloyloxy)ethyl]trimethylammonium chloride, and N,N′-methylenebisacrylamide is 1:(2 - 10):(1 - 10), preferably the volume ratio of acrylamide, [2-(methacryloyloxy)ethyl]trimethylammonium chloride, and sodium polystyrene sulfonate is 1:(3 - 7):(1 - 6), and is, for example, 1:6:3.
[0020] According to an embodiment of the present invention, the volume ratio of PSSNa to acrylamide is (25-30):1, for example, 27:1.
[0021] According to an embodiment of the present invention, the volume ratio of water to acrylamide is (20-30):1, for example, 25:1, 20:1.
[0022] According to an embodiment of the present invention, the concentration of N,N'-methylenebisacrylamide is 1%-4%.
[0023] According to an embodiment of the present invention, in step S2, the concentration of the initiator added to the pre-gel solution is 22-28 mg / ml.
[0024] According to an embodiment of the present invention, in step S2, an anaerobic environment is achieved by the following method: after sealing the reaction vessel, an inert gas is introduced into the reaction vessel until the oxygen in the reaction environment is exhausted.
[0025] According to an embodiment of the present invention, the inert gas is selected from at least one of nitrogen, helium, and carbon dioxide gas, for example, nitrogen.
[0026] According to an embodiment of the present invention, the reaction time in step S2 is 30-60 h, for example, 48 h.
[0027] In a second aspect, the present invention provides a composite hydrogel material prepared by the above method. The composite hydrogel material has mechanical response properties, and the elastic modulus range of the composite hydrogel material is 6.51-406440 Pa.
[0028] According to an embodiment of the present invention, the elastic modulus of the composite hydrogel material is 11308-406440 Pa.
[0029] According to an embodiment of the present invention, the change in the elastic modulus of the composite hydrogel material is +62433 times, where the "+" means an increase.
[0030] As an example, when the molecular weight of PSSNa is 200 kDa, the elastic modulus of the composite hydrogel material is 406440 Pa.
[0031] In a third aspect, the present invention provides a use of the above composite hydrogel material as a buffer protection material.
[0032] Beneficial effects
[0033] In the present invention, charged monomers are selected as hydrogel monomers, so that the molecular chains of the hydrogel itself carry charges. Then, polymer macromolecules with charges opposite to those of the charged monomers are added thereto. During the reaction process, the molecular chains of the polymer macromolecules form microphase regions inside the gel, providing huge modulus support for the gel. In the present invention, the inventors obtained excellent mechanical properties of the gel after synthesis by changing the molecular weight of the polymer added to the inside of the gel, and obtained a complete gel system by adjusting the molecular weight of the polymer. Description of the Drawings
[0034] Figure 1 Graph comparing the moduli of the composite hydrogel prepared in Example 3 and the hydrogel prepared in Comparative Example 1;
[0035] Figure 2 Graph comparing the viscoelastic properties of the composite hydrogel prepared in Example 1 and the hydrogel prepared in Comparative Example 1.
[0036] Figure 3 From top to bottom are the physical pictures of the compression experiments of the composite hydrogels prepared in Example 1, Example 3, and Example 2 stacked;
[0037] Figure 4 Physical picture after the compression experiment of the composite hydrogels prepared in Examples 1-3 stacked;
[0038] Figure 5 Compression stress-compression strain graph of the composite hydrogels prepared in Examples 1-3;
[0039] Figure 6 Compression experiment graph of the hydrogel prepared in Example 3;
[0040] Figure 7 Physical picture after the compression experiment of the hydrogel prepared in Example 3;
[0041] Figure 8 Compression stress-compression strain graph of a single gel material;
[0042] Figure 9 Rheological test graph of the hydrogel prepared in Example 2;
[0043] Figure 10 Rheological test graph of the hydrogel prepared in Example 3;
[0044] Figure 11 Rheological test graph of the hydrogel prepared in Example 4. Detailed Description of the Invention
[0045] The following will further elaborate on the composite hydrogel material of the present invention, its preparation method, and applications in combination with specific embodiments. It should be understood that the following embodiments are only for exemplarily illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope intended to be protected by the present invention.
[0046] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products, or can be prepared by known methods.
[0047] The water used in the following examples is deionized water obtained by an ultrapure water instrument.
[0048] Preparation Example 1
[0049] Add [2-(methacryloyloxy)ethyl]trimethylammonium chloride to water to prepare solution A with a concentration of 60% - 85%.
[0050] Add acrylamide to water to prepare solution B with a concentration of 32% - 41%.
[0051] Add N,N'-methylenebisacrylamide to water to prepare solution C with a concentration of 1% - 4%.
[0052] Add PSSNa (Sodium Polystyrene Sulfonate) to water to prepare solution D with a concentration of 18% - 45%.
[0053] According to the proportions in Table 1, first take the corresponding volumes of solution A, solution B, and solution C and add them to a reaction vessel for mixing until uniform, then add solution D for mixing, add the corresponding co-initiator and water, and stir until uniformly mixed to obtain a pre-gel solution.
[0054] Seal the reaction vessel with a sealing film, introduce nitrogen into the reaction vessel for 15 minutes, exhaust the oxygen in the reaction environment, and then allow the pre-gel solution to react under anaerobic conditions for 48 hours. Remove the sealing film to obtain the composite hydrogel material with buffer protection function.
[0055] Among them, the time for introducing nitrogen can be adjusted according to actual needs as long as the oxygen in the reaction environment is exhausted; and the gas introduced can also be other inert gases, such as argon, helium, etc.
[0056] In this gel system, [2-(methacryloyloxy)ethyl]trimethylammonium chloride is positively charged. According to the molar amount of positive charge in the solution, solution D is added to it to make the ratio of positive and negative charges reach a specific ratio. TEMED (tetramethylethylenediamine) is added as a co-initiator, and then water is added to prepare a pre-gel solution. The solution is sealed and nitrogen is introduced to create an anaerobic environment. After the nitrogen fills the entire reaction vessel, 5 mg of APS (ammonium persulfate) solution is added, and the reaction is carried out for 48 hours.
[0057] Table 1 Reactant ratios of different examples and comparative examples
[0058]
[0059]
[0060] In the test examples, the composite hydrogel materials obtained from Examples 1-4 and Comparative Examples 1-2 were subjected to mechanical tests, including modulus tests and compression experiment tests.
[0061] Among them, the modulus test was carried out by the following method: The corresponding composite hydrogel was cut into discs with a diameter of 27 mm and subjected to a shear rheology experiment on a rheometer.
[0062] The compression experiment test and the destructive experiment test were carried out by the following method: Three different gels were stacked with the softest and most elastic (Example 1) on the top, the gel with the highest modulus (Example 3) in the middle, and another gel with a moderate modulus (Example 2) at the bottom (see Figure 3 ). Then, the position of the fixture was adjusted so that the upper clamping plate was as close as possible to the gel. Then, the parameters were set, the maximum deformation and load were adjusted, and then the machine pressurized the composite gel material under program control to obtain the test results.
[0063] The mechanical properties of the obtained gels were measured, and it was found that their changes were significant. An expansion of 62,433 times in the modulus could be achieved through this gel system.
[0064] See Figure 1 As shown, compared with the composite hydrogel material prepared in Comparative Example 1 without adding a polymer, the modulus of the composite hydrogel material prepared in Example 1 by adding a polymer with a molecular weight of 200 kDa was expanded by 62,433 times.
[0065] See Figure 2 As shown, compared with the hydrogel material of Comparative Example 1 without adding a polymer, the viscoelasticity of the composite hydrogel material prepared in Example 1 was increased.
[0066] See Figure 3As shown, the composite hydrogel materials prepared in Examples 1-3 were selected for compression experiments. The composite hydrogel materials prepared in Example 1, Example 3, and Example 2 were stacked in order from top to bottom and then subjected to a destructive experiment. See Figure 4 As shown, after the experiment was completed, the corresponding composite hydrogel materials did not break, but only showed some honeycomb-like cracks; because under different compression strains, the stress of the composite hydrogel materials against compression was different, resulting in the segmented presentation of the compression stress of the composite hydrogel materials. See Figure 5 As shown, the compression experiment results showed that the first-stage compression stress was fitted to 0.56 MPa, and the interval was 15.83%-46.54%; the second-stage compression stress was fitted to 3.03 MPa, and the interval was 49.5%-65.56%; the final compression stress was 1.48 MPa, and the final compression strain was 79%.
[0067] For the composite hydrogels prepared in Comparative Example 1 and Comparative Example 2, due to their too low modulus, they could hardly resist external impact, so it was difficult to conduct a destructive experiment.
[0068] See Figure 6 As shown, a compression experiment was conducted on the single gel material prepared in Example 3. See Figure 7 As shown, a destructive experiment was conducted on the composite hydrogel material prepared in Example 3. After the experiment was completed, there were a large number of cracks and broken traces on the corresponding composite hydrogel material.
[0069] See Figure 8 As shown, the compression test results showed that the compression stress of the single gel material prepared in Comparative Example 1 was fitted to 0.33 MPa, and the interval was 20.23%-50.38%; the final compression stress was 0.47 MPa, and the final compression strain was 81.9%.
[0070] As mentioned above, the composite hydrogel material prepared by the present invention has a relatively large elastic modulus, and when the compression stress reaches 1.48 MPa, the final compression strain is 79%, which is much greater than that of the single gel material when the compression stress is 0.47 MPa and the compression strain reaches 81.9%, that is, the composite hydrogel prepared by the present invention has good elasticity; at the same time, under the action of a relatively large compression stress, the composite hydrogel does not break, but only shows some honeycomb-like cracks. Therefore, when encountering a strong impact force, the composite hydrogel material will not break to produce sharp and pointed fracture surfaces, but only produce cracks on the flexible body, which is relatively safe.
[0071] Based on this, the above composite hydrogel material can be used as an elastic material, such as a sports protection material.
[0072] For example, the application scenarios are exemplified as follows:
[0073] In the field of sports protection, most products use woven materials to wrap hard plastics, and at the same time, sponge-like protective materials are filled inside the hard plastics to protect joint parts such as elbows and knees. When encountering a strong impact, the protective shell may be broken, and the hard plastic will have sharp and pointed fracture surfaces, which are likely to cause secondary injuries. To solve this problem, a layer of material with buffer protection function that will not break or shatter can be additionally installed around the outer shell materials such as hard plastics, or the internal sponge-like protective material can be replaced with the composite hydrogel material prepared by the present invention to achieve this goal.
[0074] The specific implementation modes of the present invention have been exemplarily described above through embodiments. However, the protection scope of the present invention is not limited to the above exemplary implementation modes. Any modifications, equivalent replacements, improvements, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.
Claims
1. A preparation method of a composite hydrogel material with a buffer protection function, characterized in that, The method includes the following steps: A free radical polymerization reaction is carried out between a hydrogel monomer and a polymer macromolecule to obtain a composite hydrogel material. At least a part of the hydrogel monomer is charged, and the polymer macromolecule has a charge opposite to that of the hydrogel monomer on its polymer chain.
2. The preparation method of the composite hydrogel material with a buffer protection function according to claim 1, characterized in that, The hydrogel monomer includes at least one of acrylamide, N-isopropylacrylamide, polyethylene glycol diacrylate, hydroxyethyl methacrylate, and polypropylene glycol diacrylate. Preferably, the hydrogel monomer at least includes a charged hydrogel monomer, and the charged hydrogel monomer is selected from at least one of acryloyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, 2-(acryloyloxy)ethyl trimethyl ammonium bromide, and [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride.
3. The preparation method of the composite hydrogel material with a buffer protection function according to claim 1, characterized in that, The polymer macromolecule is selected from at least one of sodium polyvinyl sulfonate, sodium polyacrylate, and sodium polystyrene sulfonate. Preferably, the molecular weight of the sodium polystyrene sulfonate is 1-4000 kDa.
4. The preparation method of the composite hydrogel material with a buffer protection function according to any one of claims 1-3, characterized in that, The method includes the following steps: S1. Add the hydrogel monomer, crosslinking agent, and polymer macromolecule into a reaction vessel and mix them, then add a co-initiator and water and mix to obtain a pre-gel solution; S2. Under an anaerobic environment, add an initiator to the pre-gel solution and react to obtain a composite hydrogel material.
5. The preparation method of the composite hydrogel material with a buffer protection function according to claim 4, characterized in that, The crosslinking agent is selected from at least one of ethylene glycol, trimethylolpropane, polyoxypropylene ether triol, and N,N'-methylenebisacrylamide. Preferably, the co-initiator is selected from at least one of potassium persulfate, ammonium persulfate, polyvinylpyrrolidone, and a photoinitiator.
6. The preparation method of the composite hydrogel material with a buffer protection function according to claim 4, characterized in that, Step S1 includes the following steps: Mix acrylamide with a concentration of 32%-41%, [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride with a concentration of 60%-85%, and N,N'-methylenebisacrylamide with a concentration of 1%-4%, then add sodium polystyrene sulfonate with a concentration of 18%-45% and mix, and then add TEMED and water and mix to obtain a pre-gel solution.
7. The preparation method of the composite hydrogel material with a buffer protection function according to claim 6, characterized in that, The concentration of the N,N'-methylenebisacrylamide is 1%-4%.
8. The preparation method of the composite hydrogel material with a buffer protection function according to claim 6, characterized in that, The reaction time in step S2 is 30-60 h.
9. A composite hydrogel material prepared by the method according to any one of claims 1-8, characterized in that the composite hydrogel material has mechanical response performance, and the elastic modulus range of the composite hydrogel material is 6.51-406440 Pa. Preferably, the elastic modulus of the composite hydrogel material is 11308-406440 Pa.
10. Use of a composite hydrogel material prepared by the method according to any one of claims 1-8 or the composite hydrogel material according to claim 9 as a buffer protection material.