Preparation method of superhard glassy hydrogel
By soaking the polysaccharide polymer hydrogel in a monohydroxy alcohol solution, glass hydrogels with high modulus and high tensile strength are prepared, which solves the problems of complex operation and high cost of existing methods, and achieves a simple and efficient preparation process.
Patent Information
- Application Number
- CN202510189563.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-20
- Publication Date
- 2025-06-13
AI Technical Summary
The existing glassy hydrogel preparation methods have many complex operating steps, the ionic liquid costs are high, and the crosslinking network is difficult to control.
By dissolving the polysaccharide polymer in deionized water, cooling it after hydrothermal reaction, a polysaccharide polymer hydrogel is obtained, and soaked in a monohydroxy alcohol solution to achieve a glassy hydrogel preparation with high modulus and high tensile strength.
This method is simple, avoids tedious reaction conditions, and uses solvent competition to make glassy hydrogels with high solid content, and the preparation process is green and pollution-free.
Smart Images
Figure CN120137209A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of polymer materials, and more specifically, it relates to a preparation method of a superhard vitreous hydrogel. Background Art
[0002] Currently, most hydrogels are highly hydrated soft-matter composite materials, while vitreous hydrogels are less. The existing preparation methods of vitreous hydrogels are as follows: integrating an appropriate amount of rigid hydrophobic polymers into the hydrophilic network of the hydrogel to endow it with high modulus and tensile strength; replacing the medium water with ionic liquids; enhancing the mechanical strength of the hydrogel by highly chemically crosslinking the polymer network.
[0003] Such preparation methods have numerous and complex operation steps, high costs of ionic liquids, and difficult control of crosslinked networks, etc. Summary of the Invention
[0004] In order to solve the above technical problems, the present invention provides a preparation method of a superhard vitreous hydrogel.
[0005] The present invention provides a preparation method of a superhard vitreous hydrogel, comprising the following steps: Step 1: Dissolve polysaccharide polymers in deionized water and disperse evenly. Step 2: Transfer the evenly dispersed polysaccharide polymer solution to a hydrothermal reaction kettle, tighten it, and place it in an oven for heating.
[0006] Step 3: After cooling to room temperature, a polysaccharide polymer hydrogel is obtained.
[0007] Step 4: Immerse the polysaccharide polymer hydrogel in a monohydroxy alcohol solution to obtain a hydrogel with high modulus and high tensile strength.
[0008] Preferably: In step S2, after tightening, place it in an oven for heating at 100 °C.
[0009] Preferably: In step S2, the heating time is 20 min.
[0010] A superhard vitreous hydrogel is prepared by the above method. The raw material composition of this hydrogel is: polysaccharide polymers, deionized water, and monohydroxy alcohol solution.
[0011] The beneficial effects of the present invention are as follows: The preparation method proposed by the present invention is simple, avoiding cumbersome reaction conditions; through a simple method of solvent competition, the water inside the hydrogel is replaced by the alcohol solution to form a vitreous hydrogel with a high solid content; the hydrogel prepared by the present invention is green and pollution-free, and the raw materials are polysaccharides, alcohols, and aqueous solutions. Brief Description of the Drawings
[0012] Figure 1It is the infrared spectrogram in Embodiment 2 of the present invention; Figure 2 It is the stress-strain curve diagram in Embodiment 2 of the present invention; Figure 3 It is the bar chart of Young's modulus in Embodiment 2 of the present invention; Figure 4 It is the bar chart of toughness in Embodiment 2 of the present invention; Figure 5 It is the bar chart of stress in Embodiment 2 of the present invention; Figure 6 It is the bar chart of strain in Embodiment 2 of the present invention; Figure 7 It is the test result diagram of water contact angle in Embodiment 2 of the present invention; Figure 8 It is the bar chart of contact angle in Embodiment 2 of the present invention; Figure 9 It is the scanning electron micrograph in Embodiment 2 of the present invention; Figure 10 It is the weight change curve diagram in Embodiment 2 of the present invention; Figure 11 It is the appearance change diagram in Embodiment 2 of the present invention. Detailed implementation manners
[0013] Now, the subject matter described herein will be discussed with reference to exemplary embodiments. It should be understood that discussing these embodiments is only to enable those skilled in the art to better understand and thus implement the subject matter described herein. Without departing from the scope of protection of the content of this specification, changes can be made to the functions and arrangements of the elements discussed. Each example can omit, substitute, or add various processes or components as needed. Additionally, the features described relative to some examples can also be combined in other examples. Embodiment 1
[0014] In this embodiment, a preparation method of a superhard vitreous hydrogel is proposed, including.
[0015] Step 1: Dissolve 0.2 g of polysaccharide polymer in 9.8 ml of deionized water and disperse it evenly; Step 2: Transfer the evenly dispersed polysaccharide polymer solution to a hydrothermal reaction kettle, tighten it, and place it in an oven at 100 °C (higher than the glass transition temperature of the hydrogel) and heat for 20 min.
[0016] Step 3: After cooling to room temperature, a polysaccharide polymer hydrogel is obtained.
[0017] Step 4: Immerse the polysaccharide polymer hydrogel in a monohydroxy alcohol solution, and after several hours, a hydrogel with high modulus and high tensile strength is obtained. Example 2
[0018] In this example, a superhard vitreous hydrogel is proposed, which is prepared by the method in the example. The raw material composition of the hydrogel is: polysaccharide polymer, deionized water and monohydroxy alcohol solution. Example 3 This example
[0019] This example is used to study the influence of polysaccharide polymer hydrogel immersed in monohydroxy alcohol solution on the mechanical properties of the hydrogel.
[0020] The monohydroxy alcohol includes methanol, ethanol, n-propanol, n-butanol and n-pentanol.
[0021] The current experimental law is analyzed from the hydrophilic and hydrophobic properties of the alcohol solution.
[0022] Methanol: Methanol small molecules can freely pass through the inside of the hydrogel. Due to its tail having a methyl group, it has relatively low hydrophobicity, can drain the water inside the hydrogel, increase the skeleton density, and improve the mechanical properties; Ethanol: Ethanol small molecules can freely pass through the inside of the hydrogel. Due to its tail having an ethyl group, it has hydrophobicity, can drain the water inside the hydrogel, increase the skeleton density, and improve the mechanical properties; n-Propanol: Propanol molecules can pass through the inside of the hydrogel. Due to its tail having a propyl group (3 carbons), it has relatively high hydrophobicity, can drain the water inside the hydrogel, and prevent water molecules from entering the hydrogel again, further increasing the skeleton density and improving the mechanical properties; n-Butanol: Butanol molecules can enter the inside of the hydrogel, but due to its tail having a butyl group (4 carbons), it is not easy to carry out solvent exchange, has relatively strong hydrophobicity, can retain the water inside the hydrogel, the skeleton density changes little, and the mechanical properties are not improved significantly; n-Pentanol: Pentanol molecules are difficult to enter the inside of the hydrogel, but due to its tail having a pentyl group (5 carbons), it is difficult to carry out solvent exchange, has relatively strong hydrophobicity, can retain the water inside the hydrogel, the skeleton density changes little, and the mechanical properties are not improved significantly.
[0023] Taking the example of carrageenan soaked in methanol, ethanol, n-propanol, n-butanol and n-pentanol solutions and then obtaining samples for research and analysis.
[0024] I. Infrared analysis is carried out on each sample, as shown in the infrared spectrogram in the appendix Figure 1 below.
[0025] Infrared analysis: 3300 - 3600 cm -1 : -OH stretching vibration peak, which can prove the enhancement of hydrogen bond interaction.
[0026] 2900 - 2950 cm -1 : C - H stretching vibration peaks of methyl and methylene groups. Symmetric and asymmetric stretching vibration peaks of C - H are at 2850 - 2960 cm⁻¹, which prove whether there are methyl groups inside the hydrogel.
[0027] 1600 - 1680 cm -1 : 1) The hydrogel has an ordered structure. 2) It may be due to the water absorption peak generated during the operation.
[0028] 1250 - 1260 cm -1 : C - O stretching vibration peak, which proves that alcohol has entered the hydrogel.
[0029] II. Methanol, ethanol, propanol (n - propanol and isopropanol): As the carbon chain increases, after entering the hydrogel, regions are formed, providing the skeletal density of the hydrogel, making the hydrogel more compact, enhancing the number of hydrogen bonds, and thus improving the mechanical properties.
[0030] n - Butanol, pentanol: As the number of carbon atoms increases, it is more difficult to enter the hydrogel, and the improvement of the mechanical properties of the hydrogel is not obvious.
[0031] The mechanical properties of each sample were tested, see the Figure 2 stress - strain curve diagram in the appendix, Figure 3 the bar chart of Young's modulus in the Figure 4 bar chart of toughness in the Figure 5 bar chart of stress in the Figure 6 and bar chart of strain in the
[0032] Among them: Modulus: Measuring the strength of the hydrogel, the slope of the stress - strain curve.
[0033] Toughness: The integral area of the stress - strain curve.
[0034] Stress: The maximum fracture stress of the hydrogel, the maximum value on the y - axis.
[0035] Strain: The maximum fracture elongation rate of the hydrogel, the maximum value on the x - axis.
[0036] As can be seen above, the hydrogel soaked in n - propanol has obtained a greater increase in stress, strain, and toughness.
[0037] III. The water contact angle of each sample was tested (isopropanol was added to the sample) See the Figure 7 water contact angle test result diagram of each sample in the appendix and Figure 8 the bar chart of contact angle in the
[0038] After the water contact angle experiment of the soaked alcohol solution to simulate the hydrophilic-hydrophobic behavior in the later stage of the hydrogel soaking, it was found that: The hydrophobicity of methyl alcohol, ethyl alcohol, and propyl alcohol gradually increases because hydrophobic regions are formed after the molecules of methyl alcohol, ethyl alcohol, and propyl alcohol enter the interior of the hydrogel. There are a small number of butyl alcohol molecules in the hydrogel, with high hydrophobicity. The content of amyl alcohol in the hydrogel is relatively small, and its hydrophobicity is worse than that of butyl alcohol. This is basically consistent with the expected results.
[0039] IV. Electron microscopy scanning of each sample See the Figure 9 scanning electron micrographs in the appendix.
[0040] The surface topography diagram at 1000 times magnification of the scanning electron microscope is consistent with the results of mechanical characterization and weight change rate. Methyl alcohol, ethyl alcohol, and propyl alcohol drain the moisture inside the hydrogel, increasing the density of the hydrogel skeleton and making the interior of the hydrogel more dense.
[0041] V. Study on the soaking duration of each sample See the Figure 10 weight change curve graph and Figure 11 appearance change graph.
[0042] As the soaking time increases, the moisture inside the hydrogel is drained, achieving the effect of increasing the density of the skeleton and enhancing the mechanical strength.
[0043] The embodiments of the present invention are described above, but these embodiments are not limited to the above specific implementation manners. The above specific implementation manners are merely illustrative rather than restrictive. Under the inspiration of these embodiments, those of ordinary skill in the art can also make many forms, all of which fall within the protection scope of these embodiments.
Claims
1. A method for preparing a superhard glassy hydrogel, characterized in that: The steps include: Step 1: Dissolve the polysaccharide polymer in deionized water and disperse evenly; Step 2: Transfer the evenly dispersed polysaccharide polymer solution to the hydrothermal reactor, tighten it and place it in an oven for heating; Step 3: After cooling to room temperature, a polysaccharide polymer hydrogel is obtained; Step 4: Soak the polysaccharide polymer hydrogel in a monohydroxy alcohol solution to obtain a hydrogel with high modulus and high tensile strength.
2. The method for preparing a superhard glassy hydrogel according to claim 1, characterized in that: In step S2, after tightening, place in an oven and heat at 100°C.
3. The method for preparing a superhard glassy hydrogel according to claim 1, characterized in that: In step S2, the heating time is 20 minutes.
4. A superhard glassy hydrogel prepared by the method of claim 1, characterized in that: The raw materials of the hydrogel include polysaccharide polymer, deionized water and monohydroxy alcohol solution.