CN114805859A - Preparation method of heat-setting chitosan hydrogel - Google Patents
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 63
- 239000000017 hydrogel Substances 0.000 title claims abstract description 42
- 238000009998 heat setting Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000006196 deacetylation Effects 0.000 claims abstract description 12
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims 17
- 239000002184 metal Substances 0.000 claims 2
- 239000012266 salt solution Substances 0.000 claims 2
- 239000000499 gel Substances 0.000 abstract description 26
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 9
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 3
- -1 amino polysaccharide Chemical class 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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Abstract
Description
技术领域technical field
本发明涉及水凝胶的制备方法，特别涉及热定型壳聚糖水凝胶的制备方法，属于化学技术领域。The invention relates to a preparation method of a hydrogel, in particular to a preparation method of a heat-setting chitosan hydrogel, and belongs to the technical field of chemistry.
背景技术Background technique
水凝胶是一种能够吸收并保持大量水分的三维网络结构交联物，它具有良好的生物相容性、刺激响应性和易于功能化等特点，在生物化学、医药卫生、农业和环保等领域有着广泛的应用。热可逆凝胶是一种可以根据温度进行融化和改造的凝胶。大多数热可逆凝胶的特点是随着温度的降低，从溶胶变成凝胶，再次加热时，又从凝胶转化为溶胶，具有热可逆性。根据凝胶分子的来源，水凝胶可以分为天然水凝胶和人工合成水凝胶。其中，人工合成水凝胶的材料也可以分为天然高分子和人工合成的分子。人工合成分子往往是通过石油化工提炼或者有机合成聚合而得到的，制备过程繁琐、费用昂贵，且不可再生。因此，基于天然可再生的高分子开发水凝胶具有重要意义。Hydrogel is a three-dimensional network-structured cross-linker that can absorb and retain a large amount of water. It has the characteristics of good biocompatibility, stimuli responsiveness and easy functionalization. field has a wide range of applications. Thermoreversible gels are gels that can be melted and reformed depending on temperature. Most thermoreversible gels are characterized by changing from sol to gel as the temperature is lowered, and then from gel to sol when heated again, which is thermoreversible. According to the source of gel molecules, hydrogels can be divided into natural hydrogels and synthetic hydrogels. Among them, the materials of artificially synthesized hydrogels can also be divided into natural polymers and artificially synthesized molecules. Synthetic molecules are often obtained through petrochemical refining or organic synthesis polymerization. The preparation process is cumbersome, expensive, and non-renewable. Therefore, it is of great significance to develop hydrogels based on natural and renewable polymers.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于基于天然可再生的高分子开发热定型水凝胶。The aim of the present invention is to develop heat-setting hydrogels based on natural and renewable macromolecules.
为实现本发明的目的，采用了下述的技术方案：一种热定型壳聚糖水凝胶的制备方法，采用以下步骤：In order to achieve the purpose of the present invention, the following technical scheme is adopted: a preparation method of heat-setting chitosan hydrogel, adopts the following steps:
S1：将脱乙酰度达95%以上的壳聚糖溶于体积浓度为1%乙酸溶液、或者溶于摩尔浓度为1%的盐酸溶液，配制成浓度为（1-3）wt%壳聚糖溶液，壳聚糖的粘度为100-200 mpa.s；S1: Dissolve chitosan with a degree of deacetylation of more than 95% in acetic acid solution with a volume concentration of 1%, or in a hydrochloric acid solution with a molar concentration of 1%, to prepare a concentration of (1-3) wt% chitosan solution, the viscosity of chitosan is 100-200 mpa.s;
S2：向壳聚糖溶液中搅拌下加入NaOH溶液，搅拌均匀，每毫升、每1 wt%壳聚糖溶液滴加的NaOH折合为（1.25-25）× 10-6 mol，NaOH溶液的浓度为0.4-0.7 M；S2: Add NaOH solution to the chitosan solution with stirring, and stir evenly. The amount of NaOH added dropwise per ml, per 1 wt% chitosan solution is equivalent to (1.25-25) × 10 -6 mol, and the concentration of the NaOH solution is 0.4-0.7 M;
S3：向步骤S2得到的体系中加入硝酸金属盐溶液，搅拌均匀；所述的金属硝酸盐溶液包括Ni(NO3)2、Cu(NO3)2、Zn(NO3)2、Cd(NO3)2、Co(NO3)2溶液，金属硝酸盐溶液的浓度为0.4-0.7M，每毫升浓度为2.0 wt%壳聚糖溶液加入的硝酸盐量为（0.9-1.1）× 10-4 mol；S3: Add metal nitrate solution to the system obtained in step S2, and stir evenly; the metal nitrate solution includes Ni(NO 3 ) 2 , Cu(NO 3 ) 2 , Zn(NO 3 ) 2 , Cd(NO 3 ) 2 3 ) 2 , Co(NO 3 ) 2 solution, the concentration of metal nitrate solution is 0.4-0.7M, and the amount of nitrate added per milliliter concentration of 2.0 wt% chitosan solution is (0.9-1.1) × 10 -4 mol;
S4：将步骤S3得到的体系加热到80℃以上100℃以下，即可得到热定型壳聚糖水凝胶。S4: heating the system obtained in step S3 to a temperature above 80°C and below 100°C to obtain a heat-set chitosan hydrogel.
进一步的；将步骤S4得到的热定型壳聚糖水凝胶降温至常温，热定型壳聚糖水凝胶变为流动性良好的溶胶。Further; the heat-set chitosan hydrogel obtained in step S4 is cooled to normal temperature, and the heat-set chitosan hydrogel becomes a sol with good fluidity.
进一步的；所述的硝酸金属盐溶液为Ni(NO3)2溶液，采用以下制备方法：将脱乙酰度达95%以上的壳聚糖溶于体积浓度为1%的乙酸溶液，配制成浓度为2.0 wt%壳聚糖溶液，取2 mL所配溶液，搅拌加入30 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入400 μL浓度为0.5 M的Ni(NO3)2溶液，搅拌均匀，然后加热到95℃，即得到热定型壳聚糖水凝胶。Further; the metal nitrate solution is Ni(NO 3 ) 2 solution, and the following preparation method is adopted: chitosan with a degree of deacetylation of more than 95% is dissolved in an acetic acid solution whose volume concentration is 1%, and the concentration is For 2.0 wt% chitosan solution, take 2 mL of the prepared solution, add 30 μL NaOH solution with a concentration of 0.5 M, stir evenly, and then add 400 μL Ni(NO 3 ) 2 solution with a concentration of 0.5 M, stir evenly , and then heated to 95°C to obtain heat-setting chitosan hydrogel.
进一步的；所述的热定型壳聚糖水凝胶成胶时间小于等于3min。Further; the gelation time of the heat-setting chitosan hydrogel is less than or equal to 3min.
进一步的；所述的热定型壳聚糖水凝胶澄清透明，可循环次数大于100次。Further; the heat-setting chitosan hydrogel is clear and transparent, and the cycle number is more than 100 times.
本发明的积极有益技术效果在于：壳聚糖是由天然甲壳素通过去乙酰化反应而形成的一种碱性氨基多糖，在自然界中广泛存在。本发明以天然的壳聚糖为原料，以乙酸、盐酸为溶剂，加入金属离子后，通过升高溶液温度制备得到了完全可逆的热定型水凝胶。结果表明，当温度升高后，壳聚糖分子中质子化的氨基能够解离出氢离子，从而导致pH降低，游离的氨基可以和金属离子络合，从而交联形成高弹性热可逆水凝胶。该热定型凝胶澄清透明，可以循环100次以上。热可逆凝胶是一种可以根据温度进行融化和改造的凝胶，目前的热可逆凝胶的特点是随着温度的降低，从溶胶变成凝胶，再次加热时，又从凝胶转化为溶胶，具有热可逆性，然而，本发明涉及的通过加热形成凝胶、降温变成溶胶的热可逆凝胶的报道较少，在加热状态下形成水凝胶进一步开拓了水凝胶的应用空间。The positive and beneficial technical effects of the present invention are that: chitosan is a basic amino polysaccharide formed by deacetylation of natural chitin, and widely exists in nature. In the present invention, natural chitosan is used as raw material, acetic acid and hydrochloric acid are used as solvents, and after adding metal ions, a fully reversible heat-setting hydrogel is prepared by increasing the temperature of the solution. The results show that when the temperature increases, the protonated amino groups in the chitosan molecule can dissociate hydrogen ions, resulting in a decrease in pH. glue. The heat setting gel is clear and transparent and can be cycled more than 100 times. Thermoreversible gel is a gel that can be melted and transformed according to temperature. The current thermoreversible gel is characterized by changing from sol to gel as the temperature decreases, and then from gel to gel when heated again. Sols are thermally reversible. However, there are few reports on the thermally reversible gels formed by heating and cooling into sols. The formation of hydrogels under heating further opens up the application space of hydrogels. .
附图说明Description of drawings
图1是不同水凝胶的照片。Figure 1 is a photograph of different hydrogels.
图2是温度对凝胶前驱溶液pH的影响图。Figure 2 is a graph showing the effect of temperature on the pH of the gel precursor solution.
图3是壳聚糖-镍离子溶液的流变性与温度的关系图。Figure 3 is a graph showing the relationship between rheology and temperature of chitosan-nickel ion solution.
具体实施方式Detailed ways
为了更充分的解释本发明的实施，提供本发明的实施实例，这些实施实例仅仅是对本发明的阐述，不限制本发明的范围。In order to more fully explain the implementation of the present invention, the implementation examples of the present invention are provided, and these implementation examples are only illustrative of the present invention and do not limit the scope of the present invention.
实施例1：Example 1:
将脱乙酰度达95%以上的壳聚糖溶于体积浓度为1%的乙酸溶液，配制成浓度为2.0wt%壳聚糖溶液，取2 mL所配溶液，搅拌下缓慢加入30 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入400 μL浓度为0.5 M的Ni(NO3)2溶液，搅拌均匀。然后加热到约95℃，即得到澄清透明高弹水凝胶。室温冷却后凝胶慢慢变回原来的溶液。Dissolve chitosan with a degree of deacetylation above 95% in acetic acid solution with a volume concentration of 1% to prepare a chitosan solution with a concentration of 2.0wt%, take 2 mL of the prepared solution, and slowly add 30 μL of the solution under stirring to a concentration of 2.0 wt%. 0.5 M NaOH solution, stir evenly, then add 400 μL of 0.5 M Ni(NO 3 ) 2 solution, stir evenly. Then heated to about 95°C to obtain a clear and transparent high elastic hydrogel. The gel slowly returned to its original solution after cooling at room temperature.
实施例2：Example 2:
将脱乙酰度达95%以上的壳聚糖溶于体积浓度为1%的乙酸溶液，配制成浓度为2.0wt%壳聚糖溶液，取3 mL所配溶液，搅拌下缓慢加入15 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入600 μL浓度为0.5 M的Cu(NO3)2溶液，搅拌均匀。然后加热到约85℃，即得到澄清透明高弹水凝胶。室温冷却后凝胶慢慢变回原来的溶液。Dissolve chitosan with a degree of deacetylation of more than 95% in acetic acid solution with a volume concentration of 1% to prepare a 2.0wt% chitosan solution, take 3 mL of the prepared solution, and slowly add 15 μL of the solution under stirring to a concentration of 0.5 M NaOH solution, stir well, then add 600 μL Cu(NO 3 ) 2 solution with a concentration of 0.5 M, stir well. Then heated to about 85°C to obtain a clear and transparent high elastic hydrogel. The gel slowly returned to its original solution after cooling at room temperature.
实施例3：Example 3:
将脱乙酰度达95%以上的壳聚糖溶于体积浓度为1%的乙酸溶液，配制成浓度为2.0wt%壳聚糖溶液，取2 mL所配溶液，搅拌下缓慢加入100 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入400 μL浓度为0.5 M的Zn(NO3)2溶液，搅拌均匀。然后加热到约95℃，即得到澄清透明高弹水凝胶。室温冷却后凝胶慢慢变回原来的溶液。Dissolve chitosan with a degree of deacetylation of more than 95% in acetic acid solution with a volume concentration of 1% to prepare a chitosan solution with a concentration of 2.0wt%, take 2 mL of the prepared solution, and slowly add 100 μL of the solution under stirring. 0.5 M NaOH solution, stir evenly, then add 400 μL of 0.5 M Zn(NO 3 ) 2 solution and stir evenly. Then heated to about 95°C to obtain a clear and transparent high elastic hydrogel. The gel slowly returned to its original solution after cooling at room temperature.
实施例4：Example 4:
将脱乙酰度达95%以上的壳聚糖溶于体积浓度为1%的乙酸溶液，配制成浓度为2.0wt%壳聚糖溶液，取3 mL所配溶液，搅拌下缓慢加入300 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入600 μL浓度为0.5 M的Co(NO3)2溶液，搅拌均匀。然后加热到约90℃，即得到澄清透明高弹水凝胶。室温冷却后凝胶慢慢变回原来的溶液。Dissolve chitosan with a degree of deacetylation of more than 95% in acetic acid solution with a volume concentration of 1% to prepare a chitosan solution with a concentration of 2.0wt%, take 3 mL of the prepared solution, and slowly add 300 μL of the solution under stirring. 0.5 M NaOH solution, stir well, then add 600 μL Co(NO 3 ) 2 solution with a concentration of 0.5 M, stir well. Then heated to about 90°C to obtain a clear and transparent high elastic hydrogel. The gel slowly returned to its original solution after cooling at room temperature.
实施例5：Example 5:
将脱乙酰度达95%以上的壳聚糖溶于摩尔浓度为1 %的盐酸溶液，配制成浓度为1.0 wt%壳聚糖溶液，取2 mL所配溶液，搅拌下缓慢加入80 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入200 μL浓度为0.5 M的Zn(NO3)2溶液，搅拌均匀。然后加热到约90℃，即得到澄清透明高弹水凝胶。室温冷却后凝胶慢慢变回原来的溶液。The chitosan with a degree of deacetylation of more than 95% was dissolved in a hydrochloric acid solution with a molar concentration of 1 % to prepare a chitosan solution with a concentration of 1.0 wt%. 0.5 M NaOH solution, stir evenly, then add 200 μL of 0.5 M Zn(NO 3 ) 2 solution, and stir evenly. Then heated to about 90°C to obtain a clear and transparent high elastic hydrogel. The gel slowly returned to its original solution after cooling at room temperature.
实施例6：Example 6:
将脱乙酰度达95%以上的壳聚糖溶于摩尔浓度为1 %的盐酸溶液，配制成浓度为3wt%壳聚糖溶液，取2mL所配溶液，搅拌下缓慢加入200 μL浓度为0.5 M的NaOH溶液，搅拌均匀，然后加入600 μL浓度为0.5 M的Ni(NO3)2溶液，搅拌均匀。然后加热到约95℃，即得到澄清透明高弹水凝胶。室温冷却后凝胶慢慢变回原来的溶液。The chitosan with a degree of deacetylation of more than 95% is dissolved in a hydrochloric acid solution with a molar concentration of 1%, and the concentration is 3wt% chitosan solution. Take 2mL of the prepared solution, and slowly add 200 μL under stirring. NaOH solution, stir evenly, then add 600 μL of Ni(NO 3 ) 2 solution with a concentration of 0.5 M, and stir evenly. Then heated to about 95°C to obtain a clear and transparent high elastic hydrogel. The gel slowly returned to its original solution after cooling at room temperature.
图1是本发明得到的凝胶照片。Fig. 1 is a photograph of the gel obtained by the present invention.
本发明的机理解析：图2是用于本发明机理探讨和解释的图，图中CS为壳聚糖，UP为升温，down为降温，采用的是盐酸溶解壳聚糖。图2只是为了说明本发明的机理。图2中，壳聚糖（质子化）溶液在40℃时，壳聚糖上的氨基主要以铵盐形式存在，铵盐与镍离子的作用力很低。因此溶液呈流动状态，此时的pH约为3.5。随着温度的逐渐升高，质子化壳聚糖分子上的铵盐解离，生成游离的氨基及H+，H+使溶液的pH下降，同时，游离的氨基可以和溶液中的镍离子形成强烈的络合，交联形成动态分子网络。当加入镍离子、温度升高到某个临界点时，镍离子与氨基络合形成的交联点足够多，高分子网络束缚水分子，生成高弹水凝胶。降温时，以上过程完全可逆，游离的H+重新和氨基结合，生成铵盐。而镍离子重新被释放到溶液中，使凝胶转变为溶液态。Mechanism analysis of the present invention: Fig. 2 is a diagram for discussing and explaining the mechanism of the present invention, in which CS is chitosan, UP is heating, and down is cooling, and hydrochloric acid is used to dissolve chitosan. Figure 2 is only for illustrating the mechanism of the present invention. In Figure 2, when the chitosan (protonated) solution is at 40 °C, the amino groups on chitosan mainly exist in the form of ammonium salts, and the interaction between ammonium salts and nickel ions is very low. The solution is therefore in a fluid state, at which point the pH is about 3.5. As the temperature gradually increases, the ammonium salts on the protonated chitosan molecules dissociate to generate free amino groups and H + , and H + reduces the pH of the solution. At the same time, the free amino groups can form with nickel ions in the solution. Strong complexation, cross-linking to form dynamic molecular network. When nickel ions are added and the temperature rises to a certain critical point, there are enough cross-linking points formed by the complexation of nickel ions and amino groups, and the polymer network binds water molecules to form a highly elastic hydrogel. When the temperature is lowered, the above process is completely reversible, and the free H + is recombined with the amino group to form an ammonium salt. The nickel ions are released back into the solution, which turns the gel into a solution state.
图3是壳聚糖-镍离子溶液的流变性与温度的关系。常温时，质子化壳聚糖与镍离子作用力很弱，不能形成交联，因此为溶液态。此时，样品的损耗模量（G”）大于储能模量（G’）。当温度升高到某个临界点时（约68℃），壳聚糖分子上的铵盐解离，游离的氨基与镍离子形成强烈的交联反应，从而形成了凝胶。此时，样品的储能模量（G’）大于损耗模量（G）。Figure 3 is the relationship between the rheology of chitosan-nickel ion solution and temperature. At room temperature, protonated chitosan has weak interaction with nickel ions and cannot form cross-links, so it is in solution state. At this time, the loss modulus (G") of the sample is greater than the storage modulus (G'). When the temperature rises to a certain critical point (about 68 °C), the ammonium salt on the chitosan molecule dissociates, and the free The amino groups of the samples form a strong cross-linking reaction with nickel ions, thereby forming a gel. At this time, the storage modulus (G') of the sample is greater than the loss modulus (G).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL444765A1 (en) * | 2023-05-07 | 2024-11-12 | Instytut Biochemii I Biofizyki Polskiej Akademii Nauk | Chitosan-copper hydrogel, methods of making it, compositions containing it, methods of using it, surface, fabric, nonwoven fabric coated therewith, and uses of chitosan-copper hydrogel |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070141142A1 (en) * | 2004-03-22 | 2007-06-21 | Universite De Geneve | Pseudo-thermosetting neutralized chitosan composition forming a hydrogel and a process for producing the same |
| WO2011069441A1 (en) * | 2009-12-07 | 2011-06-16 | 广州美能材料科技有限公司 | Method for preparing composite multilayer porous hollow fiber membrane and device and product thereof |
| CN102585303A (en) * | 2012-03-27 | 2012-07-18 | 天津大学 | Chitosan/polylysine in-situ gel and preparation method thereof |
| CN106146913A (en) * | 2015-04-21 | 2016-11-23 | 南方科技大学 | Chitosan-based hydrogel and preparation method and application thereof |
| CN108341977A (en) * | 2018-03-13 | 2018-07-31 | 武汉理工大学 | A kind of citric acid cross-linked chitosan hydrogel and preparation method thereof |
| CN109180970A (en) * | 2018-08-30 | 2019-01-11 | 武汉理工大学 | A kind of citric acid cross-linked chitosan and the hydrogel of dopamine and preparation method thereof |
| CN110698698A (en) * | 2019-09-29 | 2020-01-17 | 同济大学 | A kind of preparation method of chitosan hydrogel |
| CN111171346A (en) * | 2020-01-23 | 2020-05-19 | 同济大学 | Chitosan hydrogel material and preparation method and application thereof |
| CN112573528A (en) * | 2021-01-13 | 2021-03-30 | 安阳师范学院 | Preparation method of aerogel with high transparency and high mechanical strength |
-
2022
- 2022-06-16 CN CN202210679092.5A patent/CN114805859B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070141142A1 (en) * | 2004-03-22 | 2007-06-21 | Universite De Geneve | Pseudo-thermosetting neutralized chitosan composition forming a hydrogel and a process for producing the same |
| WO2011069441A1 (en) * | 2009-12-07 | 2011-06-16 | 广州美能材料科技有限公司 | Method for preparing composite multilayer porous hollow fiber membrane and device and product thereof |
| CN102585303A (en) * | 2012-03-27 | 2012-07-18 | 天津大学 | Chitosan/polylysine in-situ gel and preparation method thereof |
| CN106146913A (en) * | 2015-04-21 | 2016-11-23 | 南方科技大学 | Chitosan-based hydrogel and preparation method and application thereof |
| CN108341977A (en) * | 2018-03-13 | 2018-07-31 | 武汉理工大学 | A kind of citric acid cross-linked chitosan hydrogel and preparation method thereof |
| CN109180970A (en) * | 2018-08-30 | 2019-01-11 | 武汉理工大学 | A kind of citric acid cross-linked chitosan and the hydrogel of dopamine and preparation method thereof |
| CN110698698A (en) * | 2019-09-29 | 2020-01-17 | 同济大学 | A kind of preparation method of chitosan hydrogel |
| CN111171346A (en) * | 2020-01-23 | 2020-05-19 | 同济大学 | Chitosan hydrogel material and preparation method and application thereof |
| CN112573528A (en) * | 2021-01-13 | 2021-03-30 | 安阳师范学院 | Preparation method of aerogel with high transparency and high mechanical strength |
Non-Patent Citations (1)
| Title |
|---|
| 韦少慧;刘波;吕维忠;张小虎;龙俊杰;吴奕光;: "体温致壳聚糖智能水凝胶", 稀有金属材料与工程, no. 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL444765A1 (en) * | 2023-05-07 | 2024-11-12 | Instytut Biochemii I Biofizyki Polskiej Akademii Nauk | Chitosan-copper hydrogel, methods of making it, compositions containing it, methods of using it, surface, fabric, nonwoven fabric coated therewith, and uses of chitosan-copper hydrogel |
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