US-12624195-B2 - Hydroxybutyl chitin, hydroxybutyl chitin hydrogel and preparation methods thereof

Abstract

Disclosed in the present disclosure are a hydroxybutyl chitin, a hydroxybutyl chitin hydrogel and a preparation method thereof. Chitin is subjected to pulverization, dissolution, modification with epoxybutane, and purification to obtain a final product, namely the hydroxybutyl chitin. The hydroxybutyl chitin prepared by the method has good solubility in purified water, and a hydrogel with a low solid content can be formed. The hydroxybutyl chitin hydrogel will have a wide application aspect in biomedicine, absorbable materials, and other fields.

Inventors

• Jue Wang
• Jie Zheng
• Xingyu Liu
• Meiqin Zhu
• Qianqian Jia

Assignees

• Hangzhou Singclean Medical Products Co., Ltd

Dates

Publication Date

20260512

Application Date

20221229

Priority Date

20220531

Claims (5)

1. 1 . A method for preparing a hydroxybutyl chitin, comprising the following steps: (1) dispersing chitin in an alkaline aqueous solution at a temperature within a range of −20° C to −2° C to obtain a chitin alkaline aqueous solution; (2) adding epoxybutane to the chitin alkaline aqueous solution, and stirring for a reaction, wherein before being added to the chitin alkaline aqueous solution, the epoxybutane is diluted with a mixed reagent comprising i) one or more alcohol reagents selected from the group consisting of methanol, ethanol, isopropanol and n-butanol; ii) purified water; iii) one or more selected from the group consisting of sodium dodecyl sulfate, sodium iodide and potassium iodide; and iv) one or more selected from the group consisting of lithium chloride, sodium chloride, potassium chloride and cesium chloride; and (3) after the reaction is completed, conducting dialysis and freeze-drying to obtain the hydroxybutyl chitin.
2. 2 . The method for preparing a hydroxybutyl chitin according to claim 1 , wherein in step (2), the epoxybutane is added to the chitin alkaline aqueous solution, and stirred for a reaction at 0° C.-45° C. for 1-7 days.
3. 3 . The method for preparing a hydroxybutyl chitin according to claim 1 , wherein the one or more alcohol reagents account for 20%-80% of a volume fraction of the mixed reagent; the purified water accounts for 20%-80% of the volume fraction of the mixed reagent; the one or more of the sodium dodecyl sulfate, the sodium iodide and the potassium iodide have a total concentration of 0.01-0.1 g/mL in the mixed reagent; and the one or more of the lithium chloride, the sodium chloride, the potassium chloride and the cesium chloride have a total concentration of 0.01-0.1 g/mL in the mixed reagent.
4. 4 . The method for preparing a hydroxybutyl chitin according to claim 1 , wherein in step (3), after the reaction is completed, the chitin alkaline aqueous solution is diluted 1-20 times with purified water, followed by dialysis and freeze-drying.
5. 5 . A method for preparing a hydroxybutyl chitin hydrogel, comprising the following preparation steps: adding the hydroxybutyl chitin prepared by the preparation method according to claim 1 to purified water, and conducting stirring at 0° C.-30° C. for complete dissolution to form the hydroxybutyl chitin hydrogel.

Description

CROSS-REFERENCE TO RELATED APPLICATION The present application claims priority from Chinese Patent Application No. 202210610383.9 filed on May 31, 2022, the contents of which are incorporated herein by reference in their entirety. TECHNICAL FIELD The present disclosure belongs to the technical field of materials, and relates to a hydroxybutyl chitin hydrogel and a preparation method thereof. BACKGROUND Chitin is a natural linear polysaccharide polymer with 2-acetylamino-(1,4)-β-glucose as a repeating unit. The chitin is widely found in nature, and mainly derived from shells of fishes, shrimps, crabs and other animals and cell walls of fungi. The chitin is a nitrogen-containing organic substance with the largest number in nature, and also one of polymers with the highest content in nature. The chitin has many excellent properties, such as excellent biocompatibility, low immunogenicity, and good hemostatic property. Thus, the chitin has a broad application prospect in biomedicine, absorbable materials, and other fields. A chitin derivative hydrogel is an excellent absorbable material. Due to the interaction of intramolecular or intermolecular sugars of the chitin, a hydrogen bond and a linear molecular structure likely to induce dense molecular stacking, the chitin has poor solubility. Most of structural materials like carapaces are found in nature. When the chitin is modified with some reagents, the dense molecular packing capacity of a chitin derivative is reduced, and the water solubility is improved. The balance of the hydrophilicity and hydrophobicity of a chitin derivative molecule can be adjusted by changing the type and amount of the reagents to obtain a chitin derivative hydrogel. Two common chitin modification reagents include a halogenated hydrocarbon reagent and an epoxy reagent. The halogenated hydrocarbon reagent includes chloroacetic acid, chloroethanol and the like. Carboxymethyl chitin and hydroxyethyl chitin are obtained after a substitution reaction of hydroxyl of the chitin. The common epoxy reagent includes propylene oxide and the like, and an obtained derivative is hydroxypropyl chitin. Hydrogel can be formed by the above chitin derivatives through physical crosslinking, and the hydrogel has become one of research hotspots at present. SUMMARY Objectives of the present disclosure are to find a novel chitin derivative and explore a novel chitin hydrogel. A prepared hydroxybutyl chitin has good dispersibility in an aqueous phase, can be prepared into a physical hydrogel, and has a wide application prospect in tissue engineering, cell culture, Class III medical apparatuses and instruments, and other aspects. Therefore, based on research conducted by the inventor and experimental results, the following technical schemes are proposed. According to a first aspect of the present disclosure, the following technical solutions are used in the present disclosure. A method for preparing a hydroxybutyl chitin, including the following steps: (1) subjecting chitin to standing and dispersion in an alkaline aqueous solution at low temperature;(2) adding epoxybutane or diluted epoxybutane to a chitin aqueous phase system, and conducting stirring for a reaction; and(3) after the reaction is completed, conducting dialysis and freeze-drying to obtain the hydroxybutyl chitin. On the basis of the above technical scheme, the following further technical schemes may also be adopted or combined in the present disclosure to form different kinds of further optimized technical schemes. In step (1), a chitin powder is added to the alkaline aqueous solution for treatment at −20° C. to room temperature for 1-30 days. In step (2), before being added to the chitin alkaline aqueous solution, the epoxybutane is diluted with a mixed reagent to adjust a gelatination effect of the hydroxybutyl chitin. The mixed reagent includes one or more of methanol, ethanol, isopropanol and n-butanol (all alcohol reagents preferably account for 20%-80% of a volume fraction of the mixed reagent), purified water (preferably accounting for 20%-80% of the volume fraction of the mixed reagent), one or more of sodium dodecyl sulfate, sodium iodide and potassium iodide (preferably having a total concentration of 0-0.1 g/mL in the mixed reagent), and one or more of lithium chloride, sodium chloride, potassium chloride and cesium chloride (preferably having a total concentration of 0-0.1 g/mL in the mixed reagent). A method for preparing the mixed agent includes: adding the alcohol reagent, the purified water, and the salt reagent to the epoxybutane in sequence, and conducting stirring uniformly for use. In step (2), the epoxybutane or the diluted epoxybutane is added to the chitin alkaline aqueous solution, and stirred for a reaction at 0° C.-45° C. for 1-7 days. In step (3), after the reaction is completed, the system is diluted 1-20 times with purified water, followed by dialysis and freeze-drying. According to a second aspect of the present discl