CN110483810B - Preparation method of nano-cellulose antibacterial hydrogel - Google Patents

Preparation method of nano-cellulose antibacterial hydrogel Download PDF

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CN110483810B
CN110483810B CN201910680387.2A CN201910680387A CN110483810B CN 110483810 B CN110483810 B CN 110483810B CN 201910680387 A CN201910680387 A CN 201910680387A CN 110483810 B CN110483810 B CN 110483810B
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cellulose
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hydrogel
guanidine hydrochloride
polyhexamethylene guanidine
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CN110483810A (en
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吴敏
刘仁
鲁鹏
郑璐
王志伟
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Guangxi University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/04—Oxycellulose; Hydrocellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C08J2401/04—Oxycellulose; Hydrocellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00

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Abstract

The invention discloses a preparation method of nano-cellulose antibacterial hydrogel. The method comprises the following steps: (1) preparing TEMPO oxidized nano cellulose colloid; (2) preparing an aqueous solution of polyhexamethylene guanidine hydrochloride; (3) placing TEMPO oxidized nano-cellulose colloid into a polytetrafluoroethylene mold, then dripping aqueous solution of polyhexamethylene guanidine hydrochloride, standing for 24-48 h, and performing electrostatic adsorption coupling effect on the both to form the nano-cellulose antibacterial hydrogel. The method has simple process and environment-friendly raw materials, and the prepared nano-cellulose hydrogel has higher strength and good antibacterial performance and is widely applied to a plurality of fields of drug loading, controllable release, chemical sensors and the like.

Description

Preparation method of nano-cellulose antibacterial hydrogel
Technical Field
The invention belongs to the technical field of hydrogel materials and antibacterial material preparation, and particularly relates to a preparation method of nano-cellulose antibacterial hydrogel.
Background
The hydrogel is a three-dimensional network structure system which can be swelled by water and is insoluble in water, wherein the three-dimensional network structure system is formed by physically or chemically crosslinking a high molecular polymer under certain conditions, and liquid water is dispersed and filled in the structural gaps. The hydrogel formed by natural polymers such as cellulose, chitosan, sodium alginate, starch and the like is gradually applied to the fields of agriculture, food, tissue engineering and the like due to good biocompatibility and degradability. Wherein, the cellulose is hydrophilic macromolecular polysaccharide composed of D-glucosyl, and is rich in natural content and natural and renewable. The nano-cellulose prepared from the cellulose has the characteristics of high mechanical strength, high crystallinity, high transparency, large specific surface area, strong hydrophilicity and the like, and has wide application prospect in the field of new material preparation.
At present, many methods for preparing cellulose hydrogel are reported, and mainly include a solvent dissolution displacement method, a chemical modification crosslinking method and the like. For example, patent CN101445609B and patent CN103055347B respectively dissolve cellulose in NaOH/Urea aqueous solution system at low temperature, and then prepare hydrogel by chemical crosslinking and solvent replacement. In patent CN106928472B, cellulose is dissolved in a LiCl/DMAc solvent system in a heating and cooling circulation mode to obtain a cellulose solution system, and transparent cellulose gel is prepared by a standing gel method. In contrast, relatively few reports of obtaining hydrogel by using nanofibers as a base material currently mainly use a synthetic water-soluble polymer composite method, for example, the preparation method of nano-cellulose gel reported in patents CN108160053A and CN109457472A mixes nanocellulose with a cross-linking agent, an initiator, a binder and an accelerator, and carries out hydrothermal reaction to obtain the nano-cellulose hydrogel. The preparation process of the nano-cellulose hydrogel is complex, and the nano-cellulose hydrogel is poor in environmental friendliness because the synthesized hydrophilic polymer is often used as a gel main body. In addition, the antibacterial function of the nanocellulose hydrogel is endowed by adopting the existing preparation method, and often, an antibacterial agent needs to be additionally mixed or loaded, so that the operation process is complex. Therefore, the development of the preparation method of the nano-cellulose antibacterial hydrogel with simple process and environmental friendliness has important practical significance.
The environment-friendly high molecular polymer polyhexamethylene guanidine hydrochloride has the advantages of long-term bacteriostasis, broad-spectrum sterilization, low effective concentration, no color, no odor, no toxicity and the like, is a good antibacterial agent, is easy to dissolve in water, has positive charges on the surface and has an antibacterial function. However, no report of preparing the nano-cellulose antibacterial hydrogel by using the polyhexamethylene guanidine hydrochloride with the antibacterial function as a cross-linking agent is found at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of nano-cellulose antibacterial hydrogel, which directly obtains the nano-cellulose antibacterial hydrogel by utilizing the electrostatic adsorption coupling effect between the polyhexamethylene guanidine hydrochloride with the antibacterial function and TEMPO oxidized nano-cellulose colloid, and the obtained hydrogel has good antibacterial function, does not need to add a catalyst, an initiator and an antibacterial agent, and has simple preparation process.
The invention solves the technical problems by the following technical scheme:
the preparation method of the nano-cellulose antibacterial hydrogel comprises the following operation steps:
(1) preparing TEMPO oxidized nano-cellulose colloid: pretreating the nano-cellulose by a TEMPO oxidation method to obtain TEMPO oxidized nano-cellulose with the surface carboxyl content of 600-1200 mmol/Kg, then concentrating by a solvent evaporation method until the mass concentration is 3%, and degassing in vacuum to obtain TEMPO oxidized nano-cellulose colloid;
(2) preparation of aqueous polyhexamethyleneguanidine hydrochloride solution: dissolving polyhexamethylene guanidine hydrochloride powder in distilled water according to the weight ratio of 2:98 to obtain a polyhexamethylene guanidine hydrochloride aqueous solution with the mass concentration of 2%;
(3) and (3) a gelation process: placing the TEMPO oxidized nano-cellulose colloid prepared in the step (1) into a polytetrafluoroethylene mold, dropwise adding the aqueous solution of the polyhexamethylene guanidine hydrochloride prepared in the step (2) to the surface layer of the TEMPO oxidized nano-cellulose colloid along the mold wall at the speed of 1mL/min by using a peristaltic injection pump, wherein the using amount of the TEMPO oxidized nano-cellulose colloid and the aqueous solution of the polyhexamethylene guanidine hydrochloride is 40-80: 20-60 in parts by weight, standing at 4 ℃ for 24-48 hours to form hydrogel, and soaking and washing the hydrogel for 2 times with deionized water, wherein each time lasts for 1 minute, so as to obtain the nano-cellulose antibacterial hydrogel.
The nano-cellulose in the step (1) is prepared from bleached softwood fiber, bleached hardwood fiber or bleached bagasse fiber by a mechanical grinding method.
The molecular weight range of the polyhexamethylene guanidine hydrochloride in the step (2) is 500-600.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the nano-cellulose hydrogel is directly prepared by utilizing the electrostatic adsorption coupling effect between the polyhexamethylene guanidine hydrochloride and the TEMPO oxidized nano-cellulose colloid, and the obtained hydrogel has a good antibacterial function, does not need to be added with a catalyst, an initiator and an antibacterial agent, and is simple in preparation process.
(2) The invention utilizes renewable biomass resource cellulose and polyhexamethylene guanidine hydrochloride with low cost, spectrum antibiosis and no side effect to prepare the new biomass-based antibacterial hydrogel material, can effectively solve the resource and environmental problems in the hydrogel preparation field, and has good development prospect.
(3) The preparation method has simple process and easily obtained raw materials, and directly obtains the nano-cellulose antibacterial hydrogel by utilizing the electrostatic adsorption coupling effect between the poly (hexamethylene guanidine) hydrochloride with the antibacterial function and the TEMPO oxidized nano-cellulose colloid, wherein the poly (hexamethylene guanidine) hydrochloride has double functions of an antibacterial agent and a cross-linking agent in the preparation process of the hydrogel, and the obtained product has better mechanical strength and excellent antibacterial performance and has wide application prospects in the aspects of medicine loading, controllable release, chemical sensors, tissue engineering and the like.
Detailed Description
The present invention is further described below with reference to specific examples, but the present invention is not limited to the following examples, in which the chemical reagents and raw materials used are all analytical grade.
Example 1
A preparation method of nano-cellulose antibacterial hydrogel comprises the following steps:
(1) preparing TEMPO oxidized nano-cellulose colloid: pretreating the nano-cellulose obtained by mechanically grinding bleached softwood fibers by a TEMPO oxidation method to obtain TEMPO oxidized nano-cellulose with the surface carboxyl content of 600mmol/Kg, then concentrating by a solvent evaporation method until the mass concentration is 3%, and performing vacuum degassing to obtain TEMPO oxidized nano-cellulose colloid;
(2) preparation of aqueous polyhexamethyleneguanidine hydrochloride solution: dissolving polyhexamethylene guanidine hydrochloride powder (molecular weight is 500) in distilled water, wherein the using amount of the polyhexamethylene guanidine hydrochloride and the distilled water is 2:98 parts by weight, and obtaining a polyhexamethylene guanidine hydrochloride aqueous solution with the mass concentration of 2% after dissolving;
(3) and (3) a gelation process: placing the TEMPO oxidized nano-cellulose colloid prepared in the step (1) into a polytetrafluoroethylene mold, dropwise adding the aqueous solution of the polyhexamethylene guanidine hydrochloride prepared in the step (2) to the surface layer of the TEMPO oxidized nano-cellulose colloid along the mold wall at the speed of 1mL/min by using a peristaltic injection pump, wherein the using amount of the TEMPO oxidized nano-cellulose colloid and the aqueous solution of the polyhexamethylene guanidine hydrochloride is 40:60 in parts by weight, standing at 4 ℃ for 24 hours to form hydrogel, and soaking and washing the hydrogel for 2 times with equal volume of deionized water, wherein each time lasts for 1 minute, so that the nano-cellulose antibacterial hydrogel is obtained.
The nano-cellulose antibacterial hydrogel prepared by the embodiment has good mechanical strength and antibacterial performance, and the bacteriostatic rate of the nano-cellulose antibacterial hydrogel on escherichia coli and listeria is more than 99.99% through laboratory determination.
Example 2
A preparation method of nano-cellulose antibacterial hydrogel comprises the following steps:
(1) preparing TEMPO oxidized nano-cellulose colloid: pretreating the nano-cellulose obtained by mechanically grinding bleached hardwood fibers by using a TEMPO oxidation method to obtain TEMPO oxidized nano-cellulose with the surface carboxyl content of 900mmol/Kg, then concentrating by using a solvent evaporation method until the mass concentration is 3%, and performing vacuum degassing to obtain TEMPO oxidized nano-cellulose colloid;
(2) preparation of aqueous polyhexamethyleneguanidine hydrochloride solution: dissolving polyhexamethylene guanidine hydrochloride powder (molecular weight is 550) in distilled water, wherein the using amount of the polyhexamethylene guanidine hydrochloride and the distilled water is 2:98 parts by weight, and after the polyhexamethylene guanidine hydrochloride powder and the distilled water are dissolved, obtaining a polyhexamethylene guanidine hydrochloride aqueous solution with the mass concentration of 2%;
(3) and (3) a gelation process: placing the TEMPO oxidized nano-cellulose colloid prepared in the step (1) into a polytetrafluoroethylene mold, dropwise adding the aqueous solution of the polyhexamethylene guanidine hydrochloride prepared in the step (2) to the surface layer of the TEMPO oxidized nano-cellulose colloid along the mold wall at the speed of 1mL/min by using a peristaltic injection pump, wherein the using amount of the TEMPO oxidized nano-cellulose colloid and the aqueous solution of the polyhexamethylene guanidine hydrochloride is 60:40 in parts by weight, standing at 4 ℃ for 36 hours to form hydrogel, and soaking and washing the hydrogel for 2 times with equal volume of deionized water, wherein each time lasts for 1 minute, so that the nano-cellulose antibacterial hydrogel is obtained.
The nano-cellulose antibacterial hydrogel prepared by the embodiment has good mechanical strength and antibacterial performance, and the bacteriostatic rate of the nano-cellulose antibacterial hydrogel on escherichia coli and listeria is more than 99.99% through laboratory determination.
Example 3
A preparation method of nano-cellulose antibacterial hydrogel comprises the following steps:
(1) preparing TEMPO oxidized nano-cellulose colloid: pretreating the nano-cellulose obtained by mechanically grinding bleached bagasse fibers by using a TEMPO oxidation method to obtain TEMPO oxidized nano-cellulose with the surface carboxyl content of 1200mmol/Kg, then concentrating by using a solvent evaporation method until the mass concentration is 3%, and performing vacuum degassing to obtain TEMPO oxidized nano-cellulose colloid;
(2) preparation of aqueous polyhexamethyleneguanidine hydrochloride solution: dissolving polyhexamethylene guanidine hydrochloride powder (molecular weight is 600) in distilled water, wherein the using amount of the polyhexamethylene guanidine hydrochloride and the distilled water is 2:98 in parts by weight, and obtaining a polyhexamethylene guanidine hydrochloride aqueous solution with the mass concentration of 2% after dissolution;
(3) and (3) a gelation process: placing the TEMPO oxidized nano-cellulose colloid prepared in the step (1) into a polytetrafluoroethylene mold, dropwise adding the aqueous solution of the polyhexamethylene guanidine hydrochloride prepared in the step (2) to the surface layer of the TEMPO oxidized nano-cellulose colloid along the mold wall at the speed of 1mL/min by using a peristaltic injection pump, wherein the using amount of the TEMPO oxidized nano-cellulose colloid and the aqueous solution of the polyhexamethylene guanidine hydrochloride is 80:20 in parts by weight, standing at 4 ℃ for 48 hours to form hydrogel, and soaking and washing the hydrogel for 2 times with equal volume of deionized water, wherein each time lasts for 1 minute, so that the nano-cellulose antibacterial hydrogel is obtained.
The nano-cellulose antibacterial hydrogel prepared by the embodiment has good mechanical strength and antibacterial performance, and the bacteriostatic rate of the nano-cellulose antibacterial hydrogel on escherichia coli and listeria is more than 99.99% through laboratory determination.

Claims (2)

1. A preparation method of nano-cellulose antibacterial hydrogel is characterized by comprising the following operation steps:
(1) preparing TEMPO oxidized nano-cellulose colloid: pretreating the nano-cellulose by a TEMPO oxidation method to obtain TEMPO oxidized nano-cellulose with the surface carboxyl content of 600-1200 mmol/Kg, then concentrating by a solvent evaporation method until the mass concentration is 3%, and degassing in vacuum to obtain TEMPO oxidized nano-cellulose colloid; the nano-cellulose is prepared from bleached softwood fiber, bleached hardwood fiber or bleached bagasse fiber by a mechanical grinding method;
(2) preparation of aqueous polyhexamethyleneguanidine hydrochloride solution: dissolving polyhexamethylene guanidine hydrochloride powder in distilled water according to the weight ratio of 2:98 to obtain a polyhexamethylene guanidine hydrochloride aqueous solution with the mass concentration of 2%;
(3) and (3) a gelation process: placing the TEMPO oxidized nano-cellulose colloid prepared in the step (1) into a polytetrafluoroethylene mold, dropwise adding the aqueous solution of the polyhexamethylene guanidine hydrochloride prepared in the step (2) to the surface layer of the TEMPO oxidized nano-cellulose colloid along the mold wall at the speed of 1mL/min by using a peristaltic injection pump, wherein the using amount of the TEMPO oxidized nano-cellulose colloid and the aqueous solution of the polyhexamethylene guanidine hydrochloride is 40-80: 20-60 in parts by weight, standing at 4 ℃ for 24-48 hours to form hydrogel, and soaking and washing the hydrogel for 2 times with deionized water, wherein each time lasts for 1 minute, so as to obtain the nano-cellulose antibacterial hydrogel.
2. The method for preparing the nano-cellulose antibacterial hydrogel according to claim 1, wherein the molecular weight of the polyhexamethylene guanidine hydrochloride in the step (2) is 500-600.
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CN111647196B (en) * 2020-04-24 2022-03-11 南京林业大学 Preparation method of wood-based carbon nanotube composite conductive film
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