CN110256735B - Preparation method of amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel - Google Patents
Preparation method of amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method of amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan composite aerogel, which comprises the following steps: (1) preparing dialdehyde chitosan; (2) preparing an amidoxime-hydroxylamine oxime cellulose dispersion liquid; (3) in-situ preparation of nano silver on the surface of amidoxime-hydroxylamine oxime cellulose and formation of composite sol of nano silver and dialdehyde chitosan; (4) injection molding, freeze drying and aerogel forming of the composite sol. The nano-silver reduction process in the method is green and environment-friendly, and the aerogel preparation process is simple. The obtained composite aerogel has excellent mechanical property, regular tissue structure and good biocompatibility, and can be used for industrial wastewater treatment such as adsorption filtration and synergetic adsorption degradation, and the like, and the biomedical fields such as medical dressings, tissue engineering and the like.
Description
Technical Field
The invention relates to a preparation method of amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel, belonging to the field of natural polymer composite materials.
Background
Aerogels, also known as xerogels. Most of the solvent is removed from the wet gel, so that the liquid content in the gel is far less than the solid content, or the space network structure of the gel is filled with gas, and the structure preserves the complete solid bulk material. The porous material is generally characterized in that the porous material is a network porous structure formed by interconnected or closed pores, has low density, extremely high porosity, ultrahigh specific surface area and material transmission performance, and is widely applied to a plurality of fields. Since Tan et al (Advanced Materials,2001,13, 644-plus 646) succeeded in preparing cellulose aerogel from cellulose derivatives in 2001, natural polymer aerogel rapidly developed into the third generation aerogel Materials, surpassing inorganic aerogel and artificially synthesized organic polymer aerogel. The aerogel has the characteristics of the traditional aerogel and integrates the excellent performances of the aerogel, such as low cost, good biocompatibility, biodegradability and environmental friendliness, and becomes a hotspot for researching natural polymer materials.
The chitosan is a natural alkaline polysaccharide with rich sources, has rich hydroxyl and amino active groups on the surface, has the characteristics of good hygroscopicity, film forming property, permeability, good biocompatibility, biodegradation and the like, and is an environment-friendly material without toxicity, harm and secondary pollution. Therefore, the method is often used for adsorbing and removing organic pollutants such as heavy metal ions, dyes and the like in industrial wastewater. However, with the rapid development of society, the requirements for material properties are continuously increasing, and the defects of the natural polymer aerogel represented by chitosan are gradually highlighted, such as insufficient mechanical properties, single functional effect and the like, which limits the application of the natural polymer aerogel in the fields of high requirements and multifunctional requirements.
Microcrystalline cellulose or nanocellulose, which is a free-flowing short rod-shaped crystalline material hydrolyzed by natural cellulose through mechanical pressure, chemical force or enzyme to the ultimate degree of polymerization, has no fibrous property, and only contains hydroxyl groups on the surface; but has strong fluidity, large specific surface area, high Young modulus and high mechanical strength, and is widely applied to the field of reinforcement and toughening of composite materials. In addition, the nano silver has a plurality of remarkable advantages as one of inorganic antibacterial agents, such as extremely strong antibacterial activity, broad-spectrum bactericidal performance, no drug resistance and the like, and the composite material prepared by using the nano silver as a component has good antibacterial performance.
Although some research reports on chitosan/cellulose/nano-material composites or similar research reports (CN108440794A, CN 106832437a) exist at present, the preparation method mostly adopts a sol blending method, a nano-particle doping method, or a combination method of the two methods, the preparation process is tedious, the nano-particle load fastness is insufficient, the dispersion is not uniform, or the process involves toxic and harmful substances, etc., and the material form is also formed into a film by a tape casting method.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a convenient, efficient and high-purity preparation method of amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel. Firstly, taking amidoxime-hydroxylamine oxime cellulose self-made in the earlier stage as a carrier, silver nitrate as a precursor and dialdehyde chitosan as a reducing agent, and carrying out in-situ reduction to prepare nano silver so as to obtain the amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan ternary composite sol. And then defoaming, injection molding, gelling, freezing and drying the composite sol to obtain the amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel. The aerogel can integrate functions of all components, and endows the aerogel with excellent mechanical strength, antibacterial property, adsorbability, biocompatibility and biodegradability.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
an amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel comprises the following components in parts by weight: 2-5 parts of amidoxime-hydroxylamine oxime cellulose, 0.05-2 parts of nano silver and 3-8 parts of chitosan.
The invention also provides a preparation method of the amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel, which comprises the following steps:
step 1, adding chitosan into an acetic acid solution with the concentration of 2 wt% according to a bath ratio of 1: 100-1: 10, stirring until the chitosan solution is completely dissolved to obtain a chitosan solution, introducing nitrogen, adding a sodium periodate solution into the chitosan solution, wherein the sodium periodate is 13-66% of the chitosan by mass, oxidizing the chitosan solution at 30-60 ℃ in the dark for 1-10 hours, adding an alcohol solution to terminate the reaction, performing vacuum drying to obtain dialdehyde chitosan, and dissolving the dialdehyde chitosan in deionized water to prepare a dialdehyde chitosan solution with the concentration of 0.5-5 wt%;
step 2, putting amidoxime-hydroxylamine oxime cellulose into deionized water, and performing ultrasonic dispersion uniformly to obtain 1.5-10 wt% amidoxime-hydroxylamine oxime cellulose dispersion liquid;
step 3, adding 0.001-0.1 mol/L silver nitrate solution into the amidoxime-hydroxylamine oxime cellulose dispersion liquid prepared in the step 2 according to the volume ratio of 1: 10-100: 1, and uniformly stirring at room temperature; then adding the dialdehyde chitosan solution obtained in the step 1 into a reaction system according to the volume ratio of 2: 1-1: 10, and reacting for 0.5-6 h at 50-90 ℃ to obtain amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan ternary composite sol;
and 4, ultrasonically defoaming the ternary composite sol, injecting the ternary composite sol into a mold, freezing the mold at-50 ℃ for 4-10 hours, and drying to obtain the amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel.
Further, the deacetylation degree of the chitosan in the step 1 is 85-95%.
Further, the alcohol solution in step 1 is one of ethanol, ethylene glycol or glycerol solution.
Further, the preparation steps of the amidoxime-hydroxylamine oxime cellulose in the step 2 are as follows:
s1, placing the cellulose into a 0.5-5 wt% NaOH solution according to a bath ratio of 1: 100-1: 10, and boiling for 30-150 min; then, placing the mixture in 10-30 wt% NaOH solution according to the bath ratio of 1: 100-1: 10, and stirring for 30-180 min at room temperature; filtering, washing and drying to obtain the alkalized cellulose;
s2, placing the alkalized cellulose into acetone according to a bath ratio of 1: 20-1: 50, and condensing and refluxing for 10-45 min at 50-60 ℃ under the protection of nitrogen; then adding 2-cyano-3-ethoxy ethyl acrylate, wherein the weight of the 2-cyano-3-ethoxy ethyl acrylate is 0.2-2 times that of the alkalized cellulose, magnetically stirring for 10-45 min, then adding ammonium ceric nitrate, and continuing to react for 1-8 h, wherein the ammonium ceric nitrate is 0.2-3% of the alkalized cellulose by mass; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer cellulose;
s3, adding the graft copolymerization cellulose into 1mol/L hydroxylamine solution according to a bath ratio of 1: 15-1: 50, reacting for 1-6 h at the temperature of 65-75 ℃ under the condition of magnetic stirring, washing the product with methanol, and drying to obtain the amidoxime-hydroxylamine oxime cellulose.
Further, the cellulose is one or a mixture of two of rod-shaped microcrystalline cellulose and nano cellulose.
Further, the cellulose is derived from one of natural cellulose and products thereof, regenerated cellulose and products thereof, cellulose-rich agricultural and sideline products or microcrystalline cellulose.
The method selects amidoxime-hydroxylamine oxime cellulose, chitosan and nano-silver to prepare the aerogel in a composite way, and the basis is as follows: amidoxime-hydroxylamine oxime cellulose is used as a carrier to load the nano-silver material in situ, and abundant functional groups on the surface provide basis for the firm loading and uniform dispersion of the nano-silver; the dialdehyde chitosan is used as a reducing agent and an aerogel component, the reduction process is green and environment-friendly, the preparation process is simple, and the obtained aerogel has high purity. In addition, the three components have the advantages that: the amidoxime-hydroxylamine oxime cellulose is used as an aerogel framework structure, so that not only is the mechanical strength of the aerogel ensured, but also an active group is provided for the adsorption performance of the aerogel; the nano silver load endows the aerogel with an antibacterial function; on the basis of realizing in-situ reduction of nano-silver, functional groups such as surface aldehyde groups, hydroxyl groups, amino groups and the like are combined with amidoxime-hydroxylamine oxime cellulose through hydrogen bonds, electrostatic attraction and the like. The materials of all components are synergistic, and the obtained aerogel has outstanding mechanical properties, excellent adsorbability, antibacterial activity, biocompatibility and biodegradability.
The invention has the beneficial effects that:
(1) the nano silver is generated on the surface of amidoxime-hydroxylamine oxime cellulose in situ, and has firm load, uniform distribution and uniform size
(2) Dialdehyde chitosan is used as a reducing agent and also used as an aerogel component, the reduction process is green and environment-friendly, the gel flow is simple and efficient, and the purity of the aerogel is high.
(3) The obtained aerogel has high mechanical strength, regular tissue structure, large pores and high component activity, and can be used in the fields of adsorption filtration, catalytic degradation, tissue engineering, medical dressing and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a pure dialdehyde chitosan aerogel;
FIG. 2 is a scanning electron microscope image of amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan composite aerogel prepared in example 1;
FIG. 3 is a further enlarged scanning electron micrograph taken in accordance with FIG. 2.
Detailed Description
In order to clarify the technical solution and technical object of the present invention, the present invention will be further described with reference to the accompanying drawings and specific examples.
Example 1:
adding 5g of chitosan into 2 wt% acetic acid solution, and stirring until the chitosan is completely dissolved to obtain 1 wt% chitosan solution; introducing nitrogen, adding 20mL of sodium periodate solution with the concentration of 0.3mol/L into the chitosan solution, oxidizing for 5 hours at 45 ℃ in the dark, adding ethylene glycol solution to terminate the reaction, and freeze-drying to obtain the dialdehyde chitosan. Dissolving the mixture in deionized water to prepare a dialdehyde chitosan solution with the concentration of 3.5 wt%.
Amidoxime-hydroxylamine oxime microcrystalline cellulose was prepared according to the following procedure:
s1, placing 5g of microcrystalline cellulose in 200mL of 1.25 wt% NaOH solution, and boiling for 80 min; then placing the mixture into 120mL NaOH solution with the concentration of 20 wt% according to the same bath ratio, and stirring for 45min at room temperature; filtering, washing and drying to obtain the alkalized microcrystalline cellulose;
s2 placing 2g of alkalized microcrystalline cellulose into acetone at a bath ratio of 1:25, and condensing and refluxing at 55 ℃ for 40min under the protection of nitrogen; then 2g of 2-cyano-3-ethoxy ethyl acrylate is added for reaction for 15min, and then 0.008g of cerium ammonium nitrate is added for continuous reaction for 4 h; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer microcrystalline cellulose;
s3, adding the graft copolymerization microcrystalline cellulose into 1mol/L hydroxylamine solution according to the bath ratio of 1:30, reacting for 4 hours at the temperature of 70 ℃ under the condition of magnetic stirring, washing the product with methanol and water in sequence, and drying to obtain the amidoxime-hydroxylamine oxime microcrystalline cellulose.
50mL of a 2 wt% amidoxime-hydroxylamine oxime microcrystalline cellulose homogeneous aqueous dispersion was prepared. Adding 10mL of silver nitrate solution with the concentration of 0.08mol/L into the amidoxime-hydroxylamine oxime microcrystalline cellulose dispersion liquid, and uniformly stirring at room temperature; and then adding 40mL of dialdehyde chitosan solution to react for 4h at 80 ℃ to obtain amidoxime-hydroxylamine oxime microcrystalline cellulose/nano-silver/chitosan ternary composite sol.
And (3) ultrasonically defoaming the ternary composite sol, injecting the ternary composite sol into a mold, freezing the mold at the temperature of-50 ℃ for 6 hours, and drying to obtain the amidoxime-hydroxylamine oxime microcrystalline cellulose/nano silver/chitosan composite aerogel.
Example 2:
adding 2g of chitosan into 2 wt% acetic acid solution, and stirring until the chitosan is completely dissolved to obtain 2 wt% chitosan solution; introducing nitrogen, adding 30mL of sodium periodate solution with the concentration of 0.1mol/L into the chitosan solution, oxidizing for 4 hours at 35 ℃ in the dark, adding ethanol solution to terminate the reaction, and drying in vacuum to obtain the dialdehyde chitosan. Dissolving the mixture in deionized water to prepare a dialdehyde chitosan solution with the concentration of 2 wt%.
The amidoxime-hydroxylamine oxime nanocellulose was prepared according to the following procedure:
s1, putting 4g of nano-cellulose into 120mL of NaOH solution with the concentration of 3 wt%, and boiling for 60 min; then, placing the mixture into 200mL of NaOH solution with the concentration of 15 wt% according to the same bath ratio, and stirring the mixture for 60min at room temperature; filtering, washing and drying to obtain the alkalized nano-cellulose;
s2 placing 2.5g of alkalized nano-cellulose into acetone according to the bath ratio of 1:25, and carrying out condensation reflux for 15min at 50 ℃ under the protection of nitrogen; then adding 1g of 2-cyano-3-ethoxy ethyl acrylate for reaction for 10min, adding 0.01g of ammonium ceric nitrate for continuous reaction for 2 h; filtering the product, washing with methanol and water for several times, and drying to obtain graft copolymerization nanocellulose;
s3, adding the graft copolymerization nanocellulose into 1mol/L hydroxylamine solution according to the bath ratio of 1:45, reacting for 6 hours at the temperature of 75 ℃ under the condition of magnetic stirring, and sequentially washing and drying the product with methanol to obtain the amidoxime-hydroxylamine oxime nanocellulose.
100mL of amidoxime-hydroxylamine oxime nanocellulose uniform water dispersion with the concentration of 6 wt% is prepared. Adding 50mL of silver nitrate solution with the concentration of 0.1mol/L into the amidoxime-hydroxylamine oxime nanocellulose dispersion liquid, and uniformly stirring at room temperature; then adding 30mL of dialdehyde chitosan solution to react for 2h at 50 ℃ to obtain amidoxime-hydroxylamine oxime nanocellulose/nano silver/chitosan ternary composite sol.
And (3) ultrasonically defoaming the ternary composite sol, injecting the ternary composite sol into a mold, freezing the mold at-50 ℃ for 4 hours, and drying to obtain the amidoxime-hydroxylamine oxime nanocellulose/nano-silver/chitosan composite aerogel.
Example 3:
adding 3g of chitosan into 2 wt% acetic acid solution, and stirring until the chitosan is completely dissolved to obtain 3 wt% chitosan solution; introducing nitrogen, adding 10mL of sodium periodate solution with the concentration of 0.7mol/L into the chitosan solution, oxidizing for 8 hours at 60 ℃ in the dark, adding a certain amount of glycerol solution to terminate the reaction, and freeze-drying to obtain dialdehyde chitosan; dissolving the mixture in deionized water to prepare a dialdehyde chitosan solution with the concentration of 2.5 wt%.
Amidoxime-hydroxylamine oxime microcrystalline cellulose was prepared according to the following procedure:
s1 placing 3g microcrystalline cellulose in 100mL NaOH solution with concentration of 2 wt%, boiling for 120 min; then placing the mixture into 150mL of NaOH solution with the concentration of 10 wt% according to the same bath ratio, and stirring the mixture for 120min at room temperature; filtering, washing and drying to obtain the alkalized microcrystalline cellulose;
s2 placing 2g of alkalized microcrystalline cellulose in 75mL of acetone, and carrying out condensation reflux at 50 ℃ for 45min under the protection of nitrogen; then 6g of 2-cyano-3-ethoxy ethyl acrylate is added for reaction for 45min, and 0.03g of ammonium ceric nitrate is added for continuous reaction for 8 h; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer microcrystalline cellulose;
s3, adding the graft copolymerization microcrystalline cellulose into 1mol/L hydroxylamine solution according to the bath ratio of 1:50, reacting for 6h at the temperature of 70 ℃ under the condition of magnetic stirring, washing the product with methanol and water in sequence, and drying to obtain the amidoxime-hydroxylamine oxime microcrystalline cellulose.
75mL of a 3 wt% amidoxime-hydroxylamine oxime microcrystalline cellulose homogeneous aqueous dispersion was prepared. Adding 75mL of silver nitrate solution with the concentration of 0.075mol/L into the amidoxime-hydroxylamine oxime microcrystalline cellulose dispersion liquid, and uniformly stirring at room temperature; and then adding 75mL of dialdehyde chitosan solution to react for 6h at 85 ℃ to obtain amidoxime-hydroxylamine oxime microcrystalline cellulose/nano-silver/chitosan ternary composite sol.
And (3) ultrasonically defoaming the ternary composite sol, injecting the ternary composite sol into a mold, freezing the mold at the temperature of-50 ℃ for 8 hours, and performing vacuum drying to obtain the amidoxime-hydroxylamine oxime microcrystalline cellulose/nano silver/chitosan composite aerogel.
Taking the amidoxime-hydroxylamine oxime microcrystalline cellulose/nano silver/chitosan composite aerogel prepared in example 1 as an example, the research and analysis are further carried out. In order to characterize the influence of the amidoxime-hydroxylamine oxime microcrystalline cellulose component on the structural morphology of the aerogel, a pure dialdehyde chitosan aerogel is prepared as a control according to the same method. As shown in figure 1, the pure dialdehyde chitosan aerogel shows a three-dimensional network interpenetrating porous structure, the pore size is 40-100 μm, and the holes are dispersed relatively uniformly. In contrast, the amidoxime-hydroxylamine oxime microcrystalline cellulose/nano silver/chitosan composite aerogel shown in fig. 2 has a layered porous structure, the density of pores is increased, the size is reduced, and amidoxime-hydroxylamine oxime microcrystalline cellulose with a rod-like structure can be obviously found among pores. Further enlarging, uniform nano silver particles (figure 3) can be observed on the surface of the rod-shaped cellulose, and the size is 20-40 nm. In addition, due to abundant active groups on the surface of the amidoxime-hydroxylamine oxime microcrystalline cellulose and the in-situ reduction preparation process, the nano silver is firmly loaded, uniformly dispersed and uniform in size.
The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The preparation method of the amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel is characterized in that the composite aerogel comprises the following components in parts by weight: 2-5 parts of amidoxime-hydroxylamine oxime cellulose, 0.05-2 parts of nano silver and 3-8 parts of chitosan, wherein the preparation method comprises the following steps:
step 1, adding chitosan into an acetic acid solution with the concentration of 2 wt% according to a bath ratio of 1: 100-1: 10, stirring until the chitosan solution is completely dissolved to obtain a chitosan solution, introducing nitrogen, adding a sodium periodate solution into the chitosan solution, wherein the sodium periodate is 13-66% of the chitosan by mass, oxidizing the chitosan solution at 30-60 ℃ in the dark for 1-10 hours, adding an alcohol solution to terminate the reaction, and performing vacuum drying to obtain dialdehyde chitosan, dissolving the dialdehyde chitosan in deionized water to prepare a dialdehyde chitosan solution;
step 2, putting amidoxime-hydroxylamine oxime cellulose into deionized water, and performing ultrasonic dispersion uniformly to obtain 1.5-10 wt% amidoxime-hydroxylamine oxime cellulose dispersion liquid;
step 3, adding 0.001-0.1 mol/L silver nitrate solution into the amidoxime-hydroxylamine oxime cellulose dispersion liquid prepared in the step 2 according to the volume ratio of 1: 10-100: 1, and uniformly stirring at room temperature; then adding the dialdehyde chitosan solution obtained in the step 1 into a reaction system according to the volume ratio of 2: 1-1: 10, and reacting for 0.5-6 h at 50-90 ℃ to obtain amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan ternary composite sol;
step 4, ultrasonically defoaming the ternary composite sol, injecting the ternary composite sol into a mold, freezing the mold at-50 ℃ for 4-10 hours, and drying to obtain amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel;
wherein the preparation of the amidoxime-hydroxylamine oxime cellulose in the step 2 comprises the following steps:
s1, placing the cellulose into a 0.5-5 wt% NaOH solution according to a bath ratio of 1: 100-1: 10, and boiling for 30-150 min; then, placing the mixture in 10-30 wt% NaOH solution according to the bath ratio of 1: 100-1: 10, and stirring for 30-180 min at room temperature; filtering, washing and drying to obtain the alkalized cellulose;
s2, placing the alkalized cellulose into acetone according to a bath ratio of 1: 20-1: 50, and condensing and refluxing for 10-45 min under the protection of nitrogen at 50-60 ℃; then adding 2-cyano-3-ethoxy ethyl acrylate, wherein the weight of the 2-cyano-3-ethoxy ethyl acrylate is 0.2-2 times that of the alkalized cellulose, magnetically stirring for 10-45 min, then adding ammonium ceric nitrate, and continuing to react for 1-8 h, wherein the ammonium ceric nitrate is 0.2-3% of the alkalized cellulose by mass; filtering the product, washing with methanol and water for several times, and drying to obtain the graft copolymer cellulose;
s3, adding the graft copolymerization cellulose into 1mol/L hydroxylamine solution according to a bath ratio of 1: 15-1: 50, reacting for 1-6 h at the temperature of 65-75 ℃ under the condition of magnetic stirring, washing the product with methanol, and drying to obtain the amidoxime-hydroxylamine oxime cellulose.
2. The preparation method of the amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel according to claim 1, wherein the deacetylation degree of the chitosan in the step 1 is 85-95%.
3. The method for preparing the amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan composite aerogel according to claim 1, wherein the alcohol solution in the step 1 is one of ethanol, glycol or glycerol solution.
4. The preparation method of the amidoxime-hydroxylamine oxime cellulose/nano silver/chitosan composite aerogel according to claim 3, wherein the cellulose is rod-shaped microcrystalline cellulose or nano cellulose or a mixture of the microcrystalline cellulose and the nano cellulose.
5. The preparation method of the amidoxime-hydroxylamine oxime cellulose/nano-silver/chitosan composite aerogel according to claim 4, wherein the cellulose is derived from one of natural cellulose and products thereof, regenerated cellulose and products thereof, cellulose-rich agricultural and sideline products or microcrystalline cellulose.
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