CN114197088A - Method for preparing nano-fiber or nano-microsphere by ultrasonic induction and film formed by nano-material - Google Patents
Method for preparing nano-fiber or nano-microsphere by ultrasonic induction and film formed by nano-material Download PDFInfo
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- CN114197088A CN114197088A CN202111319255.0A CN202111319255A CN114197088A CN 114197088 A CN114197088 A CN 114197088A CN 202111319255 A CN202111319255 A CN 202111319255A CN 114197088 A CN114197088 A CN 114197088A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N19/00—Investigating materials by mechanical methods
- G01N19/10—Measuring moisture content, e.g. by measuring change in length of hygroscopic filament; Hygrometers
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- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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- 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
- 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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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention belongs to the technical field of self-assembly nano materials, and discloses a method for preparing nano fibers or nano microspheres by ultrasonic induction and a film formed by nano materials. The method comprises the following steps: in a solvent, mixing sodium alginate and chitosan, and carrying out ultrasonic treatment to obtain the nano material, wherein the nano material is nano fiber or nano microsphere. The invention uses the interaction between raw materials to drive self-assembly and uses the ultrasonic flow field to prepare supermolecule nano-fiber or nano-microsphere. The nano material of the invention has stable structure. The method of the invention is simple. The nano material of the invention forms a film with high mechanical strength, good water resistance and humidity stimulation response by film formation. The film of the invention is used in the field of humidity response, in particular in the field of smart sensing and actuation. The films may also be used as flexible substrates or as plastic substitutes.
Description
Technical Field
The invention belongs to the technical field of self-assembly nano materials, and particularly relates to a preparation method of ultrasonic-induced nano fibers or nano microspheres and a film formed by the nano fibers or the nano microspheres.
Background
Supramolecules in biological systems are of interest because of their unique structure and function. Natural supramolecules always work in non-equilibrium states. Researchers strive to seek kinetically controlled self-assembly that is not achievable by the self-thermodynamic process. Despite recent advances, the synthesis of kinetically controlled supramolecular nanofibers from biological macromolecules remains a significant challenge due to the complexity of natural macromolecules. Most of the existing natural polymer nanofibers are prepared by adopting a top-down electrostatic spinning method for natural polymers, the preparation process is complex and greatly influenced by raw materials, and the structure of the materials is difficult to regulate and control.
The invention patent CN201610856609.8 prepares the nano-fiber of chitosan and sodium alginate by a standing method, but the standing method has long time (6-120 hours) for forming the nano-fiber, and the appearance is difficult to regulate and control. Because a random three-dimensional network structure is easily formed under the condition of strong electrostatic acting force, the nano-fiber and the nano-microsphere are difficult to efficiently prepare by using chitosan and sodium alginate as raw materials through a standing method.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a method for preparing nano fibers or nano microspheres by ultrasonic induction. The invention prepares the nano material with controllable appearance and stable dynamics through ultrasonic induction. The method is simple and efficient.
Another object of the present invention is to provide a thin film formed of the nanomaterial prepared by the above method. The film of the invention is a biodegradable film material. The invention utilizes the nano material (nano fiber or nano microsphere) prepared by the ultrasonic induced sodium alginate and the chitosan to form the film with high mechanical strength, good water resistance and humidity stimulation response.
The film of the invention is used in the field of humidity response, in particular in the field of smart sensing and actuation. The film may also be used as a flexible substrate.
The purpose of the invention is realized by the following technical scheme:
a method for preparing nano-fibers or nano-microspheres by ultrasonic induction comprises the following steps:
1) mixing sodium alginate and chitosan in a solvent, and performing ultrasonic treatment to obtain a nano material, wherein the nano material is nano fiber or nano microsphere;
when the mass ratio of sodium alginate to chitosan is 1: 1, the ultrasonic treatment time is 1-8 hours, and the nano material is nano fiber;
when the mass ratio of the sodium alginate to the chitosan is 1: 1, the ultrasonic treatment time is 10 seconds to 15 minutes, and the nano material is nano microspheres;
when the mass ratio of the sodium alginate to the chitosan is not 1: 1, the nano material is nano microspheres (in this case, the nano material is in an ellipsoid shape).
The mass ratio of the chitosan to the sodium alginate is 1: 10-10: 1.
The solvent is a solution formed by acid and water, and the acid is hydrochloric acid, acetic acid, oxalic acid, citric acid, diluted hydrochloric acid/sulfuric acid and the like.
The mass concentration of the acid solution is 0.02-15%.
The molecular weight of the chitosan is 5-500 kDa, and the deacetylation degree is 30-99%; the molecular weight of the sodium alginate is 5kDa to 100 kDa.
The ultrasonic frequency of the ultrasonic treatment is 20 kHz-50 kHz, and the power is 10W-750W.
The specific steps of the step 1) are respectively preparing sodium alginate and chitosan into solutions to obtain a sodium alginate solution and a chitosan solution; mixing the sodium alginate solution with the chitosan solution, and carrying out ultrasonic treatment to obtain the nano material.
The sodium alginate solution is a sodium alginate aqueous solution; the mass concentration of the sodium alginate solution is 0.01-10%;
the chitosan solution is an acid solution of chitosan, and is obtained by dissolving chitosan in the acid solution; the mass concentration of chitosan in the chitosan solution is 0.01-10%; the concentration of the acid solution is 0.1-20%.
The mass ratio of the chitosan solution to the sodium alginate solution is 1: 10-10: 1.
The chitosan can be replaced by other polycations (polyallylamine hydrochloride, cationic starch and the like), and the sodium alginate can be replaced by other polyanions (sodium carboxymethyl cellulose, polyacrylic acid and the like).
At this time, the method for preparing the nano-fiber or the nano-microsphere by ultrasonic induction comprises the following steps: mixing a cationic polymer and an anionic polymer compound in a solvent, and carrying out ultrasonic treatment to obtain a nano material, wherein the nano material is nano fiber or nano microsphere;
when the cationic polymer is a cationic polymer other than chitosan; the polycation polymer is more than one of polyallylamine hydrochloride and cationic starch;
when the anionic polymer is an anionic polymer other than sodium alginate; the anionic polymer is more than one of sodium carboxymethylcellulose and polyacrylic acid.
The nano-fiber or the nano-microsphere is used for preparing a film.
A film prepared from the nanofiber or the nano microsphere;
the preparation method of the film comprises the following steps: and forming a film by using the dispersion liquid of the nano fibers or the nano microspheres to obtain the film of the nano material.
The specific preparation method of the film comprises the following steps: mixing a cationic polymer and an anionic polymer compound in a solvent, and carrying out ultrasonic treatment to obtain a nano material dispersion liquid, wherein the nano material is nano fiber or nano microsphere; then forming a film from the nano material dispersion liquid to obtain a film;
when the mass ratio of the cationic polymer to the anionic polymer is 1: 1, the ultrasonic treatment time is 1-8 hours, and the nano material is nano fiber;
when the mass ratio of the cationic polymer to the anionic polymer is 1: 1, the ultrasonic treatment time is 10 seconds to 15 minutes, and the nano material is nano microspheres;
when the mass ratio of the cationic polymer to the anionic polymer is not 1: 1, the nano material is a nano microsphere.
The cationic polymer is more than one of chitosan, polyallylamine hydrochloride and cationic starch;
the anionic polymer is more than one of sodium alginate, sodium carboxymethylcellulose and polyacrylic acid.
The film can be formed by suction filtration or air drying, or can be formed by coating or spin coating and drying.
The concentration of the dispersion is 0.01 wt% -10 wt%.
When the cationic polymer is chitosan and the anionic polymer is sodium alginate, the specific preparation method of the nano material dispersion liquid comprises the following steps: preparing sodium alginate and chitosan into solutions respectively to obtain a sodium alginate solution and a chitosan solution; mixing the sodium alginate solution with the chitosan solution, and carrying out ultrasonic treatment to obtain the nano material.
The sodium alginate solution is a sodium alginate aqueous solution; the mass concentration of the sodium alginate solution is 0.01-10%;
the chitosan solution is an acid solution of chitosan, and is obtained by dissolving chitosan in the acid solution; the mass concentration of chitosan in the chitosan solution is 0.01-10%; the concentration of the acid solution is 0.1-20%.
The film of the invention has high mechanical strength, good water resistance and humidity stimulation response.
The films are used in the field of humidity response, in particular in the field of smart sensing and actuation. The film may also be used as a flexible substrate.
The principle of the invention is as follows: natural polysaccharide is used as a raw material, and the supermolecule nano-fiber and the supermolecule microsphere are prepared by a kinetic control way of an ultrasonic flow field. The electrostatic interaction between natural polysaccharides (sodium alginate and chitosan) drives self-assembly. The ultrasonic energy promotes intermolecular aggregation, and the ultrasonic flow field overcomes disordered arrangement of molecules, so that the parallel orientation of polysaccharide chains is induced, and the formation of dynamically stable nanofibers and nanospheres is accelerated. Initially, the formation of irregular clusters was due to electrostatic interactions between the molecules that were interwoven. Electrostatic interactions drive microphase separation, followed by massive aggregation immediately after mixing and complexation. Typically, large-scale aggregates are converted to spherical micelles after thermodynamic equilibrium. The spherical micelle can minimize Gibbs free energy of the whole system and stabilize the system. In sharp contrast to the thermodynamically controlled approach, parallel oriented molecules can form metastable structures after sonication, with energies in the minima of the local energy landscape. Thus, the assembled supramolecules may remain stable for a longer time. Finally, the transition from nanofibrils to spherical micelles can be achieved over time, after the re-establishment of electrostatic interactions (fission/fusion processes), chain rearrangements and chain exchange processes. Thus, we achieve kinetically controlled self-assembly of polysaccharide supramolecules by overcoming disordered aggregation of the molecules. The supermolecule structure can be accurately regulated and controlled through experimental conditions, and the invention realizes the self-assembly of the supermolecule fiber and the supermolecule microsphere. And through simple filtration, the supermolecule nanofiber and the supermolecule microsphere can form a film with high mechanical strength and water resistance, and can replace a plastic film. Furthermore, supramolecular films exhibit a humidity stimulating response.
The preparation method and the obtained nano-fiber and nano-microsphere have the following advantages and beneficial effects:
(1) the raw materials for preparation are derived from natural polysaccharides, so that the cost is low, and the green and renewable raw materials are obtained;
(2) the preparation method is simple and short in time consumption;
(3) the nanofiber prepared by the method is stable in structure and can be stably stored for 1-3 months;
(4) the nano-form prepared by the method is controllable, the controllable preparation of the fiber and the microsphere can be realized, and the method is beneficial to the application in various fields;
(5) the chitosan/sodium alginate film prepared by the invention has excellent mechanical property and water resistance, and can be used for plastic substitution;
(6) the chitosan/sodium alginate film prepared by the invention has humidity response behavior and quick response, and can be applied to the field of braking.
Drawings
FIG. 1 is an aqueous solution of sodium alginate (left), an acetic acid solution of chitosan (center) and a dispersion of sodium alginate/chitosan nanofibers (right) prepared in example 1;
FIG. 2 is an AFM plot of different sonication times (10 seconds, 0.5 hours, 1 hour, and 2 hours) prepared in example 1; a, b, c and d correspond to the graphs of 10 seconds, 0.5 hour, 1 hour and 2 hours of ultrasound respectively;
FIG. 3 is an electron microscope (a) and an atomic force microscope (b) of the sodium alginate/chitosan nanospheres prepared in example 2;
FIG. 4 is an atomic force micrograph of sodium alginate/chitosan nanospheres prepared in example 3; mixing the chitosan solution and the sodium alginate solution in a ratio of 2: 1 correspondingly, and mixing the chitosan solution and the sodium alginate solution in a ratio of 1: 2 correspondingly;
FIG. 5 is a graph showing the effect of water resistance of the sodium alginate/chitosan nanofiber composite membrane prepared in example 4; a corresponds to the sodium alginate/chitosan nanofiber composite membrane prepared in the embodiment 4, and b corresponds to a thin film formed by chitosan;
FIG. 6 is a graph showing the humidity response of the sodium alginate/chitosan nanofiber composite membrane prepared in example 4 and the effect thereof in a brake;
FIG. 7 is a graph of the mechanical properties of the sodium alginate/chitosan membrane prepared in example 4; 1-1 corresponds to the film prepared in example 4, and 1-2 and 2-1 correspond to the films prepared by mixing the chitosan solution and the sodium alginate solution in a mass ratio of 1: 2 and 2: 1, respectively, in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Dissolving sodium alginate (50kDa) in water to obtain a sodium alginate solution with the mass fraction of 5%; dissolving chitosan (50kDa, deacetylation degree of 90%) in acetic acid solution with mass fraction of 1 wt% to obtain chitosan solution with mass fraction of 5%;
(2) mixing the sodium alginate solution and the chitosan solution in the step (1) according to the mass ratio of 1: 1, and performing ultrasonic treatment for 2 hours (500W, 20kHz) to obtain a dispersion liquid of chitosan/sodium alginate nano fibers;
(3) and (3) performing film formation (suction filtration or air drying treatment) on the chitosan/sodium alginate nanofiber dispersion liquid obtained in the step (2) to obtain the chitosan/sodium alginate film.
FIG. 1 is an aqueous solution of sodium alginate (left), an acetic acid solution of chitosan (center) and a dispersion of sodium alginate/chitosan nanofibers (right) prepared in example 1. FIG. 2 is an AFM plot of different sonication times (10 seconds, 0.5 hours, 1 hour, and 2 hours) prepared in example 1; a, b, c and d correspond to the graphs of 10 seconds, 0.5 hour, 1 hour and 2 hours of ultrasound respectively. FIG. 2 shows the formation of supramolecular fibers in example 1. The ultrasonic effect is an important factor for promoting molecular motion and reconstructing a gel network, and the chitosan and sodium alginate molecules can be oriented by a sound field and a flow field. The flow field and the sound field of the ultrasound are beneficial to the formation of the nano-fibers. After 0.5 hours of sonication, the randomly formed gel network (10 seconds of sonication, a in fig. 2) was stretched by the flow field into a prolate structure (b in fig. 2) with some nanofibers appearing. The formation of nanofibers can be attributed to the orientation and attachment of the chitosan and sodium alginate molecules. The formation of elongated clusters is related to the charge balancing process and the shearing action of the flow field. The reorganization and orientation of the random gel network is energy-demanding and requires a period of time under the action of ultrasound to form the nanofibers. After 1h of sonication (c in fig. 2), more gel network was converted to supramolecular nanofibers. After 2h of sonication, isolated nanofibers may form (d in fig. 2).
Example 2
(1) Dissolving sodium alginate (50kDa) in water to obtain a sodium alginate solution with the mass fraction of 2%; dissolving chitosan (50kDa, deacetylation degree 95%) in 1 wt% acetic acid to obtain a chitosan solution with mass fraction of 2%;
(2) mixing the sodium alginate solution and the chitosan solution in the step (1) according to the mass ratio of 1: 1, and performing ultrasonic treatment for 10 minutes (500W, 20kHz) to obtain a dispersion liquid of dispersed spherical microgel;
(3) and (3) carrying out suction filtration or air drying treatment on the dispersion liquid of the chitosan/sodium alginate spherical microgel obtained in the step (2) to obtain the chitosan/sodium alginate film.
Fig. 3 is an electron micrograph (a) and an atomic force micrograph (b) of the spherical microgel obtained in example 2, which are different from the supramolecular fiber obtained in example 1, and the formation of spherical micelles is a thermodynamically controlled spontaneous process, which is accelerated by sonication.
In this example, spherical micelles are formed, and if the time of ultrasound is 1 hour, 2 hours or 8 hours, the micelles are converted into fibers with the time.
Example 3
(1) Dissolving sodium alginate (75kDa) in water to obtain a sodium alginate aqueous solution with the mass fraction of 2%; dissolving chitosan (100kDa, degree of deacetylation 85%) in 1 wt% acetic acid to obtain chitosan solution;
(2) mixing the chitosan solution and the sodium alginate solution in the step (1) according to the mass ratio of 2: 1 and 1: 2 respectively, and carrying out ultrasonic field orientation for 1 hour (750W, 20kHz) to obtain dispersion liquid with the mass fraction of chitosan/sodium alginate nano microspheres;
(3) and (3) placing the dispersion liquid of the chitosan/sodium alginate nano microspheres obtained in the step (2) into a plastic box (45mm multiplied by 60mm multiplied by 18mm) for airing to obtain the chitosan/sodium alginate film.
FIG. 4 is an atomic force micrograph of the supramolecular ellipsoid obtained in example 3 (the microsphere is an ellipsoid in step (2)), and the obtained ellipsoid microgel is different from the microsphere gel in example 3, and the molecules of the microgel are stretched by a flow field to show a prolate structure, wherein the excessive chitosan makes the surface of a 2-1 sample (corresponding to the mixing of a chitosan solution and a sodium alginate solution in a mass ratio of 2: 1) to be positively charged (a in FIG. 4) and the excessive sodium alginate makes the surface of a 1-2 sample (the mixing of the chitosan solution and the sodium alginate solution in a mass ratio of 1: 2 respectively) (b in FIG. 4) to be negatively charged, and the strong charge repulsion prevents the growth in the axial direction, so that the final structures of the two are ellipsoidal structures.
Example 4
(1) Dissolving sodium alginate (100kDa) in water to obtain a sodium alginate aqueous solution with the mass fraction of 1%; dissolving chitosan (200kDa, degree of deacetylation greater than 70%) in 1 wt% hydrochloric acid to obtain chitosan solution;
(2) mixing the sodium alginate aqueous solution and the chitosan solution in the step (1) according to the mass ratio of 1: 1, and carrying out ultrasonic field orientation for 1 hour (500W, 20kHz) to obtain dispersion liquid with the mass fraction of chitosan/sodium alginate nano fibers;
(3) and (3) carrying out suction filtration or air drying treatment on the chitosan/sodium alginate nano fiber dispersion liquid obtained in the step (2) to obtain the chitosan/sodium alginate film.
The effect graph of the chitosan/sodium alginate film obtained in the embodiment in the water resistance test is shown in fig. 5; a corresponds to the sodium alginate/chitosan nanofiber composite membrane prepared in example 4, and b corresponds to the thin film formed by chitosan. The chitosan/sodium alginate film has excellent water resistance. The traditional biomass-based film has a large number of oxygen-containing functional groups on the molecules of biomass, so that hydrogen bonds are easily formed among the molecules in an aqueous solution to cause permeation and swelling, and the performance of the material is greatly reduced. Unlike traditional biomass-based films, electrostatic interactions make intermolecular binding forces large, water molecules are not prone to damaging electrostatic interactions, and reestablishing strong electrostatic interactions between carboxylic acids and amino groups takes a significant amount of time. Water molecules are difficult to penetrate into the fiber. Only the fibers can be penetrated by water molecules. The strong electrostatic interaction makes the chitosan/sodium alginate film relatively stable in water. The material also shows a humidity response behavior, when the chitosan/sodium alginate film is placed under infrared radiation, the upper surface of the chitosan/sodium alginate film is shrunk due to the escape of water molecules among fibers on the upper surface of the chitosan/sodium alginate film, so that the chitosan/sodium alginate film is bent upwards, and the chitosan/sodium alginate film can absorb water vapor in the air and recover to the original shape after the infrared lamp is removed (figure 6), so that the chitosan/sodium alginate film can be applied to the field of intelligent sensing and actuation. Meanwhile, the chitosan/sodium alginate film has higher strength. The tensile strength can reach 85MPa (strength per unit area) (figure 7), the film has excellent ductility (tensile strain can reach 27.2%), and the performance of the film can be comparable to that of other high-performance biomass-based films such as nano-cellulose. The high strength and excellent water resistance make the chitosan/sodium alginate film useful as a plastic substitute, a flexible substrate, a multifunctional actuator, and the like.
Fig. 6 is a graph showing the humidity response of the sodium alginate/chitosan nanofiber composite membrane prepared in example 4 and the effect of the sodium alginate/chitosan nanofiber composite membrane applied to a brake.
FIG. 7 is a graph of the mechanical properties of the sodium alginate/chitosan membrane prepared in example 4; 1-1 corresponds to the film prepared in example 4, and 1-2 and 2-1 correspond to the films prepared by mixing the chitosan solution and the sodium alginate solution in a mass ratio of 1: 2 and 2: 1, respectively, in example 3.
In the method, the chitosan can be replaced by other polycations (polyallylamine hydrochloride, cationic starch and the like), and the sodium alginate can be replaced by other polyanions (sodium carboxymethyl cellulose, polyacrylic acid and the like).
At this time, the method for preparing the nano-fiber or the nano-microsphere by ultrasonic induction comprises the following steps: mixing a cationic polymer and an anionic polymer compound in a solvent, and carrying out ultrasonic treatment to obtain a nano material, wherein the nano material is nano fiber or nano microsphere;
when the cationic polymer is a cationic polymer other than chitosan; the polycation polymer is more than one of polyallylamine hydrochloride and cationic starch;
when the anionic polymer is an anionic polymer other than sodium alginate; the anionic polymer is more than one of sodium carboxymethylcellulose and polyacrylic acid;
when the molar ratio of cations in the cationic polymer to anions in the anionic polymer is 1: 1, the ultrasonic treatment time is 1-8 hours, and the nano material is nano fiber;
when the molar ratio of the cations in the cationic polymer to the anions in the anionic polymer is 1: 1, the ultrasonic treatment time is 10 seconds to 15 minutes, and the nano material is nano microspheres;
when the molar ratio of the cations in the cationic polymer to the anions in the anionic polymer is not 1: 1, the nano-material is a nano-microsphere.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing nano-fiber or nano-microsphere by ultrasonic induction is characterized in that: the method comprises the following steps:
mixing sodium alginate and chitosan in a solvent, and performing ultrasonic treatment to obtain a nano material, wherein the nano material is nano fiber or nano microsphere;
when the mass ratio of sodium alginate to chitosan is 1: 1, the ultrasonic treatment time is 1-8 hours, and the nano material is nano fiber;
when the mass ratio of the sodium alginate to the chitosan is 1: 1, the ultrasonic treatment time is 10 seconds to 15 minutes, and the nano material is nano microspheres;
when the mass ratio of the sodium alginate to the chitosan is not 1: 1, the nano material is nano microspheres.
2. The method for preparing the nano-fiber or the nano-microsphere by the ultrasonic induction according to claim 1, which is characterized in that:
the solvent is a solution formed by acid and water;
the molecular weight of the chitosan is 5-500 kDa, and the deacetylation degree is 30-99%; the molecular weight of the sodium alginate is 5kDa to 100 kDa;
the mass ratio of the chitosan to the sodium alginate is 1: 10-10: 1.
3. The method for preparing the nano-fiber or the nano-microsphere by the ultrasonic induction according to claim 1, which is characterized in that: the ultrasonic treatment comprises the following steps: the ultrasonic frequency is 20 kHz-50 kHz, and the power is 10W-750W;
the mixing specifically means dissolving sodium alginate in water to obtain a sodium alginate solution; dissolving chitosan in an acid solution to obtain a chitosan solution; the sodium alginate solution is then mixed with the chitosan solution.
4. The method for preparing the nano fiber or the nano microsphere by the ultrasonic induction according to claim 3, which is characterized in that: the concentration of the chitosan solution is 0.01-10 wt%, and the concentration of the sodium alginate solution is 0.01-10 wt%; the concentration of the acid solution in the chitosan solution is 0.1-20 percent; the mass ratio of the chitosan solution to the sodium alginate solution is 1: 10-10: 1.
5. The method for preparing the nano-fiber or the nano-microsphere by the ultrasonic induction according to claim 1, which is characterized in that: mixing a cationic polymer and an anionic polymer compound in a solvent, and carrying out ultrasonic treatment to obtain a nano material, wherein the nano material is nano fiber or nano microsphere;
in this case, the cationic polymer refers to a cationic polymer other than chitosan; the cationic polymer is more than one of polyallylamine hydrochloride and cationic starch;
the anionic polymer is an anionic polymer except sodium alginate; the anionic polymer is more than one of sodium carboxymethylcellulose and polyacrylic acid;
when the mass ratio of the cationic polymer to the anionic polymer is 1: 1, the ultrasonic treatment time is 1-8 hours, and the nano material is nano fiber;
when the mass ratio of the cationic polymer to the anionic polymer is 1: 1, the ultrasonic treatment time is 10 seconds to 15 minutes, and the nano material is nano microspheres;
when the mass ratio of the cationic polymer to the anionic polymer is not 1: 1, the nano material is a nano microsphere.
6. A nanomaterial obtained by the method of any one of claims 1 to 5, wherein: the nano material is nano fiber or nano microsphere.
7. A film, characterized by: is prepared by film forming of nano materials; the nanomaterial is as defined in claim 6.
8. The film of claim 7, wherein: the preparation method comprises the following steps: mixing a cationic polymer and an anionic polymer compound in a solvent, and carrying out ultrasonic treatment to obtain a nano material dispersion liquid, wherein the nano material is nano fiber or nano microsphere; then forming a film from the nano material dispersion liquid to obtain a film;
when the mass ratio of the cationic polymer to the anionic polymer is 1: 1, the ultrasonic treatment time is 1-8 hours, and the nano material is nano fiber;
when the mass ratio of the cationic polymer to the anionic polymer is 1: 1, the ultrasonic treatment time is 10 seconds to 15 minutes, and the nano material is nano microspheres;
when the mass ratio of the cationic polymer to the anionic polymer is not 1: 1, the nano material is a nano microsphere.
9. Use of a film according to any one of claims 7 to 8, wherein: the film is used in the fields of plastic substitutes, flexible substrates and humidity response.
10. Use according to claim 9, characterized in that: the films are useful in the field of intelligent humidity responsive sensing and/or braking.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111319255.0A CN114197088B (en) | 2021-11-09 | 2021-11-09 | Method for preparing nanofiber or nanoparticle by ultrasonic induction and film formed by nanomaterial |
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| CN202111319255.0A CN114197088B (en) | 2021-11-09 | 2021-11-09 | Method for preparing nanofiber or nanoparticle by ultrasonic induction and film formed by nanomaterial |
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