CN110373735B - Preparation method of antibacterial nanofiber based on polyelectrolyte-surfactant composite - Google Patents
Preparation method of antibacterial nanofiber based on polyelectrolyte-surfactant composite Download PDFInfo
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- CN110373735B CN110373735B CN201910585238.8A CN201910585238A CN110373735B CN 110373735 B CN110373735 B CN 110373735B CN 201910585238 A CN201910585238 A CN 201910585238A CN 110373735 B CN110373735 B CN 110373735B
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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Abstract
The invention relates to a preparation method of antibacterial nanofiber based on a polyelectrolyte-surfactant compound. The method comprises the following steps: hydrolyzing polyacrylonitrile to obtain polyelectrolyte high polymer, then self-assembling the polyelectrolyte high polymer with surfactant quaternary ammonium salt to obtain a polyelectrolyte-surfactant compound, and finally performing electrostatic spinning to obtain the polyelectrolyte-surfactant compound antibacterial nanofiber. The method has the advantages of simple preparation route, mild reaction conditions, low cost and no toxicity; the obtained nano-fiber has better antibacterial effect and long-acting performance, reduces subsequent finishing procedures and expands the application range of the polyelectrolyte-surfactant composite.
Description
Technical Field
The invention belongs to the field of preparation of antibacterial nanofibers, and particularly relates to a preparation method of antibacterial nanofibers based on a polyelectrolyte-surfactant composite.
Background
Microorganisms pose great harm to human health and life, and rapidly reproduce under appropriate conditions to spread diseases, thereby affecting the living environment of human beings. The textile is an important medium for transmitting germs and can provide conditions for the reproduction and living of microorganisms. Therefore, the research on the antibacterial textile has important significance. The antibacterial fiber is a novel functional material with sterilization and bacteriostasis performance, and the core component of the antibacterial fiber is an antibacterial material. The preparation of the antibacterial fiber mainly comprises the following steps: the antibacterial agent is mixed into the fiber by a physical method, the polymer structure of the chemical fiber is chemically modified or grafted, and a composite spinning technique is used.
The electrostatic spinning technology is a simple and effective method for preparing the antibacterial nanofibers, and the electrospun nanofibers have huge specific surface area and wide application prospect. Polyelectrolyte self-assembly with oppositely charged surfactants in dilute solution can form molecularly ordered solid material-polyelectrolyte-surfactant complexes. Researchers have made more intensive studies on the interaction between the two in aqueous solution, but the polyelectrolyte-surfactant complex of solid structure has been less studied, especially in terms of its functional application. According to the invention, the polyelectrolyte and the quaternary ammonium salt cationic surfactant with antibacterial property are self-assembled to obtain the polyelectrolyte-surfactant compound, and the antibacterial nanofiber is obtained by an electrostatic spinning technology, so that the application range of the antibacterial nanofiber is expanded.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of antibacterial nanofiber based on polyelectrolyte-surfactant composite, and expanding the application range of the polyelectrolyte-surfactant composite.
The preparation method of the antibacterial nanofiber based on the polyelectrolyte-surfactant composite comprises the steps of hydrolyzing polyacrylonitrile to obtain a polyelectrolyte high polymer, then self-assembling the polyelectrolyte high polymer with surfactant quaternary ammonium salt to obtain the polyelectrolyte-surfactant composite, and finally performing electrostatic spinning to obtain the antibacterial nanofiber based on the polyelectrolyte-surfactant composite.
The invention relates to a preparation method of antibacterial nanofiber based on polyelectrolyte-surfactant complex, which comprises the following specific steps:
(1) hydrolyzing Polyacrylonitrile (PAN) with alkali to obtain PAN hydrolysate, namely anionic polyelectrolyte high polymer;
(2) dissolving the anionic polyelectrolyte high polymer in the step (1) in deionized water, slowly dropwise adding a surfactant-quaternary ammonium salt water solution, stirring, filtering, cleaning and drying to obtain a polyelectrolyte-surfactant compound, wherein the mass ratio of the surfactant-quaternary ammonium salt to the polyelectrolyte high polymer is 2: 1;
(3) and (3) dissolving the polyelectrolyte-surfactant compound in the step (2) in a solvent, stirring, and performing electrostatic spinning on the obtained spinning solution to obtain the antibacterial nanofiber based on the polyelectrolyte-surfactant compound, wherein the mass fraction of the polyelectrolyte-surfactant compound in the spinning solution is 10%.
The step (1) of hydrolyzing polyacrylonitrile PAN with alkali specifically comprises the following steps: adding PAN and sodium hydroxide into water according to the mass ratio of 1:1, stirring for more than 3h at 100 ℃, precipitating, cleaning and drying to obtain the anionic polyelectrolyte high polymer.
The drying temperature is 40-60 ℃.
In the step (2), the quaternary ammonium salt is dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride.
And (3) stirring in the step (2) at the temperature of 40-60 ℃ for 30 min.
The drying in the step (2) comprises the following steps: vacuum drying at 40-60 deg.C.
In the step (3), the solvent is one or a mixture of two of isopropanol, dichloromethane and trichloromethane.
And (4) in the step (3), the stirring temperature is room temperature, and the stirring time is more than 6 hours.
The electrostatic spinning in the step (3) comprises the following technological parameters: the applied voltage is 10-20 KV, the receiving distance is 10-20cm, and the solution flow rate is 0.5-1.0 mL/h.
The invention provides an antibacterial nanofiber prepared by the method based on a polyelectrolyte-surfactant compound.
The invention provides an application of the antibacterial nanofiber prepared by the method based on the polyelectrolyte-surfactant compound.
The nano-fiber obtained in the invention has better antibacterial effect and long-acting performance, reduces subsequent finishing procedures and expands the application range of the polyelectrolyte-surfactant composite.
Advantageous effects
The antibacterial nanofiber based on the polyelectrolyte-surfactant composite has better antibacterial effect and long-acting performance, and reduces subsequent finishing procedures. In addition, the preparation method has the advantages of simple preparation route, mild reaction conditions, low cost and no toxicity. And the prepared antibacterial nanofiber can be widely applied to the fields of biology, medical use, textile and the like.
Drawings
FIG. 1 is an SEM electron micrograph of electrospun nanofibers after self-assembly of polyelectrolyte and dodecyltrimethylammonium chloride in example 1;
FIG. 2 is an SEM electron micrograph of electrospun nanofibers after self-assembly of polyelectrolyte with tetradecyltrimethylammonium chloride in example 2;
FIG. 3 is an SEM electron micrograph of electrospun nanofibers after self-assembly of polyelectrolyte with cetyltrimethylammonium chloride in example 3;
fig. 4 is an antibacterial effect diagram of polyelectrolyte and cetyltrimethylammonium chloride electrospun nanofiber in example 3, wherein a and d are antibacterial effect diagrams of blank samples on escherichia coli (e.coli) and staphylococcus aureus (s.aureus), b and e are antibacterial effect diagrams of PAN samples on escherichia coli (e.coli) and staphylococcus aureus (s.aureus), and c and f are antibacterial effect diagrams of sample 16 on escherichia coli (e.coli) and staphylococcus aureus (s.aureus), respectively;
FIG. 5 is an SEM electron microscope image of electrospun nanofibers after self-assembly of polyelectrolyte and octadecyl trimethyl ammonium chloride in example 4.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Preparing a polyelectrolyte high polymer:
10g of sodium hydroxide was added to 200mL of the aqueous solution, and after dissolving the mixture with stirring, the mixture was heated to 100 ℃. 10g PAN polymer powder was added, and the mixture was stirred for 3 hours under condensation. Precipitating the obtained solution, cleaning, and drying in an oven at 50 deg.C to obtain hydrolyzed PAN high polymer, i.e. polyelectrolyte high polymer.
(2) Preparation of polyelectrolyte-surfactant complexes:
dissolving 4g of polyelectrolyte in 100mL of deionized water, dissolving 8g of dodecyl trimethyl ammonium chloride in 200mL of deionized water, slowly dripping a surfactant solvent into the polyelectrolyte solution until white precipitate is generated, continuously stirring for 30 minutes at 50 ℃, filtering and washing the reacted solution, and drying in vacuum at 50 ℃ to obtain the polyelectrolyte-surfactant antibacterial compound.
(3) Preparing the polyelectrolyte-surfactant composite antibacterial nanofiber:
and (3) dissolving the polyelectrolyte-surfactant compound obtained in the step (2) in isopropanol and trichloromethane (the volume ratio of the isopropanol to the trichloromethane is 5: 5), preparing a spinning solution with the material mass fraction of 10%, stirring at room temperature for 10 hours, carrying out electrostatic spinning, applying a voltage of 11KV, allowing the receiving distance to be 12cm, and allowing the solution flow rate to be 0.8 mL/h. The obtained nanofiber membrane was vacuum dried for 12 h. The prepared submicron fiber film (12) is used for a scanning electron microscope, and the test result is shown in figure 1, which shows that the fiber has thicker diameter and is in a network structure.
Example 2
The procedure of example 1 was repeated except that "dodecyltrimethylammonium chloride" in step (3) of example 1 was changed to "tetradecyltrimethylammonium chloride", thereby obtaining a nanofiber membrane in the same manner as in example 1. The prepared submicron fiber film (14) is used for a scanning electron microscope, and the test result is shown in figure 2, which shows that the fiber has thicker diameter and is in a network structure.
Example 3
The procedure of example 1 was repeated except for changing "dodecyltrimethylammonium chloride" to "hexadecyltrimethylammonium chloride" in step (3) of example 1, thereby obtaining a nanofiber membrane. The prepared submicron fiber film (16) is used for a scanning electron microscope, and the test result is shown in figure 3, which shows that the fiber has thicker diameter and is in a network structure. The antibacterial effect of the electrospun nanofibers on escherichia coli (e.coli) and staphylococcus aureus (s.aureus) is shown in fig. 4, and it can be seen that bacteria on the blank sample and PAN sample petri dish are propagated in a large amount, and there is no antibacterial performance. The sample 16 has good antibacterial performance for both escherichia coli and staphylococcus aureus, and the antibacterial rate for escherichia coli reaches 98%, and the antibacterial rate for staphylococcus aureus reaches 99%.
Example 4
The procedure of example 1 was repeated except that "dodecyltrimethylammonium chloride" in step (3) of example 1 was changed to "octadecyltrimethylammonium chloride", thereby obtaining a nanofiber membrane. The prepared submicron fiber film (18) is used for a scanning electron microscope, and the test result is shown in figure 5, which shows that the fiber has thicker diameter and is in a network structure.
Claims (6)
1. A preparation method of antibacterial nanofiber based on polyelectrolyte-surfactant complex comprises the following steps: hydrolyzing polyacrylonitrile to obtain polyelectrolyte high polymer, then self-assembling the polyelectrolyte high polymer with surfactant quaternary ammonium salt to obtain polyelectrolyte-surfactant compound, and finally performing electrostatic spinning to obtain the polyelectrolyte-surfactant compound-based antibacterial nanofiber, wherein the specific steps of the method comprise:
(1) adding PAN and sodium hydroxide into water according to the mass ratio of 1:1, stirring for more than 3 hours at 100 ℃, precipitating, cleaning and drying to obtain an anionic polyelectrolyte high polymer;
(2) dissolving the anionic polyelectrolyte high polymer in the step (1) in deionized water, slowly dropwise adding a surfactant-quaternary ammonium salt water solution, stirring, filtering, cleaning and drying to obtain a polyelectrolyte-surfactant compound, wherein the mass ratio of the surfactant-quaternary ammonium salt to the anionic polyelectrolyte high polymer is 2:1, and the surfactant-quaternary ammonium salt is dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride or octadecyl trimethyl ammonium chloride;
(3) and (3) dissolving the polyelectrolyte-surfactant compound in the step (2) in a solvent, stirring, and performing electrostatic spinning on the obtained spinning solution to obtain the antibacterial nanofiber based on the polyelectrolyte-surfactant compound, wherein the mass fraction of the polyelectrolyte-surfactant compound in the spinning solution is 10%.
2. The method according to claim 1, wherein the stirring temperature in the step (2) is 40 to 60 ℃ and the stirring time is 30 min.
3. The method according to claim 1, wherein the solvent in the step (3) is one or a mixture of two of isopropanol, dichloromethane and trichloromethane; the stirring temperature is room temperature, and the stirring time is more than 6 h.
4. The method according to claim 1, wherein the electrostatic spinning in the step (3) comprises the following process parameters: the applied voltage is 10-20 KV, the receiving distance is 10-20cm, and the solution flow rate is 0.5-1.0 mL/h.
5. An antibacterial nanofiber based on polyelectrolyte-surfactant complex prepared according to the method of claim 1.
6. Use of antibacterial nanofibres based on polyelectrolyte-surfactant complexes prepared according to the process of claim 1.
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| CN111518356A (en) * | 2020-05-20 | 2020-08-11 | 中国科学院长春应用化学研究所 | Modified polypropylene and preparation method thereof |
| CN113215727A (en) * | 2021-05-21 | 2021-08-06 | 南京工业大学 | Preparation method of air purification membrane with antibacterial property |
| CN114797503A (en) * | 2022-06-28 | 2022-07-29 | 南通纳爱斯环保科技有限公司 | Graphene-quaternary ammonium salt modified polyacrylonitrile composite fiber filtering membrane and preparation method thereof |
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