CN102776709A - Method for preparing polyvinylpyrrolidone/chitosan composite nano-fiber film by static spinning - Google Patents
Method for preparing polyvinylpyrrolidone/chitosan composite nano-fiber film by static spinning Download PDFInfo
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- CN102776709A CN102776709A CN2012102381865A CN201210238186A CN102776709A CN 102776709 A CN102776709 A CN 102776709A CN 2012102381865 A CN2012102381865 A CN 2012102381865A CN 201210238186 A CN201210238186 A CN 201210238186A CN 102776709 A CN102776709 A CN 102776709A
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Abstract
The invention relates to a method for preparing a polyvinylpyrrolidone/chitosan composite nano-fiber film by static spinning. The method comprises the steps of: (1) mixing ethanol and formic acid based on volume ratio of 5:5 to 1:9, and transferring the mixture into a reaction container for ultrasonically vibrating for 30 to 60min, and then cooling in ice water; (2) adding the CS (chitosan) and PVP (polyvinylpyrrolidone) into the reaction container used following the step (1) based on the mass ratio of 1:1 to 1:9 along with agitating, and continuously agitating until the mixture is completely swelled, and then vibrating until the mixture is completely dissolved so as to obtain the spinning solution; and (3) statically spinning through the spinning solution, and collecting the nano-fiber, and finally drying the collected nano-fiber in vacuum at 40 to 60 DEG C so as to obtain the PVP/CS composite nano-fiber film. The method is simple in operation, and the raw materials are cheap and easy to obtain, and according to the method, less time is consumed. The PVP/CS composite nano-fiber film prepared by the method has rich reactive hydrophilic functional group.
Description
Technical field
The invention belongs to the preparation field of chitosan composite nano fibre film, particularly a kind of electrostatic spinning prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film.
Background technology
Method of electrostatic spinning is a kind of important method for preparing superfine fibre.Have significantly differently with traditional method, it is with several thousand to several ten thousand volt high-pressure electrostatics on polymer solution or the molten mass band, and charged polymer liquid drops under the effect of electric field force and is stretched.When electric field force was enough big, the polymer drop can overcome surface tension and form the injection thread.Thread is the solvent evaporation in course of injection, and fiber solidifies, and finally drops on the fibrofelt that has formed similar nonwoven fabric shape on the receiving system.The fiber that makes with method of electrostatic spinning is much thinner than conventional method, and its diameter generally arrives between hundreds of nanometers at tens nanometer.
Electrospinning process can be more than 50 kinds of different polymer; For example polyester, polyurethane, polyethylene, polypropylene, polyvinyl alcohol, polyaniline, polyacrylonitrile etc. spin out diameter range from less than several nanometers to the superfine fibre that surpasses 1 μ m, resulting electrospun fibers is collected in and is deposited as non-weaving cloth on the negative plate.The acrylon nano fiber that utilizes electrostatic spinning technique to prepare can prepare high performance acrylon nano fiber on the one hand, improves the wearability of acrylic fiber; Polyacrylonitrile fibre is the main raw material of preparation carbon fiber on the other hand; With can be made into the nano-scale carbon fiber after the processing such as process pre-oxidation of nanoscale polyacrylonitrile fibre and carbonization treatment, carbon nano-fiber is in aspect extensive application such as catalyst carrier, electrode material, high-efficiency adsorbent, hydrogen storage material and polymer architecture enhancement additive.
Shitosan (CS) is a natural polymer, is only second to cellulose in the stock number of occurring in nature, contains extremely strong reactive group in its molecule---amino (NH
2) (OH), have advantages such as excellent solvent-resistance and alkali resistance with hydroxyl.But, increased the difficulty that electric spinning is equipped with nano fibrous membrane because self characteristics makes chitosan solution have very high viscosity.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of electrostatic spinning prepares polyvinylpyrrolidone/chitosan composite nano fibre film; This method is simple to operate; Consuming time less, efficient is high, and material is cheap and easy to get; Prepared film itself contains abundant reacted to hydrophilic functional group, has to use the potentiality that it does follow-up related experiment analysis.
A kind of electrostatic spinning of the present invention prepares the method for polyvinylpyrrolidone (PVP)/shitosan (CS) composite nano-fiber membrane, comprising:
(1) 5:5～1:9 mixes ethanol and formic acid by volume, places supersonic oscillations 30～60min in the reaction vessel then, in frozen water, cools off again;
(2) be that 1:1～1:9 under agitation joins shitosan CS and polyvinylpyrrolidone PVP in step (1) reaction vessel afterwards by mass ratio, continue to be stirred to complete swelling; Vibration is to dissolving fully, as spinning solution then;
(3) adopt above-mentioned spinning solution to carry out electrostatic spinning, collect nanofiber, at last with the nanofiber of collecting in 40-60 ℃ of vacuumize, promptly get the PVP/CS composite nano-fiber membrane.
The specification of polyvinylpyrrolidone is M in the said step (2)
w=1.3 * 10
6
Shitosan used in the said step (2) soaked 12 hours through 10wt%NaOH, and washing is to neutral, vacuumize afterwards.
Vibration in the said step (2) is in 40～80 ℃ water bath chader, to carry out to dissolving fully, and the water-bath time is 15～30h, and dissolution degree is a transparence for causing polymer solution.
The mass fraction sum of shitosan CS and polyvinylpyrrolidone PVP is 5-15% in the middle spinning solution of said step (2).
The syringe specification is 5mL in said step (3) electrostatic spinning, and the syringe needle internal diameter is 0.4～0.7mm.
The sample introduction speed of the spinning solution in said step (3) electrostatic spinning is 0.5～3mL/h, and voltage is at 12～20kv.
Receiving screen in said step (3) electrostatic spinning adopts the reception of aluminium foil ground connection, and the distance of syringe needle and receiving screen is 10～25cm.
Vacuum drying temperature in the said step (3) is 50～60 ℃, and be 24～36 hours drying time.
The fiber diameter range of the PVP/CS composite nano-fiber membrane in the said step (3) is 200～900nm, and fiber presents different patterns because of the different proportionings of solution.
Solubilizing reaction among the present invention is to proceed to complete swelling at interval in mechanical agitation and sonicated, and the material that is spun is polyvinylpyrrolidone (PVP, M
w=1.3 * 10
6The mixture of)/shitosan different proportion, the solvent of being selected for use is the mixed solution of the different proportion of absolute ethyl alcohol and formic acid, the absolute ethyl alcohol of the different proportion of being selected for use/formic acid mixed solution is at first to use the cold water precooling.
The present invention fully takes into account the advantage of polyvinylpyrrolidone; With polyvinylpyrrolidone is main spinning material; Through adding the shitosan powder,, successfully prepared polyvinylpyrrolidone/chitosan composite nano fibre film through groping solvent burden ratio and relevant spinning condition parameter.
Beneficial effect
(1) method of the present invention is simple to operate, and raw material are cheap and easy to get, and is consuming time less, can obtain diameter at short notice
With the aperture at nano level membrane material;
(2) the prepared PVP/CS composite nano-fiber membrane of the present invention itself contains abundant reacted to hydrophilic functional group,
Have and use the potentiality that it does follow-up related experiment analysis.
Description of drawings
Fig. 1 is 1:9 for fixation of C S/PVP mass ratio, and spinning voltage is 15kv, and receiving range is 15cm, and when the injection flow velocity was 1ml/h, the CS/PVP spinning solution of employing different quality mark carried out the stereoscan photograph of electrostatic spinning gained; (a) 6wt%; (b) 8wt%; (c) 10wt%; (d) 12wt%;
Fig. 2 is 10% for the mass fraction of fixation of C S/PVP spinning solution, and spinning voltage is 15kv, and receiving range is 15cm, when the injection flow velocity is 1ml/h, and the FT-IR collection of illustrative plates of the CS/PVP electrostatic spinning nano tunica fibrosa of different quality mark; (a) pure PVP powder; (b) pure CS powder; (c) 6wt%; (d) 8wt%; (e) 10wt%; (f) 12wt%;
Fig. 3 is 10% for the mass fraction of fixation of C S/PVP spinning solution, and spinning voltage is 15kv, and receiving range is 15cm, when the injection flow velocity is 1ml/h, and the XRD figure spectrum of the CS/PVP electrostatic spinning nano tunica fibrosa of different quality mark; (a) pure PVP powder; (b) pure CS powder; (c) 6wt%; (d) 8wt%; (e) 10wt%; (f) 12wt%.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The preparation of composite nano-fiber membrane:
(1) is that absolute ethyl alcohol and the formic acid mixed liquor of 9:1 put into reaction vessel with volume ratio, behind supersonic oscillations 30～60min, in frozen water, cools off;
(2) load weighted CS/PVP mixed-powder under agitation slowly is added in the resulting solvent of step (1) in proportion, continues stir about 20～30min to complete swelling.The solution of configuration variable concentrations (CS and PVP sum), 6wt%, 8wt%, 10wt%, 12wt%, in mixed liquor, the mass ratio of CS and PVP is 1:9;
(3) reaction vessel is placed in the water bath chader, under reflux condensation mode, slowly be heated to 60 ℃, vibration 24h gets the CS/PVP spinning solution to dissolving fully;
(4) extract the CS/PVP spinning solution with 5ml syringe (the syringe needle internal diameter is 0.7mm), be fixed on the electrostatic spinning apparatus, fixedly electrostatic pressure is 15kv, and receiving range is 15cm, and the injection flow velocity is 1mL/h, carries out electricity and spins, and obtains CS/PVP superfine nano tunica fibrosa;
(5) it is subsequent use the film of collecting to be carried out the dry back of series.
Embodiment 2
The composite nano-fiber membrane surface topography is analyzed:
Adopt the JSM-5600LV SEM of Japanese JEOL company that the compound nano fibrous membrane surface of closing for preparing is observed, metal spraying is handled 30～60s before observing.The result sees Fig. 1
Embodiment 3
The composite nano-fiber membrane infared spectrum is analyzed:
The Nicolet Nexus670 type Fourier infrared spectrograph that adopts U.S. Thermo Fisher company is analyzed the infrared spectrum (FT-IR) of the composite nano-fiber membrane for preparing.The result sees Fig. 2.
Embodiment 4
Composite nano-fiber membrane X-ray diffractogram analysis of spectrum:
Adopt the D/max-2550PC type X-ray diffractometer of Japanese Rigaku company that the crystal structure of sample is analyzed, testing used X ray is the Cu-K alpha ray, and wavelength is 0.15406nm.The result sees Fig. 3.
Claims (10)
1. an electrostatic spinning prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, comprising:
(1) 5:5～1:9 mixes ethanol and formic acid by volume, places supersonic oscillations 30～60min in the reaction vessel then, in frozen water, cools off again;
(2) be that 1:1～1:9 under agitation joins shitosan CS and polyvinylpyrrolidone PVP in step (1) reaction vessel afterwards by mass ratio, continue to be stirred to complete swelling, vibration is to dissolving fully, as spinning solution then;
(3) adopt above-mentioned spinning solution to carry out electrostatic spinning, collect nanofiber, at last with the nanofiber of collecting in 40-60 ℃ of vacuumize, promptly get the PVP/CS composite nano-fiber membrane.
2. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, it is characterized in that: the specification of polyvinylpyrrolidone is M in the said step (2)
w=1.3 * 10
6
3. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, it is characterized in that: shitosan used in the said step (2) is through alkali treatment.
4. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film; It is characterized in that: the vibration in the said step (2) is in 40～80 ℃ water bath chader, to carry out to dissolving fully, and the water-bath time is 15～30h.
5. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, it is characterized in that: the mass fraction sum of shitosan CS and polyvinylpyrrolidone PVP is 5-15% in the middle spinning solution of said step (2).
6. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, it is characterized in that: the syringe specification is 5mL in said step (3) electrostatic spinning, and the syringe needle internal diameter is 0.4～0.7mm.
7. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film; It is characterized in that: the sample introduction speed of the spinning solution in said step (3) electrostatic spinning is 0.5～3mL/h, and voltage is at 12～20kv.
8. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film; It is characterized in that: the receiving screen in said step (3) electrostatic spinning adopts the reception of aluminium foil ground connection, and the distance of syringe needle and receiving screen is 10～25cm.
9. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, it is characterized in that: the vacuum drying temperature in the said step (3) is 50～60 ℃, and be 24～36 hours drying time.
10. a kind of electrostatic spinning according to claim 1 prepares the method for polyvinylpyrrolidone/chitosan composite nano fibre film, it is characterized in that: the fiber diameter range of the PVP/CS composite nano-fiber membrane in the said step (3) is 200～900nm.
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| CN104141147A (en) * | 2014-08-01 | 2014-11-12 | 太原理工大学 | Method for making microorganism electrolytic cell generate and store hydrogen through microbial fuel cells in self-driven mode |
| CN105935694A (en) * | 2016-06-30 | 2016-09-14 | 东华大学 | Repairing system of soil combined pollutants |
| CN106283396A (en) * | 2016-08-22 | 2017-01-04 | 王利萍 | A kind of preparation method of porous chitosan fibrous membrane |
| CN108042839A (en) * | 2017-12-19 | 2018-05-18 | 湖北工程学院 | A kind of chitosan complexes bandage and preparation method thereof |
| CN108559448A (en) * | 2018-06-05 | 2018-09-21 | 张芸 | A kind of lasting antifogging agent for glass |
| CN111088528A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Conductive spinning solution, preparation method and application of conductive acrylic fiber |
| CN113862830A (en) * | 2021-10-18 | 2021-12-31 | 扬州日兴生物科技股份有限公司 | Method for preparing chitosan/polyvinylpyrrolidone composite fiber |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141147A (en) * | 2014-08-01 | 2014-11-12 | 太原理工大学 | Method for making microorganism electrolytic cell generate and store hydrogen through microbial fuel cells in self-driven mode |
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| CN105935694A (en) * | 2016-06-30 | 2016-09-14 | 东华大学 | Repairing system of soil combined pollutants |
| CN105935694B (en) * | 2016-06-30 | 2019-03-29 | 东华大学 | A kind of repair system of soil Fl object |
| CN106283396A (en) * | 2016-08-22 | 2017-01-04 | 王利萍 | A kind of preparation method of porous chitosan fibrous membrane |
| CN108042839A (en) * | 2017-12-19 | 2018-05-18 | 湖北工程学院 | A kind of chitosan complexes bandage and preparation method thereof |
| CN108559448A (en) * | 2018-06-05 | 2018-09-21 | 张芸 | A kind of lasting antifogging agent for glass |
| CN111088528A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Conductive spinning solution, preparation method and application of conductive acrylic fiber |
| CN111088528B (en) * | 2018-10-24 | 2021-12-14 | 中国石油化工股份有限公司 | Conductive spinning solution, preparation method and application of conductive acrylic fiber |
| CN113862830A (en) * | 2021-10-18 | 2021-12-31 | 扬州日兴生物科技股份有限公司 | Method for preparing chitosan/polyvinylpyrrolidone composite fiber |
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Application publication date: 20121114 |