CN101502759B - Method for preparing nylon 6/chitosan superfine nano fiber film by electrostatic blended spinning process - Google Patents
Method for preparing nylon 6/chitosan superfine nano fiber film by electrostatic blended spinning process Download PDFInfo
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- CN101502759B CN101502759B CN200910045768XA CN200910045768A CN101502759B CN 101502759 B CN101502759 B CN 101502759B CN 200910045768X A CN200910045768X A CN 200910045768XA CN 200910045768 A CN200910045768 A CN 200910045768A CN 101502759 B CN101502759 B CN 101502759B
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Abstract
The invention relates to a method for statically blending nylon 6/chitosan ultra-fine nano-fiber membranes, comprising the following steps: (1) hexafluoroisopropanol and formic acid mixed liquor are put into a reaction vessel according to volume ratio of 9:1 and are cooled in ice water after 30-60min of ultra-sonic oscillation; (2) nylon 6 and chitosan powder are added to the reaction vessel while stirring, and are stirred continuously till complete swelling; (3) the reaction vessel is put in a water bath oscillator, is slowly heated to 40-60 DEG C under reflux condensation and is continuously oscillated till complete dissolving; (4) nylon 6/chitosan spinning solution is extracted by an injector and is fixed on a static spinning device, and spinning parameter is adjusted for electrospinning; (5) the collected membranes are dried. The invention is rapid, simple, cheap and efficient, and is suitable for batch preparation of nylon 6 nanometer membranes used for analysis; the prepared membranes have abundant reactive hydrophilic active functional groups, and have the potential of being used for follow-up relative experimental analysis.
Description
Technical field
The invention belongs to electrostatic spinning nano fiber film preparation field, particularly relate to a kind of method of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa.
Background technology
Method of electrostatic spinning is a kind of important method for preparing superfine fibre, it has significantly different with traditional method, as tractive force, with several thousand to several ten thousand volt high-pressure electrostatics on polymer solution or the melt band, charged polymer liquid drops under the effect of electric field force and is stretched by electrostatic force.When electric field force was enough big, the polymer drop can overcome surface tension and form the injection thread, and thread is solvent evaporation or curing in course of injection, finally drops on the receiving system, has formed the fibrofelt of similar nonwoven shape.The fiber that makes with method of electrostatic spinning is much thinner than conventional spinning method, and diameter generally arrives hundreds of nanometers at tens nanometer, and minimum diameter can be to 1nm.
Electrospinning process can be the different polymer of kind more than 50, for example polyester, polyurethane, polyethylene, polypropylene, polyvinyl alcohol, polyaniline, polyacrylonitrile etc. be spun into 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 nylon 6/nanometer fiber of electrostatic spinning preparation can prepare high performance polyamide fibre nanofiber on the one hand, improves the wearability of nylon fiber; The fiber that blending in the natural polymers blending of some biologically active such as the nylon polymer is become can have both advantages concurrently on the other hand, the toughness of existing nylon, wearability, given composite membrane new biological nature again, extensive application aspect a lot.
Shitosan (CS) is a natural polymer, contains extremely strong reactive group amino and hydroxyl in the molecule, has advantages such as excellent solvent-resistance and alkali resistance.It is compound on the perforated membrane of various materials, can makes the composite hyperfiltration membrane in different apertures.At present, chitosan polymer is used to prepare infiltration evaporation (or being pervaporation) composite membrane mostly, and carries out blending with shitosan and synthetic high polymer nylon, makes ultrafiltration composite membrane and does not appear in the newspapers as yet.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa; this method is quick, easy, cheap, efficient; prepared in batches and large-scale production; for the research and development of novel nano bioactive materials are offered reference; but prepared film itself contains abundant reactive hydrophilic activated functional groups, has to use the potentiality that it does follow-up related experiment analysis.
The method of a kind of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa of the present invention comprises:
(1) with volume ratio be 9: 1 hexafluoroisopropanols (1,1,1,3,3,3-hexafluoroisopropanol) and the formic acid mixed liquor put into reaction vessel, behind supersonic oscillations 30～60min, in frozen water, cool off;
(2) will be with the mass concentration in hexafluoroisopropanol (HFIP) and the formic acid mixed liquor 4-8% nylon 6 and with mass concentration in hexafluoroisopropanol (HFIP) and the formic acid mixed liquor be that the shitosan powder of 0-2% slowly adds in the above-mentioned reaction vessel under stirring condition, continue to stir 2～3h to complete swelling;
(3) reaction vessel is placed in the water bath chader, under reflux condensation mode, slowly be heated to 40～60 ℃, vibration 15～30h gets nylon 6/ shitosan spinning solution to dissolving fully;
(4) extract nylon 6/ shitosan spinning solution with syringe, be fixed on the electrostatic spinning apparatus, regulate spinning parameter and carry out electrospinning, the ejection flow velocity is 0.5～2ml/h, and electrostatic pressure is 10～18kv, gets nylon 6/ shitosan superfine nano tunica fibrosa;
(5) with dry 12-18h under the film room temperature of collecting, put into baking oven 90-120 ℃ of drying 4～6h then, put into 60～70 ℃ of dry 24h of vacuum desiccator at last, promptly.
The mass concentration of hexafluoroisopropanol (HFIP) is 99%～100% in the described step (1), and water content is less than 0.1%.
Syringe specification in the described step (4) is 5ml, and the syringe needle internal diameter is about 0.4～0.7mm.
Receiving screen in the described step (4) adopts the reception of aluminium foil ground connection, and the distance of syringe needle and receiving screen is 10～20cm.
The fiber diameter range of nylon 6/ chitosan nano fiber membrane in the described step (4) is 100～900nm, and diameter is along with the mass fraction of nylon 6/ shitosan increases and increases, and mass fraction one regularly reduces along with the increase of shitosan content.
This method is main spinning material with nylon 6, and mix be rich in hydrophily functional group-OH ,-NH
2Shitosan, by adjusting solvent and relevant spinning condition parameter, successful realization blending.
Beneficial effect
(1) the inventive method is simple to operate, and is consuming time less, can obtain diameter and aperture at nano level membrane material, is applicable to large-scale production;
(2) raw material used in the present invention are cheap and easy to get, but prepared film itself contains abundant reactive hydrophilic activated functional groups, have to use the potentiality that it does follow-up related experiment analysis;
(3) hydrophily of the composite membrane after the employing blending increases greatly.
Description of drawings
Fig. 1 is that fixedly nylon 6/ chitosan mass ratio is 80/20, and spinning voltage is 16kv, and receiving range is 15cm, when the injection flow velocity is 1ml/h, and the electromicroscopic photograph of the nylon 6/ shitosan electrostatic spinning gained of different quality mark;
Fig. 2 is that fixedly nylon 6/ chitosan mass mark is 6wt.%, spinning voltage is 16kv, receiving range is 15cm, when spraying flow velocity and being 1ml/h, different proportion the electromicroscopic photograph of nylon 6/ shitosan mixing electrostatic spinning gained and the diameter distribution map of resulting nanofiber;
Fig. 3 is the dynamic contact angle figure of the electrospun fiber membrane of different nylon/shitosan blending ratio.
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 and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications 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.
(1) with volume ratio be 9: 1 hexafluoroisopropanols (1,1,1,3,3,3-hexafluoroisopropanol) and the formic acid mixed liquor put into reaction vessel, behind supersonic oscillations 30～60min, in frozen water, cool off;
2) nylon 6 and shitosan powder are slowly added in the above-mentioned reaction vessel under stirring condition, continue to stir 2～3h to complete swelling; Wherein, nylon 6 is at hexafluoroisopropanol (1,1,1,3,3,3-hexafluoroisopropanol) and the concentration in the formic acid mixed liquor adopt series concentration, be respectively 4wt%, 6wt% and 8wt%, shitosan is at hexafluoroisopropanol (1,1,1,3,3, be 20/80 3-hexafluoroisopropanol) and in the formic acid mixed liquor with the mass ratio of nylon 6;
(3) beaker is placed in the water bath chader, under reflux condensation mode, slowly be heated to 60 ℃, vibration 20h gets nylon 6/ shitosan spinning solution to dissolving fully;
(4) (the syringe needle internal diameter is 0.4～0.7mm) extraction nylon, 6/ a shitosan spinning solution, is fixed on the electrostatic spinning apparatus, and fixedly electrostatic pressure is 16kv with the 5ml syringe, receiving range is 15cm, the injection flow velocity is 1ml/h, carries out electrospinning, obtains nylon 6/ shitosan superfine nano tunica fibrosa;
(5) the serial dried drying method in the described step (5) is earlier with dry 12h under the spun film room temperature, puts into 90 ℃ of drying 4～6h of baking oven then, puts into 60～70 ℃ of dry 24h of vacuum desiccator at last.
Method according to embodiment 1, fixedly nylon 6/ chitosan mass mark is 6wt.%, spinning voltage is 16kv, receiving range is 15cm, when spraying flow velocity and being 1ml/h, by change different proportion nylon 6/ shitosan mix, carry out electrospinning, other condition is constant, and the electromicroscopic photograph of the nylon 6/ shitosan superfine nano tunica fibrosa that obtains and distribution of fiber diameters are as shown in Figure 2.With different nylon 6/ shitosan superfine nano tunica fibrosa horizontal positioned and be fixed on the observation platform of contact angle instrument, drip 0.2ml distilled water in its surface with micro syringe, the optical bevel protractor that utilizes JY-82 type contact angle instrument to carry is measured contact angle as shown in Figure 3 fast.
Claims (5)
1. the method for electrostatic blended spinning nylon 6/ a shitosan superfine nano tunica fibrosa comprises:
(1) is that 9: 1 hexafluoroisopropanols and formic acid mixed liquor are put into reaction vessel with volume ratio, behind supersonic oscillations 30～60min, in frozen water, cools off;
(2) nylon 6 and shitosan powder are slowly added in the above-mentioned reaction vessel under stirring condition, continue to stir 2～3h to complete swelling; The mass concentration of described nylon 6 particles in hexafluoroisopropanol and formic acid mixed liquor is 4～8%, and the mass concentration of shitosan in hexafluoroisopropanol and formic acid mixed liquor is 2%;
(3) reaction vessel is placed in the water bath chader, under reflux condensation mode, slowly be heated to 40～60 ℃, vibration 15～30h gets nylon 6/ shitosan spinning solution to dissolving fully;
(4) extract nylon 6/ shitosan spinning solution with syringe, be fixed on the electrostatic spinning apparatus, regulate spinning parameter and carry out electrospinning, the ejection flow velocity is 0.5～2ml/h, and electrostatic pressure is 10～18kv, gets nylon 6/ shitosan superfine nano tunica fibrosa;
(5) with dry 12-18h under the film room temperature of collecting, put into baking oven 90-120 ℃ of drying 4～6h then, put into 60～70 ℃ of dry 24h of vacuum desiccator at last, promptly.
2. the method for a kind of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa according to claim 1 is characterized in that: the mass concentration of hexafluoroisopropanol is 99%～100% in the described step (1), and water content is less than 0.1%.
3. the method for a kind of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa according to claim 1 is characterized in that: the syringe specification in the described step (4) is 5ml, and the syringe needle internal diameter is about 0.4～0.7mm.
4. the method for a kind of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa according to claim 1 is characterized in that: the receiving screen in the described step (4) adopts the reception of aluminium foil ground connection, and the distance of syringe needle and receiving screen is 10～20cm.
5. the method for a kind of electrostatic blended spinning nylon 6/ shitosan superfine nano tunica fibrosa according to claim 1, it is characterized in that: the fiber diameter range of nylon 6/ chitosan nano fiber membrane in the described step (4) is 100～900nm, diameter is along with the mass fraction of nylon 6/ shitosan increases and increases, mass fraction one regularly reduces along with the increase of shitosan content.
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| CN200910045768XA CN101502759B (en) | 2009-02-05 | 2009-02-05 | Method for preparing nylon 6/chitosan superfine nano fiber film by electrostatic blended spinning process |
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| CN200910045768XA CN101502759B (en) | 2009-02-05 | 2009-02-05 | Method for preparing nylon 6/chitosan superfine nano fiber film by electrostatic blended spinning process |
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| CN101502759B true CN101502759B (en) | 2011-04-27 |
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Families Citing this family (9)
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| CN102776709A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Method for preparing polyvinylpyrrolidone/chitosan composite nano-fiber film by static spinning |
| CN103409939B (en) * | 2013-08-21 | 2016-01-20 | 浙江和也健康科技有限公司 | A kind of Novel composite nano tunica fibrosa and its preparation method and application |
| CN105924954B (en) * | 2016-06-08 | 2018-07-24 | 宁波工程学院 | A kind of preparation method of high tensile nylon CS blend films |
| CN106283396A (en) * | 2016-08-22 | 2017-01-04 | 王利萍 | A kind of preparation method of porous chitosan fibrous membrane |
| CN106381570B (en) * | 2016-09-23 | 2018-08-21 | 江西师范大学 | A kind of electrospinning nylon 46/PVA/ boric acid composite nano fibers and preparation method thereof |
| CN106480519B (en) * | 2016-09-23 | 2018-11-09 | 江西师范大学 | Electrospinning nylon66 fiber/PVA/ boric acid nanofibers and preparation method thereof |
| CN107213799B (en) * | 2017-08-03 | 2019-08-09 | 东北林业大学 | A kind of preparation method of super hydrophilic underwater superoleophobic stalk coextrusion nylon film that capableing of oil-water separation lotion |
| CN108996530B (en) * | 2018-08-16 | 2020-09-22 | 军事科学院系统工程研究院卫勤保障技术研究所 | Preparation method of nano magnesium oxide, nano magnesium oxide-nano fiber composite felt, and preparation method and application thereof |
| CN112962216B (en) * | 2021-02-07 | 2022-02-01 | 宁波工程学院 | Preparation method of nylon 6/chitosan/precious metal nano-fiber |
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