CN105220247A - A kind of method regulating Electrospun diameter - Google Patents

A kind of method regulating Electrospun diameter Download PDF

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Publication number
CN105220247A
CN105220247A CN201510781738.0A CN201510781738A CN105220247A CN 105220247 A CN105220247 A CN 105220247A CN 201510781738 A CN201510781738 A CN 201510781738A CN 105220247 A CN105220247 A CN 105220247A
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China
Prior art keywords
diameter
electrospun
conductive
solution
polymer
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CN201510781738.0A
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Chinese (zh)
Inventor
刘太奇
张晓玲
赵云腾
张旗
哈旭然
刘永壮
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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Priority to CN201510781738.0A priority Critical patent/CN105220247A/en
Publication of CN105220247A publication Critical patent/CN105220247A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a kind of method regulating Electrospun diameter, solution electrostatic spinning technique is utilized to prepare fiber, and prepare as follows: utilize solution electrostatic spinning apparatus to configure the Polymer Solution of conductive doped material, the Polymer Solution of conductive doped material is added in syringe, voltage is added by high voltage source, make liquid be ejected on receiving system under the effect of high-pressure electrostatic, obtain the polymer nano-scale filament of conductive doped material; By regulating the addition content of conductive material to regulate the filametntary diameter of polymer nano-scale, filametntary average diameter increases with the addition content along with conductive material and reduces, and technique is simple, convenient, environmental protection.

Description

A kind of method regulating Electrospun diameter
Technical field
The present invention relates to a kind of Electrospinning, particularly relate to a kind of method regulating Electrospun diameter.
Background technology
Affect fiber use many factors in, fibre diameter is a very important parameter, when draw ratio very large or very little time, specific area just can be very large.First this mean in time being used as reinforcer, the fiber that the enhancing effect of superfine fibre wants diameter group thick good (supposing that the size at interface determines the effect strengthened here).And another advantage of superfine fibre is exactly when fibre diameter is also little than the wavelength of visible ray time, the ability of the light scattering of fiber just weakens significantly, and such as when the diameter of fiber is less than 400nm time, at this time fiber is in fact just invisible.
Superfine fibre also has many advantages.When this fiber is used for filtering material, filter effect improves along with the reduction of fibre diameter; When it is good for the effect also than common fiber during wound dressing materials; And in fabric, compared with crude fibre, use the fabric of fine fibre to have better surface nature.
The main advantage of electrostatic spinning technique is exactly to obtain the superfine fibre of diameter between nanometer to micron.Diameter range 1 ~ 2 order of magnitude less of the spun silk of common spinning process of these fibers, and have higher draw ratio, specific area is also larger.To the polymer of many different geometrical constructions, diameter and the less fiber of the degree of orientation can be obtained by electrostatic spinning technique.And the diameter of the fiber that traditional spinning process obtains is between 10 ~ 20 μm, therefore, except method of electrostatic spinning, other spinning process is difficult to obtained nano level fiber.Other advantage of electrostatic spinning technique is that the equipment of this technology is fairly simple, due to higher spinning speed, so the operating time is also shorter.In addition, in electrostatic spinning process, only need little sample, this point is particularly important with regard to what show to those expensive samples.Electrostatic spinning technique has many exclusive characteristics, and the material that it uses is very extensive, and many polymer melts or solution all can use, such as, and polyacrylonitrile, nylon-6, polyoxyethylene, polyvinyl alcohol, polycaprolactam, polystyrene and polyaniline etc.Nanofiber prepared by Electrospun is widely used: the main application of traditional micron order fibrous material especially technical fiber as: carbon fiber, glass fibre and Kevlar fiber etc. are used as in composite as reinforcing material.As biomedical material, be mainly used in organizational project, medical Co ntrolled release, biomimetic material and artificial organs.In organizational project, cytoskeleton plays the effect of extracellular matrix, is the bionical of the 26S Proteasome Structure and Function of extracellular matrix, will be subject to the composition structure influence of support during tissue cultures.
Electrospun can as filter materials.U.S. ASSCNatick is devoted to development centre to utilize electronics spinning to develop protectiveness always and takes material (Areviewonpolymersnanofibersbyelectrospinningandtheirappl icationsinnanocomposites; Zheng-MingHuang; Y.-Z.Zhang; M.Kotaki; S.Ramakrishna.; Compositesscienceandtechnology, 2003,63:2223-2253.).Because nanofiber has very high specific area, can be used as adsorbing medium, coated active carbon, biocide etc.The biochemistry protective clothing made of these fibers, can absorb and degrade harmful liquid and gas efficiently.The nanoscale nonwoven film prepared by electronics spin processes has good protective action to the biochemical preparation existed with aerosol form.It is believed that nanofiber diameter is suitable with gas molecule mean free path, when passing through nonwoven film containing aerocolloidal air-flow, gas can produce slippage at fiber surface, therefore the pressure drop loss caused by fiber reduces greatly, and he thinks that this is the immediate cause that nonwoven film has high filter efficiency.Find can obtain higher filter efficiency with very thin film by test, the such as polyamide fibre 6 of the coated polyurethane foam (part of protective clothing) containing active carbon, 6 nonwoven films, control injecting time to change covering amount, when covering amount reaches 0.001kg/m 2time, originally the easy aerosol through froth bed, almost can not enter foams.He is by comparing discovery, and nonwoven film is better than the protective garment material equipped an army now greatly to aerocolloidal strainability.In addition, the cavernous structure of nonwoven film forms inside and outside through micropore, and this is conducive to capillary suction, and compared with other film, the resistance of nonwoven film to gas phase moisture diffusion is minimum.Therefore nonwoven film not only has good strainability, and also have good gas permeability, this is advantageous particularly to protective garment.Electronics spin processes can obtain continuous print nonwoven film, can utilize this advantage, designs seamless coating film.Military affairs can utilize the liner of this method making boots and gloves, biochemistry protective clothing and the normal breathing mask by seam problems puzzlement.
In above-mentioned prior art, complicated to the adjusting process of Electrospun diameter, the feature of environmental protection is poor.
Summary of the invention
The object of this invention is to provide that a kind of technique is simple, convenient, the method for the adjustment Electrospun diameter of environmental protection.
The object of the invention is to be achieved through the following technical solutions:
The method of adjustment Electrospun diameter of the present invention, utilizes solution electrostatic spinning technique to prepare fiber, and prepares as follows:
Solution electrostatic spinning apparatus is utilized to configure the Polymer Solution of conductive doped material, the Polymer Solution of conductive doped material is added in syringe, voltage is added by high voltage source, make liquid be ejected on receiving system under the effect of high-pressure electrostatic, obtain the polymer nano-scale filament of conductive doped material;
By regulating the addition content of conductive material to regulate the filametntary diameter of polymer nano-scale, filametntary average diameter increases with the addition content along with conductive material and reduces.
As seen from the above technical solution provided by the invention, the method for the adjustment Electrospun diameter that the embodiment of the present invention provides, due to the filametntary diameter of addition content adjustment polymer nano-scale by regulating conductive material, technique is simple, convenient, environmental protection.
Accompanying drawing explanation
Fig. 1 is the MIcrosope image (carbon black 2.5%) in the embodiment of the present invention 1;
Fig. 2 is the MIcrosope image (carbon black 5.0%) in the embodiment of the present invention 1.
Detailed description of the invention
To be described in further detail the embodiment of the present invention below.
The method of adjustment Electrospun diameter of the present invention, its preferably detailed description of the invention be:
Utilize solution electrostatic spinning technique to prepare fiber, and prepare as follows:
Solution electrostatic spinning apparatus is utilized to configure the Polymer Solution of conductive doped material, the Polymer Solution of conductive doped material is added in syringe, voltage is added by high voltage source, make liquid be ejected on receiving system under the effect of high-pressure electrostatic, obtain the polymer nano-scale filament of conductive doped material;
By regulating the addition content of conductive material to regulate the filametntary diameter of polymer nano-scale, filametntary average diameter increases with the addition content along with conductive material and reduces.
Described conductive material comprise following any one or more: material with carbon element, the nano-metal particles such as carbon black, graphite, CNT, Graphene.
Described macromolecule comprise following any one or more: styrene, methyl methacrylate.
The method of adjustment Electrospun diameter of the present invention, traditional solution electrostatic spinning technique is utilized to prepare fiber, and change fibre diameter with conductive material/polymer composite fiber prepared by solution method of electrostatic spinning, utilize the effect of electrostatic force to be spun into nano silk the Polymer Solution mixing conductive material.
The present invention utilizes solution electrostatic spinning apparatus, the Polymer Solution mixing conductive material of configuration finite concentration gradient, and stir certain hour, best mixing time is 12 hours; (1) mixed solution is added in syringe, open high voltage source, add certain voltage, make melt be ejected on receiving system under the effect of high-pressure electrostatic, obtain the macromolecular fibre silk of the carbon-black doped of different-diameter.(2) mixed solution of finite concentration macromolecule, conductive material is added in syringe, open high voltage source, regulation voltage in certain limit, obtain the macromolecular fibre silk of the conductive doped material of different-diameter.
The present invention has the following advantages:
1, carbon-black doped or other nano silk diameter can regulate and control by regulating black concentration or spinning voltage;
2, solution electrostatic spinning technique avoids solvent recovery problem, and by raw material direct fabrics, need not add other may poisonous composition, can ensure spin the security of fiber;
3, the nanofiber of conductive doped material that prepared by solution method of electrostatic spinning is continuous fiber, and fibre diameter is little, and specific area is large, and application prospect is wide.
4., along with the increase of conductive material content, diameter obviously diminishes (see table 1)
Specific embodiment:
Raw material used in the present invention: the macromolecular materials such as polystyrene; The organic solvents such as N-N dimethyl formamide; The conductive materials such as carbon black.
The device used in the present invention is melt electrostatic spinning device, voltage 0.1-1000kV, and receiving range is 0.1-20cm.Utilize this electric spinning equipment, first mixed solution is added in syringe, open high-voltage D.C. generator power supply, add certain voltage, start spinning.
Embodiment 1 another name gets 20gDMF in 3 beakers, adds 0.077g, 0.158g, 0.243g carbon black respectively, stirs 12h; Add 4gPS respectively, stir 20h; Ultrasonic 20min.Get 2mL respectively in syringe, open high voltage source, add certain voltage, start spinning, spinning voltage 18kV, receiving range is 10cm.After spinning certain hour, take out fiber.Fig. 1, Fig. 2 are respectively the microphotograph of the PS fiber of carbon-black doped, and the pattern of fiber is good as can be observed from Figure, and even thickness, surface is comparatively smooth.The average diameter of fiber is respectively 1540nm, 1368nm, 1503nm; Its diameter is in first reducing rear increase tendency.
Embodiment 2 takes 20gDMF in 3 beakers, adds 0.158g carbon black, stirs 12h; Add 4gPS, stir 20h; Ultrasonic 20min.Get 2mL in syringe, open high voltage source, add certain voltage, start spinning, spinning voltage is respectively 12kV, 15kV, 18kV, 21kV, and receiving range is 10cm.After spinning certain hour, take out fiber.The average diameter of fiber with increase along with carbon black loading and reduce (see table 1).
Table 1 Electrospun diameter is with the change of carbon black content
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.

Claims (3)

1. regulate a method for Electrospun diameter, it is characterized in that, utilize solution electrostatic spinning technique to prepare fiber, and prepare as follows:
Solution electrostatic spinning apparatus is utilized to configure the Polymer Solution of conductive doped material, the Polymer Solution of conductive doped material is added in syringe, voltage is added by high voltage source, make liquid be ejected on receiving system under the effect of high-pressure electrostatic, obtain the polymer nano-scale filament of conductive doped material;
By regulating the addition content of conductive material to regulate the filametntary diameter of polymer nano-scale, filametntary average diameter increases with the addition content along with conductive material and reduces.
2. the method for adjustment Electrospun diameter according to claim 1, is characterized in that, described conductive material comprise following any one or more: material with carbon element, the nano-metal particles such as carbon black, graphite, CNT, Graphene.
3. the method for adjustment Electrospun diameter according to claim 1 and 2, is characterized in that, described macromolecule comprise following any one or more: styrene, methyl methacrylate.
CN201510781738.0A 2015-11-13 2015-11-13 A kind of method regulating Electrospun diameter Pending CN105220247A (en)

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CN110484981A (en) * 2019-08-09 2019-11-22 上海理工大学附属初级中学 A method of based on taylor cone Height Prediction electro spinning nano fiber diameter

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