CN101994161A - Method for preparing polytetrafluoroethylene superfine fiber - Google Patents
Method for preparing polytetrafluoroethylene superfine fiber Download PDFInfo
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- CN101994161A CN101994161A CN2009101841291A CN200910184129A CN101994161A CN 101994161 A CN101994161 A CN 101994161A CN 2009101841291 A CN2009101841291 A CN 2009101841291A CN 200910184129 A CN200910184129 A CN 200910184129A CN 101994161 A CN101994161 A CN 101994161A
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Abstract
The invention discloses a method for preparing a polytetrafluoroethylene superfine fiber, comprising the following steps of: firstly dissolving polyvinyl alcohol into water to prepare a polyvinyl alcohol solution, then evenly mixing the polyvinyl alcohol solution with polytetrafluoroethylene concentrated dispersion to prepare a spinning solution; then making the spinning solution into a polytetrafluoroethylene/polyvinyl alcohol superfine fiber by adopting an electrostatic spinning method; and finally, carrying out polyvinyl alcohol removal aftertreatment on the prepared polytetrafluoroethylene/polyvinyl alcohol superfine fiber to obtain the polytetrafluoroethylene superfine fiber. The prepared polytetrafluoroethylene superfine fiber is white or dark brown, and the diameter of the fiber is 30-2000nm.
Description
Technical field
The invention belongs to the superfine fibre preparation field, be specifically related to the technology that a kind of method by electrostatic spinning prepares the polytetrafluoroethylene (PTFE) superfine fibre.
Background technology
A series of performances of solely holding such as polytetrafluoroethylene (PTFE) has serviceability temperature scope wide (250～260 ℃), chemical stability is good, dielectric properties are good, self lubricity and antistick characteristic, its range of application is extremely wide.Because the polytetrafluoroethylene (PTFE) molecular weight is big, degree of crystallinity height, fusing point are also high; One deck fluorine atom shell around the C-C main chain plays shielding action, so stopped the intrusion of all ingredients again. and there is not a kind of solvent can make its dissolving and swelling in time below 300 ℃.Except sodium metal (molten condition), fluorine atom and some chloride, the various strong acid of ability, highly basic, grease, organic solvent and strong oxidizing property reagent (comprising potassium bichromate, potassium permanganate and chloroazotic acid etc.).In all engineering plastics, its corrosion resistance is best, so the title of " plastics king " is arranged.
Polytetrafluoroethylene fibre, major advantage are unique chemical resistances, comprise all known acid, alkali, halogen and oxidant etc.Its chemical resistance is the highest in all commercial organic fibers, even also be like this under high-temperature condition.At present, only find that some perfluorinate organic solvent can dissolve polytetrafluoroethylene fibre, but temperature to reach more than 300 ℃.
Because the special nature of polytetrafluoroethylene (PTFE), polytetrafluoroethylene fibre can't adopt traditional wet spinning and melt spinning preparation.At present, preparing the most frequently used also the most ripe method of polytetrafluoroethylene fibre is milk thread (emulsion spinning).Milk thread is the chemical fibre spinning process that comprises emulsion and suspension spinning, is the spining technology that grows up 40～fifties of 20th century.Certain is difficult to become fine high polymer to be dispersed in the fine carrier of easy one-tenth with solution or melt spinning, forms uniform spinning emulsion, become fine, claim the carrier spin processes by means of carrier.This method is applicable to the fiber-forming polymer that some can not use dry spinning, wet spinning to be shaped.This class high polymer just acutely decomposed before being melt into viscous state, and did not have suitable solvent can make its dissolving or plasticizing, and polytetrafluoroethylene (PTFE) is its topmost application.In order to spin polytetrafluoroethylene fibre, monomer is carried out emulsion polymerisation in autoclave pressure, obtain the water polytetrafluoroethyldispersion dispersion, with polyvinyl alcohol (PVA) aqueous solution or viscose glue as carrier, be blended into uniform emulsion with polytetrafluoroethyldispersion dispersion, it as spinning solution, after filtration, make fiber with common wet spinning process after the deaeration.As-spun fibre carries out drawing by high temperature after washing and drying, sintering when stretching decomposes carrier and is removed, and polytetrafluoroethylparticle particle then bonds (or claim " serialization ") and the formation fiber.Yet the diameter of the polytetrafluoroethylene fibre that makes by this method is usually more than 3um.At present, the report of relevant preparation polytetrafluoroethylsuperfine superfine fiber seldom, only is people (Polymer such as Sachin Borkar, 47 (2006) 8337-8343) (PTFE 601A or 7A, method Dupont) has prepared polytetrafluoroethylsuperfine superfine fiber at the following use of high temperature (260～360 ℃) high pressure draught injection super high molecular weight polytetrafluoroethylene (PTFE) in employing.This method need be carried out under High Temperature High Pressure, and used raw material is the super high molecular weight polytetrafluoroethylene (PTFE).
Electrostatic spinning is that polymer solution or melt spray stretching and the spinning process of acquisition nano-scale fiber under electrostatic interaction.In recent years, and even electrostatic spinning has caused the extensive concern of countries in the world as a kind of novel processing method for preparing the superfine fibre nanofiber.With the fiber that electrostatic spinning technique makes, diameter can reach nanoscale, than the little several magnitude of the fibre diameter that makes with conventional method.This superfine fibre has that specific area is big, porosity is high, draw ratio is big, fiber fine degree and a homogeneity advantages of higher.Yet, utilize electrostatic spinning to prepare polytetrafluoroethylene fibre and even polytetrafluoroethylsuperfine superfine fiber does not appear in the newspapers so far.Only relevant report be people such as Sun Chuiqing (Shaanxi weaving, 2009,81 (1), 8-10) use polytetrafluoroethylene (PTFE)/polyvinyl alcohol emulsion to prepare polytetrafluoroethylene (PTFE)/polyvinyl alcohol blending fibrofelt by electrostatic spinning.But polyvinyl alcohol content is very high in polytetrafluoroethylene (PTFE)/polyvinyl alcohol emulsion that people such as Sun Chuiqing use, and preparation is not pure polytetrafluoroethylene fibre, but polytetrafluoroethylene (PTFE)/polyvinyl alcohol blending fibrofelt.Because polyvinyl alcohol content is very high, the polytetrafluoroethylene (PTFE)/polyvinyl alcohol blending fibrofelt of the method preparation by people such as Sun Chuiqing can not be as the precursor of pure polytetrafluoroethylene fibre.
Summary of the invention
The objective of the invention is to prepare polytetrafluoroethylsuperfine superfine fiber " simple and convenient ", a kind of method for preparing polytetrafluoroethylsuperfine superfine fiber is provided in order to realize.
Purpose of the present invention can reach by following measure:
The present invention prepares precursor with polytetrafluoroethylene (PTFE) spinning emulsion by electrostatic spinning, then obtains polytetrafluoroethylsuperfine superfine fiber by post processing, and this method specifically may further comprise the steps:
A, preparation spinning solution
Polyvinyl alcohol is dissolved in the water makes poly-vinyl alcohol solution, concentrates dispersion emulsion with polytetrafluoroethylene (PTFE) then and mixes, and leaves standstill to obtain spinning solution after separating out bubble; The mass ratio of polyvinyl alcohol and polytetrafluoroethylene (PTFE) is 1: 5～1: 10 and does not comprise 1: 5 in the described spinning solution; General heating and/or the churned mechanically mode of adopting carried out when polyvinyl alcohol dissolved in water.
B, electrostatic spinning
Adopt the method for electrostatic spinning that spinning solution is made polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre;
C, post processing
Polytetrafluoroethylene (PTFE)/polyvinyl alcohol the superfine fibre that makes is removed the polyvinyl alcohol post processing, obtain the polytetrafluoroethylsuperfine superfine fiber that diameter is 30～2000nm.(polytetrafluoroethylsuperfine superfine fiber of indication of the present invention is the polytetrafluoroethylene fibre of diameter at 30nm～2000nm)
In the steps A, for regulating the volatility of spinning solution, can also add a certain amount of volatile micromolecule solvent during dissolve polyvinyl alcohol, volatile micromolecule solvent generally is selected from one or more in methyl alcohol, ethanol, acetone or the butanone.The mass content of polyvinyl alcohol is 8～30% in the poly-vinyl alcohol solution, and volatile micromolecule solvent accounts for 0～10% of poly-vinyl alcohol solution gross mass.
Among the above-mentioned steps A, the polytetrafluoroethylene (PTFE) of polymerization preparation in dispersion emulsion concentrated dispersion emulsion when polytetrafluoroethylene (PTFE) concentrated dispersion emulsion for the preparation polytetrafluoroethylene (PTFE), perhaps will be dispersed in behind the tetrafluoroethylene polymerization in the dispersion liquid, be concentrated into certain viscosity, and with the stable aqueous dispersions of non-ionic surface active agent; Wherein, the mass content that polytetrafluoroethylene (PTFE) concentrates polytetrafluoroethylene (PTFE) in the dispersion emulsion is 55～65%, most preferably is 60%, and the particle diameter of polytetrafluoroethylene (PTFE) is 10～500nm.Described polytetrafluoroethylene (PTFE) concentrates dispersion emulsion and can prepare voluntarily, also can adopt the commercially available prod.
In the spinning solution that steps A makes, in the gross mass of spinning solution, the mass content of polyvinyl alcohol is 3～10%, and the mass content of polytetrafluoroethylene (PTFE) is 30～55%, and volatile micromolecule solvent is 0～5%.
The method of the electrostatic spinning among the step B is: the spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 10～300ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 1～30cm; Open high voltage source, voltage is 1～40kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer.
Among the step C, the post-processing approach of removing polyvinyl alcohol has two kinds, is respectively polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre is washed or heat treatment.The method of washing is that polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre was directly placed deionized water 24～48 hours, with the molten polyvinyl alcohol that goes wherein, obtains polytetrafluoroethylsuperfine superfine fiber, and wherein deionized water was changed once in per 7～9 hours.Heat-treating methods is with after polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre drying, removes polyvinyl alcohol at 280～350 ℃ of following sintering, obtains polytetrafluoroethylsuperfine superfine fiber; Temperature when wherein dry is 100～120 ℃, and the time is 5～15 minutes, and the temperature during sintering is 280～350 ℃, and sintering time is 30～90 minutes.
By above-mentioned way, when adopting the post processing mode of washing, the polytetrafluoroethylsuperfine superfine fiber that obtains is white, fibre diameter 50-1000nm; When adopting heat treated post processing mode, the polytetrafluoroethylsuperfine superfine fiber that obtains is a dark brown, fibre diameter 30-2000nm.
Compare with the technology of preparing of existing polytetrafluoroethylsuperfine superfine fiber, the preparation method of polytetrafluoroethylsuperfine superfine fiber of the present invention is the preparation method of a kind of simple and convenient (need not High Temperature High Pressure and super high molecular weight polytetrafluoroethylene (PTFE) raw material).Compare with the mode of production of existing conventional polytetrafluoroethylene fibre milk thread:
At first, the mode of production of existing conventional polytetrafluoroethylene fibre milk thread can't be used for the production of superfine fibre.
Secondly, because the difference of spinning principle, though all use polytetrafluoroethylene (PTFE)/polyvinyl alcohol milk thread, existing conventional polytetrafluoroethylene fibre milk thread mode and the present invention are to the spinnability of spinning emulsion and wherein the proportion requirement of polytetrafluoroethylene (PTFE)/polyvinyl alcohol is also different.The spinning solution prescription of existing conventional polytetrafluoroethylene fibre milk thread (wherein the polyvinyl alcohol ratio is higher) though also can electrospinning (people's such as Sun Chuiqing as mentioned above work), can't be with this precursor for preparing polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre as the precursor of preparation polytetrafluoroethylsuperfine superfine fiber.And be used for the milk thread that polytetrafluoroethylene (PTFE) used in the present invention/polyvinyl alcohol emulsion also can't be used for conventional polytetrafluoroethylene fibre.
At last, compare with conventional polytetrafluoroethylene fibre milk thread, the spinning that the present invention removes the carrier polyvinyl alcohol also has very big-difference.Conventional polytetrafluoroethylene fibre milk thread as-spun fibre carries out drawing by high temperature after washing and drying, sintering when stretching decomposes carrier and is removed, and polytetrafluoroethylparticle particle then bonds (or claim " serialization ") and the formation fiber.The method that the present invention removes the carrier polyvinyl alcohol has two kinds, i.e. washing or heat treatment.Wherein Shui Xi method is to use and water-solublely removes polyvinyl alcohol in precursor polytetrafluoroethylene (PTFE)/polyvinyl alcohol (the superfine fibre specific area helps the stripping of polyvinyl alcohol greatly, conventional fibre can't use the method), these are different fully with the method that conventional polytetrafluoroethylene fibre milk thread is removed the carrier polyvinyl alcohol; Heat-treating methods is with after polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre drying, removes polyvinyl alcohol at 280～350 ℃ of following sintering, need not to stretch directly to obtain polytetrafluoroethylsuperfine superfine fiber.Because superfine fibre, Technology for Heating Processing and conventional polytetrafluoroethylene fibre milk thread drawing by high temperature sintering process also have very big-difference.In a word, though all use polytetrafluoroethylene (PTFE)/polyvinyl alcohol milk thread, the present invention is a kind of preparation method of brand-new polytetrafluoroethylsuperfine superfine fiber.This preparation polytetrafluoroethylsuperfine superfine fiber method is not at home and abroad appeared in the newspapers at present as yet, and this method " simple and convenient ", and important practical value is arranged.
The method that the present invention prepares polytetrafluoroethylsuperfine superfine fiber is that polytetrafluoroethylene (PTFE) is concentrated dispersion emulsion and solvent mixing, make spinning solution and carry out electrostatic spinning, remove polyvinyl alcohol through post processing then, obtain polytetrafluoroethylsuperfine superfine fiber.Its mechanism be with the polyvinyl alcohol that is easy to electrospinning as carrier, polytetrafluoroethylene (PTFE) is concentrated dispersion emulsion and this polymer solution blend, the spinning emulsion that formation uniformly can electrospinning prepares precursor by electrostatic spinning.Remove this carrier again by post processing then, make polytetrafluoroethylsuperfine superfine fiber.The present invention has broken through the fineness restriction of existing preparation polytetrafluoroethylene fibre, finally can obtain the polytetrafluoroethylsuperfine superfine fiber that diameter is 30～2000nm.
Description of drawings
Fig. 1 is the electrospinning device installation drawing
The specific embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
The preparation example of embodiment 1, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 88.1 gram water with 10.9 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.Used polyvinyl alcohol is the commercially available prod, and the degree of polymerization is 1700-1800, alcoholysis degree 88%-99%.For regulating the volatility of this solution, in whipping process, add 1 gram ethanol, make the ethanol/water solution of polyvinyl alcohol.With the ethanol/water solution and the weight percent concentration of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 200nm concentrates dispersion emulsion and mixed by weight 1: 1, obtains spinning solution after the standing and defoaming;
B, electrostatic spinning
The spinning solution that step a is obtained is injected in the charging gear of electrostatic spinning apparatus, and the feeding rate of adjusting spinning solution is 100ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 15cm; Open high voltage source, voltage is 15kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
The method that polytetrafluoroethylene (PTFE)/the polyvinyl alcohol superfine fibre washes with water that makes is carried out post processing, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.Concrete method is that the 10 gram polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibres that will make directly place the 1000ml deionized water to change deionized water every 8 hours, obtains the polytetrafluoroethylsuperfine superfine fiber of white after 24 hours.The diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 850nm.
The preparation example of embodiment 2, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 90 gram water with 10 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.With the aqueous solution and the weight percent concentration of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 250nm concentrates dispersion emulsion and mixed by weight 1: 1, and standing and defoaming obtains spinning solution;
B, electrostatic spinning
The spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 100ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 20cm; Open high voltage source, voltage is 20kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
Polytetrafluoroethylene (PTFE)/polyvinyl alcohol the superfine fibre that makes is carried out post processing with heat-treating methods, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.When adopting heat treated way to remove polyvinyl alcohol, baking temperature is 100 ℃, and the time is 15 minutes.330 ℃ of sintering temperatures, sintering time are 60 minutes.Obtain the dark brown polytetrafluoroethylsuperfine superfine fiber, the diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 780nm.
The preparation example of embodiment 3, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 93 gram water with 6 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.Be the volatility of regulator solution, in whipping process, add 1 gram ethanol, make the ethanol/water solution of polyvinyl alcohol.With the aqueous solution and the weight percent concentration of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 10nm concentrates dispersion emulsion and mixed by weight 1: 1, and standing and defoaming obtains spinning solution;
B, electrostatic spinning
The spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 10ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 30cm; Open high voltage source, voltage is 40kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
Polytetrafluoroethylene (PTFE)/polyvinyl alcohol the superfine fibre that makes is carried out post processing with heat-treating methods, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.When adopting heat treated way to remove polyvinyl alcohol, baking temperature is 120 ℃, and the time is 5 minutes.350 ℃ of sintering temperatures, sintering time are 60 minutes.Obtain the dark brown polytetrafluoroethylsuperfine superfine fiber, the diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 30nm.
The preparation example of embodiment 4, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 95 gram water with 5 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.With the aqueous solution and the weight percent concentration of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 10nm concentrates dispersion emulsion and mixed by weight 2: 1, and standing and defoaming obtains spinning solution;
B, electrostatic spinning
The spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 10ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 30cm; Open high voltage source, voltage is 40kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
The method that polytetrafluoroethylene (PTFE)/the polyvinyl alcohol superfine fibre washes with water that makes is carried out post processing, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.Concrete method is that the 10 gram polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibres that will make directly place the 1000ml deionized water, changes deionized water every 8 hours, obtains the polytetrafluoroethylsuperfine superfine fiber of white after 48 hours.The diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 50nm.
The preparation example of embodiment 5, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 80 gram water with 10 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.Be the volatility of regulator solution, in whipping process, can add 10 gram ethanol, make the ethanol/water solution of polyvinyl alcohol.With the ethanol/water solution and the weight percent concentration of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 200nm concentrates dispersion emulsion and mixed by weight 1: 1, and standing and defoaming obtains spinning solution;
B, electrostatic spinning
The spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 300ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 10cm; Open high voltage source, voltage is 15kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
To the method post processing that the polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre that makes washes with water, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.Concrete method is that the 10 gram polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibres that will make directly place the 1000ml deionized water, changes deionized water every 8 hours, obtains the polytetrafluoroethylsuperfine superfine fiber of white after 24 hours.The diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 1000nm.
The preparation example of embodiment 6, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 82 gram water with 10 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.For regulating the volatility of this solution, in whipping process, can add 8 gram ethanol, make the ethanol/water solution of polyvinyl alcohol.With the ethanol/water solution and the weight percent concentration of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 500nm concentrates dispersion emulsion and mixed by weight 1: 1, and standing and defoaming obtains spinning solution;
B, electrostatic spinning
The spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 300ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 10cm; Open high voltage source, voltage is 20kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
To the polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre heat-treating methods post processing that makes, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.When adopting heat treated way to remove polyvinyl alcohol, baking temperature is 110 ℃, and the time is 10 minutes.330 ℃ of sintering temperatures, sintering time are 60 minutes.Obtain the dark brown polytetrafluoroethylsuperfine superfine fiber, the diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 2000nm.
The preparation example of embodiment 7, polytetrafluoroethylsuperfine superfine fiber
The preparation of a, spinning solution
At first, in the polyvinyl alcohol adding 90 gram water with 10 grams,, it is dissolved fully make polyvinyl alcohol water solution by heating and mechanical agitation.With the aqueous solution and the 85 gram weight percent concentrations of the polyvinyl alcohol that makes is 60%, and the polytetrafluoroethylene (PTFE) particle diameter is that the polytetrafluoroethylene (PTFE) of 150nm concentrates dispersion emulsion and mixes, and standing and defoaming obtains spinning solution;
B, electrostatic spinning
The spinning solution that steps A is obtained is injected in the electrostatic spinning apparatus charging gear of (as shown in Figure 1), and the feeding rate of adjusting spinning solution is 50ul/min; Distance between the spinning head of charging gear and the gatherer of ground connection is 15cm; Open high voltage source, voltage is 15kV, opens the charging gear pump that spinning solution is housed, and sprays thread and is ejected on the gatherer, obtains polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre on gatherer;
C, superfine fibre post processing to preparing
To the polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre heat-treating methods post processing that makes, remove polyvinyl alcohol, obtain polytetrafluoroethylsuperfine superfine fiber.When adopting heat treated way to remove polyvinyl alcohol, baking temperature is 100 ℃, and the time is 15 minutes.327 ℃ of sintering temperatures, sintering time are 60 minutes.Obtain the dark brown polytetrafluoroethylsuperfine superfine fiber, the diameter of gained polytetrafluoroethylsuperfine superfine fiber is about 580nm.
Claims (9)
1. method for preparing polytetrafluoroethylsuperfine superfine fiber is characterized in that this method may further comprise the steps:
A, preparation spinning solution
Polyvinyl alcohol is dissolved in the water makes poly-vinyl alcohol solution, concentrates dispersion emulsion with polytetrafluoroethylene (PTFE) then and mixes, and leaves standstill to obtain spinning solution after separating out bubble; The mass ratio of polyvinyl alcohol and polytetrafluoroethylene (PTFE) is 1: 5～1: 10 and does not comprise 1: 5 in the described spinning solution;
B, electrostatic spinning
Adopt the method for electrostatic spinning that spinning solution is made polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre;
C, post processing
Polytetrafluoroethylene (PTFE)/polyvinyl alcohol the superfine fibre that makes is removed the polyvinyl alcohol post processing, obtain the polytetrafluoroethylsuperfine superfine fiber that diameter is 30～2000nm.
2. the method for claim 1 is characterized in that in the steps A, also adds 0～10% the volatile micromolecule solvent account for the poly-vinyl alcohol solution gross mass in the described poly-vinyl alcohol solution; Described volatile micromolecule solvent is selected from one or more in methyl alcohol, ethanol, acetone or the butanone.
3. method as claimed in claim 1 or 2 is characterized in that in the steps A, and the mass content of polyvinyl alcohol is 8～30% in the described poly-vinyl alcohol solution.
4. the method for claim 1 is characterized in that in the steps A, and the mass content of polyvinyl alcohol is 3～10% in the described spinning solution, and the mass content of polytetrafluoroethylene (PTFE) is 30～55%.
5. the method for claim 1, the method that it is characterized in that the electrostatic spinning among the step B is: spinning solution is injected in the charging gear of electrostatic spinning apparatus, the feeding rate of adjusting spinning solution is 10～300ul/min, the charging gear pump of opening high voltage source then and spinning solution being housed, spray thread and be ejected on the gatherer, on gatherer, obtain polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre.
6. method as claimed in claim 5 is characterized in that the distance between the gatherer of the spinning head of charging gear in the described electrostatic spinning apparatus and ground connection is 1～30cm; The voltage of described high voltage source is 1～40kV.
7. the method for claim 1 is characterized in that among the step C, describedly removes the polyvinyl alcohol post processing for polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre is washed or heat treatment.
8. method as claimed in claim 7, it is characterized in that described washing is that polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre was directly placed deionized water 24～48 hours, with the molten polyvinyl alcohol that goes wherein, obtain polytetrafluoroethylsuperfine superfine fiber, wherein deionized water was changed once in per 7～9 hours.
9. method as claimed in claim 7 is characterized in that described heat treatment is with after polytetrafluoroethylene (PTFE)/polyvinyl alcohol superfine fibre drying, removes polyvinyl alcohol at 280～350 ℃ of following sintering, obtains polytetrafluoroethylsuperfine superfine fiber; Temperature when wherein dry is 100～120 ℃, and the time is 5～15 minutes, and the temperature during sintering is 280～350 ℃, and sintering time is 30～90 minutes.
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