CN103952784A - Method for preparing polypropylene nanofiber on large scale - Google Patents
Method for preparing polypropylene nanofiber on large scale Download PDFInfo
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- CN103952784A CN103952784A CN201410196427.3A CN201410196427A CN103952784A CN 103952784 A CN103952784 A CN 103952784A CN 201410196427 A CN201410196427 A CN 201410196427A CN 103952784 A CN103952784 A CN 103952784A
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Abstract
The invention relates to a method for preparing polypropylene nanofiber on a large scale. The method aims to realize the large-scale preparation of the polypropylene nanofiber. The method has the characteristics of high production efficiency and simple process. The invention adopts the technical scheme that the method for preparing the polypropylene nanofiber on a large scale comprises the following steps in sequence of: (1) after an island phase polymer and a marine phase polymer are mixed, fusing and extruding, and directly cooling and granulating in air, wherein the island phase polymer is polypropylene, and the mass percentage concentration of the island phase polymer is 2.5-25 percent; (2) producing a master batch in the step (1) by using melt-blown equipment to obtain superfine composite fiber; (3) dissolving and removing the marine phase polymer in the superfine composite fiber by using a solvent and obtaining the polypropylene nanofiber after drying; (4) heating and recovering the marine phase polymer/solvent waste solution produced in the step (3) and recycling the solvent and the marine polymer.
Description
Technical field
The invention belongs to new chemical fibre and textile material field, be specifically related to a kind of island composite spinning technology is combined with melt blown technology and prepare in batches the method for polypropylene nano fiber, the polypropylene nano fiber making can be the upgraded product of now selling polypropylene fibre.
Background technology
Polypropylene is the current plastics variety of consumption maximum in the world, and wherein exceeding 50% consumption also can increase year after year for fiber market and expection ratio.Polypropylene fibre-forming performance is good, mainly can be prepared into various ways such as comprising short silk, long filament, monofilament, bulk filament, tow, yarn and meltblown fibers, and fiber industry has become the main drive that Polypropylene Market increases.The micron level but the polypropylene fibre diameter of large-scale production is at present everlasting, if fibre diameter can be reduced to nanoscale, mean larger specific area, more function of surface site, higher mechanical strength and more excellent application performance, how to produce polypropylene nano fiber in batches and become a nowadays polypropylene fibre industry bottleneck urgently to be resolved hurrily.
At present, polypropylene fibre large-scale production process is mainly melt-spun and melt-blown two kinds, and wherein melt-spun polypropylene fibre diameter is everlasting even thicker between 10～20 μ m.Melt blown technology is current superfine fibre manufacture method on the largest scale, it relies at a high speed, high temperature gas flow (often approaching melting point polymer) winding-up polymer melt is stretched rapidly it and obtains superfine fibre, but existing meltblown fibers diameter is many between 2～4 μ m, on nano-scale fiber, still there is certain difficulty preparing.Researcher has attempted the whole bag of tricks and has tried hard to further reduce fibre diameter, the Rayleigh-Taylor unstability that in melt blown process, nanofiber has occurred to be caused by surface tension, fiber is broken for spheric granules, and virgin pp meltblown is prepared the nanofiber diameter limit himself theoretical restriction.Prepare polypropylene fibre operating procedure complexity by template, cost is high, and the fibre length of preparation is short, is only suitable for doing theoretical research in laboratory, and is not suitable for suitability for industrialized production.Method of electrostatic spinning needs several kilovolts of volt high direct voltages even up to ten thousand, require high to solution conductivity, and polypropylene is non-polar polymer, spinnability is poor, under normal temperature, there is no suitable solvent yet, can only pass through pyrosol electrospinning or high-temperature fusant electrospinning, higher to matching requirements, greatly limit its commercial application prospect.
Island composite spinning technology is the method that another kind is prepared superfine fibre, its general principle is: in the time of two objectionable intermingling polymeric system blend melt-spuns, by controlling polymer proportion of composing and shearing/rate of extension, can lure that the inner sea-island that occurs of nascent melt-spun fibre is separated into; See that from the cross section of fiber a component is in state fine and that disperse, form discontinuous phase island phase, and another component is surrounded the component of disperseing and formed continuous phase marine facies with continuum of states, wherein island component and sea component are all upwards continuous, intensive at fiber axis; Further remove marine facies polymer by the method for dissolution with solvents, just can obtain the island gathering compound superfine fibre of pencil.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes above-mentioned background technology, and a kind of preparation method of polypropylene nano fiber is provided, and the method should be able to realize the extensive preparation of polypropylene nano fiber, and has that production efficiency is high, the simple feature of technique.
The technical solution used in the present invention is: polypropylene nano fiber batch preparation, carries out according to the following steps successively:
(1) met in island melt extrude after compound and marine facies mixed with polymers and in air direct cooling granulation, island gathering compound is wherein polypropylene, mass percent concentration is 2.5～25%;
(2) master batch in step 1 is produced and obtained superfine composite fiber with melt-blowing equipment;
(3) remove the marine facies polymer in superfine composite fiber by dissolution with solvents, after being dried, obtain polypropylene nano fiber;
(4) the marine facies polymer/solvent discard solution producing in step (3) is carried out to heating recovery, solvent and marine facies polymer recycle.
Marine facies polymer thermostable used in the present invention is high, large with polypropylene compatible and dissolubility difference, be specially at least one in cellulose acetate, acetylbutyrylcellulose, polyethylene terephthalate, polycaprolactam, PLA, polyester, polyamide, alkali soluble polyester.In the present invention, polyacrylic mass percent concentration is 2.5～25%: concentration is too high, and fibre diameter is excessively thick, and phase inversion even occurs, and cannot prepare polypropylene fibre; Concentration is too low, and production efficiency is too low, and cost increases greatly.
The solvent of dissolving marine facies polymer used in the present invention can not dissolve polyacrylic liquid for dissolving marine facies polymer, be specially the one in acetone, carrene, chloroform, butanone, oxolane, dimethyl sulfoxide (DMSO), ethyl acetate, butanols, methyl alcohol, ethanol, isopropyl alcohol, sulfuric acid solution, sodium hydroxide solution, dimethyl formamide, dimethylacetylamide, or the mixing of two or more arbitrary proportions.
Dissolution with solvents of the present invention is removed the process of marine facies polymer, is that superfine composite fiber is impregnated in flux bath, after waiting marine facies polymer dissolution completely, adopts conventional industrial stainless steel filtering net isolated by filtration.
The screw extruder pelletizer draw ratio 20～60 that the present invention uses, compression ratio 3～6, screw speed 200～600rpm; 200～260 DEG C of extrusion temperatures; extruded velocity 50～300kg/h, can, by polypropylene and the even blend of marine facies polymer, be conducive to the formation of island phase separation structure in melt blown process.
The melt-blowing equipment that the present invention uses is existing overall complete production unit, spinning technology parameter is slit shower nozzle, spinning nozzle diameter 0.2～0.85mm, 30 °～60 ° of air drain angles, slit width 0.35～0.65mm, 200～260 DEG C of die temperature, 220～280 DEG C of hot air temperatures, gas pressure 0.05～0.5Mpa, receiving range 8～30cm, spinning speed 25～150kg/h.
The polypropylene nano fiber preparation method who the present invention relates to, also may be used on going in electrostatic spinning technique, can in laboratory scope, prepare a small amount of polypropylene nano fiber sample by high-temperature fusant electrospinning.
The invention has the beneficial effects as follows:
1) realized the batch production of polypropylene nano fiber, the highest 30kg/h that can be of production efficiency of a production line;
2) production procedure is simple, and influence factor is little, by polymer proportion of composing and technological parameter regulation and control, can prepare the polypropylene nano fiber of different-diameter.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that in the embodiment of the present invention 1, polypropylene/acetylbutyrylcellulose is extruded master batch section, and multiplication factor is 1000 times, scale 20 μ m in figure.
Fig. 2 is the scanning electron microscope (SEM) photograph of the polypropylene nano fibre bundle of preparation in the embodiment of the present invention 1, and multiplication factor is 1000 times, scale 20 μ m in figure.
Detailed description of the invention
Key of the present invention be to find a kind of heat endurance high, with polypropylene compatible is poor and dissolubility difference is large marine facies polymer.Polypropylene and marine facies polymer are in the process melt extruding, polypropylene is first dispersed in marine facies polymer with micron ball form, along with melt extrusion and jet drawing process, polypropylene micron ball is deformed into a micron ellipsoid gradually, coalescence mutually, finally be drawn as nano-scale fiber, along fiber axis to being distributed in marine facies polymer.Polypropylene fibre diameter depend on polypropylene at island polymer the deployment conditions in mutually, and the stretcher strain power size being subject in production process.High pressure/high velocity air in melt-blown production process can produce extremely strong stretcher strain effect to spinning jet, and melt-blowing equipment production efficiency is high in addition, makes the preparation in enormous quantities of polypropylene nano fiber become possibility.
The process of dissolution with solvents marine facies polymer of the present invention adopts common process; Specifically the superfine composite fiber of melt-blown production is impregnated in flux bath to (the impregnation process time determines as required, be generally 1-4 hour), Deng marine facies polymer dissolution completely after, adopt conventional industrial stainless steel filtering net (screen pack aperture is selected as required) isolated by filtration to obtain respectively polypropylene nano fiber and marine facies polymer/solvent waste liquid.If residual fraction marine facies polymer is gone back on polypropylene fibre surface after filtering preliminary, and available neat solvent is rinsed well again.
The present invention combines island composite spinning technology and prepares polypropylene nano fiber (fibre diameter is 100～800nm) with melt blown technology, the marine facies polymer and the solvent that are suitable for the method are selected all quite extensive, the permutation and combination of different marine facies polymer/polypropylene/solvents can obtain very many process conditions, but general principle is constant.The whole technological process of production is very simple, mainly comprises that marine facies polymer/polypropylene extruding pelletization-melt-blown production-dissolution with solvents marine facies polymer-dry-marine facies polymer/dissolving waste liquid reclaims.
Below in conjunction with Figure of description, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1 polypropylene/acetylbutyrylcellulose/acetone system
Polypropylene is that Yanshan Petrochemical is produced wire drawing level T30s, and marine facies polymer is acetylbutyrylcellulose (butyric acid content is 35%), and solvent is acetone.First by polypropylene (polypropylene mass percent concentration is 10%) and acetylbutyrylcellulose screw extruder granulation; wherein screw extruder pelletizer draw ratio 30, compression ratio 4, screw speed 400rpm; 240 DEG C of extrusion temperatures, extruded velocity 100kg/h.The master batch sections observation preparing, as shown in Figure 1, can find to form island phase pattern.Master batch is carried out to melt-blown production, and technological parameter is slit shower nozzle, spinning nozzle diameter 0.35mm, 30 ° of air drain angles, slit width 0.52mm, 240 DEG C of die temperature, 250 DEG C of hot air temperatures, gas pressure 0.3Mpa, receiving range 15cm, spinning speed 80kg/h, obtains composite ultrafine fiber.Further be impregnated into 2h in acetone groove, to dissolve the acetylbutyrylcellulose of removing in composite fibre, then use stainless steel filtering net isolated by filtration, be drying to obtain polypropylene nano fiber, with sem observation, as shown in Figure 2, average fibre diameter is 210nm, and corresponding polypropylene nano fibre spinning speed is 8kg/h.Acetylbutyrylcellulose/acetone discard solution is heated at 60 DEG C, reclaim respectively acetone and acetylbutyrylcellulose.
Embodiment 2 polypropylene/PLLA/carrene system
Polypropylene is that Yanshan Petrochemical is produced wire drawing level T30s, and marine facies polymer is PLLA, and solvent is carrene.First by polypropylene (polypropylene mass percent concentration is 15%) and PLLA screw extruder granulation, wherein screw extruder pelletizer draw ratio 40, compression ratio 3, screw speed 250rpm, 260 DEG C of extrusion temperatures, extruded velocity 150kg/h.The master batch of preparation is carried out to melt-blown production, technological parameter is slit shower nozzle, spinning nozzle diameter 0.42mm, 40 ° of air drain angles, slit width 0.62mm, 260 DEG C of die temperature, 280 DEG C of hot air temperatures, gas pressure 0.25Mpa, receiving range 30cm, spinning speed 120kg/h, obtains composite ultrafine fiber.Further be impregnated into 2.5h in carrene groove, to dissolve the PLLA of removing in composite fibre, then use stainless steel filtering net isolated by filtration, after initial gross separation, again rinse with carrene, be drying to obtain polypropylene nano fiber, average fibre diameter is 450nm, and corresponding polypropylene nano fibre spinning speed is 18kg/h.PLLA/carrene discard solution is heated at 90 DEG C, reclaim respectively carrene and PLLA.
Above-described embodiment is only explanation technical conceive of the present invention and feature, its objective is to allow to be familiar with these those skilled in the art and can to understand content of the present invention enforcement according to this, can not limit the scope of the invention with this.Any those skilled in the art are not departing within the scope of technical solution of the present invention; when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations; in every case be the content that does not depart from technical solution of the present invention; any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, within all should being encompassed in protection scope of the present invention.
Claims (5)
1. a polypropylene nano fiber batch preparation, carries out according to the following steps successively:
(1) met in island melt extrude after compound and marine facies mixed with polymers and in air direct cooling granulation, island gathering compound is wherein polypropylene, mass percent concentration is 2.5～25%;
(2) master batch in step 1 is produced and obtained superfine composite fiber with melt-blowing equipment;
(3) remove the marine facies polymer in superfine composite fiber by dissolution with solvents, after being dried, obtain polypropylene nano fiber;
(4) the marine facies polymer/solvent discard solution producing in step (3) is carried out to heating recovery, solvent and marine facies polymer recycle.
2. polypropylene nano fiber batch preparation according to claim 1, is characterized in that described marine facies polymer is at least one in cellulose acetate, acetylbutyrylcellulose, polyethylene terephthalate, polycaprolactam, PLA, polyester, polyamide, alkali soluble polyester.
3. polypropylene nano fiber batch preparation according to claim 2, the solvent that it is characterized in that described dissolving marine facies polymer is the one in acetone, carrene, chloroform, butanone, oxolane, dimethyl sulfoxide (DMSO), ethyl acetate, butanols, methyl alcohol, ethanol, isopropyl alcohol, sulfuric acid solution, sodium hydroxide solution, dimethyl formamide, dimethylacetylamide, or the mixing of two or more arbitrary proportions.
4. according to the polypropylene nano fiber batch preparation described in claim 2 or 3; it is characterized in that described screw extruder pelletizer draw ratio 20～60, compression ratio 3～6, screw speed 200～600rpm; 200～260 DEG C of extrusion temperatures, extruded velocity 50～300kg/h.
5. polypropylene nano fiber batch preparation according to claim 4, the shower nozzle that it is characterized in that described melt-blowing equipment is slit shower nozzle, spinning nozzle diameter 0.2～0.85mm, 30 °～60 ° of air drain angles, slit width 0.35～0.65mm, 200～260 DEG C of die temperature, 220～280 DEG C of hot air temperatures, gas pressure 0.05～0.5Mpa, receiving range 8～30cm, spinning speed 25～150kg/h.
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Cited By (7)
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| CN105133062A (en) * | 2015-09-22 | 2015-12-09 | 深圳市东城绿色投资有限公司 | Preparation method of modified polypropylene nano fiber and oil absorption felt made from modified polypropylene nano fiber |
| CN105297176A (en) * | 2015-11-20 | 2016-02-03 | 东华大学 | Superfine fiber material with rough surface and preparation method thereof |
| CN106048778A (en) * | 2016-06-28 | 2016-10-26 | 武汉纺织大学 | Porous adsorptive fibers and preparation method thereof |
| CN106894108A (en) * | 2017-02-17 | 2017-06-27 | 武汉纺织大学 | Core-skin composite fiber of nanofiber surface and preparation method thereof |
| CN106978647A (en) * | 2017-04-26 | 2017-07-25 | 四川大学 | A kind of production technology of nanofiber |
| CN108342837A (en) * | 2018-02-05 | 2018-07-31 | 浙江省纺织测试研究院 | The preparation method of super oil suction polypropylene melt blown non-woven fabric |
| CN112981722A (en) * | 2021-01-26 | 2021-06-18 | 广东蒙泰高新纤维股份有限公司 | Method for preparing lithium ion battery diaphragm by sea island COPET-PP composite negative pressure spinning |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105133062A (en) * | 2015-09-22 | 2015-12-09 | 深圳市东城绿色投资有限公司 | Preparation method of modified polypropylene nano fiber and oil absorption felt made from modified polypropylene nano fiber |
| CN105297176A (en) * | 2015-11-20 | 2016-02-03 | 东华大学 | Superfine fiber material with rough surface and preparation method thereof |
| CN106048778A (en) * | 2016-06-28 | 2016-10-26 | 武汉纺织大学 | Porous adsorptive fibers and preparation method thereof |
| CN106048778B (en) * | 2016-06-28 | 2018-05-15 | 武汉纺织大学 | A kind of porous adsorbing fiber and preparation method thereof |
| CN106894108A (en) * | 2017-02-17 | 2017-06-27 | 武汉纺织大学 | Core-skin composite fiber of nanofiber surface and preparation method thereof |
| CN106978647A (en) * | 2017-04-26 | 2017-07-25 | 四川大学 | A kind of production technology of nanofiber |
| CN108342837A (en) * | 2018-02-05 | 2018-07-31 | 浙江省纺织测试研究院 | The preparation method of super oil suction polypropylene melt blown non-woven fabric |
| CN112981722A (en) * | 2021-01-26 | 2021-06-18 | 广东蒙泰高新纤维股份有限公司 | Method for preparing lithium ion battery diaphragm by sea island COPET-PP composite negative pressure spinning |
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Application publication date: 20140730 |