CN101417213A - Hollow fiber porous film melt-spinning preparation method - Google Patents
Hollow fiber porous film melt-spinning preparation method Download PDFInfo
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- CN101417213A CN101417213A CNA2008101531854A CN200810153185A CN101417213A CN 101417213 A CN101417213 A CN 101417213A CN A2008101531854 A CNA2008101531854 A CN A2008101531854A CN 200810153185 A CN200810153185 A CN 200810153185A CN 101417213 A CN101417213 A CN 101417213A
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Abstract
The invention provides a preparation method used for melting spinning of a hollow fiber porous film, comprising the processes as follows: 1. two or more thermodynamic incompatible or partly compatible polymer mixtures are used as a film-forming system, wherein, the mass content of the dispersed phase polymer is 10-50 percent of that of the substrate phase polymer; the polymer is polyurethane and polyethylene, polyurethane and polyvinylidene fluoride or polyurethane/ polyurethane/ polyvinylidene fluoride; secondly, multi-phase blends consisting of proper polymer, the good solvent thereof and inorganic grains are used as a film-forming system, wherein, the mass content of the inorganic grain is 10-50 percent of that of the substrate phase polymer; the proper polymer is polyvinylidene fluoride or polyvinyl chloride; the inorganic grain is SiO2 or CaCO3, with the particle size not more than 10 microns; and the polymer good solvent or common good solvent is dimethylacetamide or dimethyl sulfoxide or dimethylformamide; 2. the hollow fiber film is prepared by melting the spinning; and 3. the hollow fiber film is post-processed.
Description
Technical field
The present invention relates to a kind of hollow membrane technology of preparing, be specially a kind of method of utilizing interface pore principle and melt spinning manufacturing process to prepare the doughnut perforated membrane, international Patent classificating number intends being Int.Cl.D01F6/00 (2006.01) I.
Background technology
At present, the technology of preparing of doughnut perforated membrane mainly comprises solution spinning and melt spinning method.Melt spinning method mainly comprises melt spinning-pulling method and thermally induced phase separation, after wherein melt spinning-pulling method is meant polymeric material is melt extruded film forming, it is stretched, thereby radially separate along fiber between the crystalline phase that makes polymer and the amorphous phase, form microcellular structure, this method is had relatively high expectations to the aggregated structure of raw polymer, mainly be applicable to the more manageable hard elastics material of aggregated structure, as polypropylene etc., but the fenestra permeability that forms is relatively poor usually, macro manifestations is that the water flux of doughnut perforated membrane is not high, as described in the ZL901003174 patent.Thermally induced phase separation then is that blend under high temperature (being higher than polymer melting temperature) forms homogeneous system with polymer and high boiling non-solvent (or claiming diluent), then in the temperature-fall period of extrusion molding, making polymer and diluent that Yin Wendu take place descends and be separated (being that so-called thermic is separated) of generation, after forming hollow-fibre membrane, with organic solvents such as ethanol thinner composition residual in the tunica fibrosa is come together and to wash, give the loose structure of doughnut membrane permeability, as described in the ZL98807444.3 patent.The deficiency of thermally induced phase separation is the control of spinning technique is had relatively high expectations, need accurately to control the phase separation between diluent and the matrix phase polymer, otherwise very easily produce fine and close cortex and impermeable cell shape pore structure, cause hollow-fibre membrane forfeiture practical value.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, a kind of melt-spinning preparation method of new doughnut perforated membrane is provided.This preparation method utilizes interface pore principle, under the situation of not adding water-soluble pore-foaming agent, can prepare the doughnut perforated membrane with permeability interface pore structure, has that technology is simple, cost is lower, need not to increase characteristics such as special installation.
The technical scheme that the present invention solve the technical problem is: design a kind of melt-spinning preparation method of doughnut perforated membrane, this preparation method comprises following technology:
1. be prepared into film system: the one, the polymeric blends of two or more that selection thermodynamics is incompatible or part is compatible is as the film forming system, the mass content of dispersed phase polymer is the 10-50% of matrix phase polymer quality in the film forming system, the polymer of two or more that described thermodynamics is incompatible or part is compatible is meant the following polymer of respectively organizing: polyurethane and polyethylene, polyurethane and Kynoar or polyurethane/polyethylene/Kynoar; The 2nd, the heterogeneous co-mixing system of selecting suitable polymer and inorganic matter particulate composition is as the film forming system, the mass content of decentralized photo inorganic matter particulate is the 10-50% of matrix phase polymer quality in the film forming system, and described suitable polymer is meant Kynoar or polyethylene; Described inorganic matter particulate is silica or calcium carbonate, and the particle diameter of inorganic matter particulate is not more than 10 microns;
2. after premix is handled, make nascent hollow-fibre membrane by the melt blending spinning;
3. to the post processing of nascent hollow-fibre membrane, comprise that placing 10min-24h, 25-120 ℃ stretches 1.1-3 times and handle 20min-24h 25 ℃-120 ℃ following fixed length down, promptly prepares the doughnut perforated membrane.
Tradition melt spinning film-forming method is only at hard elastics materials such as polyethylene, polypropylene, is to make its amorphous area produce the pore method of " defective " by stretching, and the hollow-fibre membrane that forms membrane pore structure stretched increases the process of its original hole dimension.Compared with prior art, method of the present invention is by the nascent hollow-fibre membrane after the Stability Analysis of Structures is stretched, utilize compatibility and the difference formation matrix phase of physical-mechanical property and the hole, interface between the decentralized photo between matrix phase and the decentralized photo, and there is gained membrane micropore Stability Analysis of Structures in the post processing mode by fixed length thermal finalization, make the doughnut perforated membrane, have simple, the characteristics such as cost is lower, environmental friendliness of technology.
The specific embodiment
Further specify the present invention below in conjunction with embodiment.
The melt-spinning preparation method (hereinafter to be referred as the preparation method) of a kind of doughnut perforated membrane (hereinafter to be referred as hollow membrane) of the present invention's design comprises following technology:
1. be prepared into film system: the one, the polymeric blends of two or more that selection thermodynamics is incompatible or part is compatible is as the film forming system, the mass content of dispersed phase polymer is the 10-50% of matrix phase polymer quality in the film forming system, the polymer of two or more that described thermodynamics is incompatible or part is compatible is meant the following polymer of respectively organizing: polyurethane and polyethylene, polyurethane and Kynoar or polyurethane/polyethylene/Kynoar etc.; The 2nd, the heterogeneous co-mixing system of selecting suitable polymer and inorganic matter particulate composition is as the film forming system, the mass content of decentralized photo inorganic matter particulate is the 10-50% of matrix phase polymer quality in the film forming system, and described suitable polymer is meant Kynoar or polyvinyl chloride etc.; Described inorganic matter particulate is silica or calcium carbonate, and the particle diameter of inorganic matter particulate is not more than 10 microns;
2. after premix is handled, make nascent hollow-fibre membrane by the melt blending spinning;
3. to the post processing of nascent hollow-fibre membrane, comprise that placing 10min-24h, 25-120 ℃ stretches 1.1-3 times and handle 20min-24h in 25 ℃ of-120 ℃ of following fixed length (promptly keep in the processing procedure length of tunica fibrosa constant) down, promptly prepares the doughnut perforated membrane.
Film forming system of the present invention is made by following heterogeneous co-mixing system (abbreviation co-mixing system): one is meant the heterogeneous co-mixing system of two or more polymer formation that thermodynamics is incompatible or part is compatible, the 2nd, the heterogeneous co-mixing system that the mixture of suitable polymer and inorganic matter particulate constitutes.Can judge the thermodynamic compatibility of two or more polymeric system by Polymer Physics theories such as solubility parameter methods.If the compatibility between the polymer is better, then be difficult for being separated at the two-phase interface place, be unfavorable for the formation of hollow membrane interface pore structure, thereby need to select thermodynamics two or more mixture of polymers incompatible or that part is compatible to do co-mixing system.According to the thermodynamic compatibility theory, mixed system that preparation method of the present invention is suitable for or co-mixing system comprise the following copolymer of respectively organizing: polyurethane and polyethylene, polyurethane and Kynoar, perhaps system such as polyurethane/polyethylene/Kynoar etc.; They satisfy the requirement that thermodynamics of the present invention is incompatible or part is compatible.Simultaneously, studies show that the higher polymer of modulus is corresponding to decentralized photo, the polymer that modulus is lower is corresponding to matrix phase, and the quality of its spinning film forming is better; Otherwise it is then relatively poor relatively.Because if the modulus of decentralized photo is lower, can make its in preparation process such as stretching pore along being subjected to the force direction deformability stronger, be unfavorable for and modulus is higher, deformability is more weak matrix phase between form the good interface pore structure.
The heterogeneous mixed system that the mixture of suitable polymer of the present invention and inorganic matter particulate constitutes is meant the heterogeneous co-mixing system that Kynoar or polyethylene etc. and inorganic matter silica particle or calcium carbonate are formed, the inorganic matter particulate is a decentralized photo in the film forming system that this polyphase blend constitutes, polymer is a matrix phase, the mass content of decentralized photo inorganic matter particulate is the 10-50% of matrix phase polymer quality, the particle diameter of described inorganic matter particulate requires to be not more than 10 microns, and has good dispersiveness.
Require the mass content of dispersed phase component (comprising dispersed phase polymer or inorganic particles) to should be more than the 10-50% of matrix phase constituent mass in the film forming system of the present invention, should guarantee that mixed system has spinning spinnability preferably and gained hollow membrane that mechanical property is preferably arranged, and satisfies instructions for use.Obviously, dispersed phase component content is low excessively, and then the interface number of perforations is few, the permeability of gained hollow membrane and poor practicability; The dispersed phase component too high levels; for described particular polymers co-mixing system; easily produce continuous interface; form uneven macropore; and for polymer and inorganic matter particulate mixed system; then easily make the rheological characteristic and the spinning spinnability variation of heterogeneous mixed system, be unfavorable for carrying out smoothly of spinning membrane system process, the mechanical property of gained hollow membrane is also relatively poor.Studies show that the mass content of dispersed phase component is the 20-35% better of matrix phase constituent mass.
Co-mixing system of the present invention was tackled raw material and is carried out suitable premix processing before carrying out melt spinning, be evenly dispersed in the matrix phase component to guarantee dispersed phase component.Can adopt conical twin-screw mixer etc. to carry out premix and handle, be to strengthen the blend effect, adopts twin-screw to melt extrude spinning, obtains nascent hollow-fibre membrane.Melt-spinning technology of the present invention and conventional melt spinning filming technology do not have essential distinction.
Behind the spinning technique, the nascent hollow membrane of gained placed in air, water or steam handles 10min-24h, treat that its structure is relatively stable after, in uniform temperature and medium, it is stretched and post processing is a committed step of the present invention.Because the difference of compatibility between matrix phase polymer and the dispersed phase component, in nascent hollow membrane axially loaded process, the active force at multi phase interface place a little less than, the difference of mechanical performance causes the lower matrix phase polymer of modulus that deformation easily takes place and the higher difficult generation of the dispersed phase component deformation of modulus, concentrate thereby stress takes place, form interface of the present invention pore structure at the multi phase interface place.Drawing process can carry out in air, water-bath or steam, draft temperature can be controlled in 25 ℃-120 ℃, adopt water-bath and suitable rising temperature to help evenly carrying out of drawing process, draw ratio is at least the long 1.1-3 of nascent hollow pleurodiaphragmatic in terspace doubly, preferred draw ratio is 1.5-2 times, is advisable with the do not exert an influence defective of serviceability of hollow membrane.Last handling process is to instigate hollow membrane after the stretching to carry out fixed length (promptly keep in the processing procedure length of tunica fibrosa constant) in post-processing medium to handle, temperature is at 25 ℃-120 ℃, time 20min-24h, described post-processing medium can be water, air or steam etc., concrete technology is identical with existing fixed length heat treatment technics, and purpose is to make the interface pore structure of gained hollow membrane in use stable and not yielding.
Preparation method of the present invention is a melt spinning shaping interface pore method, need not to add water-soluble pore component in the technology of preparation hollow membrane.But the present invention does not repel the preparation method of suitable solubility pore-foaming agent (the comprising water-soluble pore-foaming agent) component of in film forming system adding yet.Add suitable water-soluble pore-foaming agent component and can further improve the porosity of gained hollow membrane, improve its microcellular structure.Suitable water-soluble pore component of the present invention is meant polyethylene glycol (PEG), polyoxyethylene (PEO), or particle diameter is not more than 10 microns water soluble inorganic substance (example hydrochloric acid salt etc.) particulate.The suitable addition of water-soluble pore component is 1-10% of a film forming system gross mass.
The present invention does not address part and is applicable to prior art.
Compare with other existing spinning membrane system technology, preparation method's of the present invention maximum characteristics are, prepare hollow membrane by matrix phase and dispersed phase interface pore with penetrating pore structure feature, thereby can be described as interface pore melt spinning system embrane method, it is simpler that it has technology, cost is lower, need not to increase special installation, is easy to characteristics such as industrializing implementation.
Further specify the present invention with specific embodiment below.Just to specifying of inventing, it does not limit claim protection domain of the present invention to embodiment.
Embodiment 1
Adopt conical twin-screw mixer with polyurethane/polyethylene (75/25, mass ratio, the abundant premix of blend down together), under 160 ℃, melt extrude, after doughnut spinning pack and water-bath cooling, obtain nascent hollow membrane, the nascent hollow membrane of gained is placed 10min in air at room temperature through double screw extruder, treat that its structure is basicly stable, in 25 ℃ of water-baths, it is stretched 2 times, in 25 ℃ of air, handle 30min under the metrostasis, promptly make described hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 350 (Lm
-2H
-1).
Embodiment 2
Adopt conical twin-screw mixer with the abundant premix of polyurethane/Kynoar/polyoxyethylene (67/23/10) blend, under 158 ℃, melt extrude through double screw extruder, after doughnut spinning pack and air bath cooling, obtain nascent hollow membrane, the nascent hollow membrane of gained is handled 24h in room temperature water, after treating its Stability Analysis of Structures, in 40 ℃ of water-baths, stretch 3 times, in 40 ℃ of water, handle 2h under the metrostasis then, and utilize the interface pore structure that produces in this process to promote washing out of water-soluble polyoxyethylene, promptly make described hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 650 (Lm
-2H
-1).
Embodiment 3
Adopt the silicon dioxide microparticle blend of conical twin-screw mixer with 10 microns of Kynoar and average grain diameters, wherein the inorganic matter fraction of particle is 30% of a Kynoar content, under 160 ℃, extrude through the double screw extruder melt blending, after doughnut spinning pack and air at room temperature bath cooling, obtain nascent hollow membrane, the nascent hollow membrane of gained handled 3h and treat its Stability Analysis of Structures in air at room temperature after, in 90 ℃ of air, stretch 2.8, in 120 ℃ of saturated vapors, handle 1h under the metrostasis then, make membrane pore structure stable, make described hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 240 (Lm
-2H
-1).
Embodiment 4
Spinning membrane system condition among the embodiment 2 is changed into: handle 10min in room temperature water, draw ratio is 1.1 times in 25 ℃ of water-baths, and handles 20min under the metrostasis in 25 ℃ of water-baths, and other condition is constant, makes described hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 230 (Lm
-2H
-1).
Embodiment 5
It is 1 micron calcium carbonate that silica among the embodiment 3 is changed to average grain diameter, and other condition is constant, makes hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 430 (Lm
-2H
-1).
Embodiment 6
In embodiment 1, the mark that polyurethane/polyethylene blend is accounted for film forming system gross mass reduces to 90%, adds 10% polyethylene glycol, and last gained hollow membrane is soaked 48h with abundant stripping polyethylene glycol in room temperature water, other condition is constant, makes hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 750 (Lm
-2H
-1).
Embodiment 7
In embodiment 6, it is calcium chloride about 5 microns that polyethylene glycol is changed to particle diameter, and other condition is constant, makes hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 780 (Lm
-2H
-1).
Embodiment 8
Adopt the silicon dioxide microparticle blend of conical twin-screw mixer with 10 microns of polyethylene and average grain diameters, wherein the inorganic matter fraction of particle is 30% of a polymerized ethylene content, under 140 ℃, extrude through the double screw extruder melt blending, after doughnut spinning pack and air at room temperature bath cooling, obtain nascent hollow membrane, the nascent hollow membrane of gained handled 3h and treat its Stability Analysis of Structures in air at room temperature after, in 90 ℃ of air, stretch 2.8, in 120 ℃ of saturated vapors, handle 1h under the metrostasis then, make membrane pore structure stable, make described hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 240 (Lm
-2H
-1).
Embodiment 9
In embodiment 1, polyurethane/polyethylene blend is changed to polyurethane/polyethylene/Kynoar (70/25/5) blend, other condition is constant, makes hollow membrane.
Under 0.1Mpa and 25 ℃, measuring gained hollow membrane water flux value is 470 (Lm
-2H
-1).
Claims (5)
1. the melt-spinning preparation method of a doughnut perforated membrane, this preparation method comprises following technology:
(1). be prepared into film system: the one, the polymeric blends of two or more that selection thermodynamics is incompatible or part is compatible is as the film forming system, the mass content of dispersed phase polymer is the 10-50% of matrix phase polymer quality in the film forming system, the polymer of two or more that described thermodynamics is incompatible or part is compatible is meant the following polymer of respectively organizing: polyurethane and polyethylene, polyurethane and Kynoar or polyurethane/polyethylene/Kynoar; The 2nd, the heterogeneous co-mixing system of selecting suitable polymer and good solvent thereof and inorganic matter particulate composition is as the film forming system, the mass content of decentralized photo inorganic matter particulate is the 10-50% of matrix phase polymer quality in the film forming system, described suitable polymer is meant Kynoar or polyvinyl chloride, described polymer good solvent is dimethylacetylamide, dimethyl sulfoxide (DMSO) or dimethyl formamide, described inorganic matter particulate is silica or calcium carbonate, and the particle diameter of inorganic matter particulate is not more than 10 microns;
(2). premix is made nascent hollow-fibre membrane by the melt blending spinning after handling;
(3). to the post processing of nascent hollow-fibre membrane, comprise placing stretching 1.1-3 times and be that 25 ℃-120 ℃ following fixed length are handled 20min-24h under 10min-24h, the 25-120 ℃ temperature, promptly prepare the doughnut perforated membrane in temperature.
2. the melt-spinning preparation method of doughnut perforated membrane according to claim 1, the mass content that it is characterized in that dispersed phase component in the described film forming system is 20-30% of a matrix phase constituent mass.
3. the melt-spinning preparation method of doughnut perforated membrane according to claim 1, in the film forming system that the polymeric blends of two or more that it is characterized in that described thermodynamics is incompatible or part is compatible constitutes, the higher polymer of modulus is made decentralized photo, and the polymer that modulus is lower is done matrix phase.
4. the melt-spinning preparation method of doughnut perforated membrane according to claim 1 is characterized in that the draw ratio of described post processing is 1.5-2 times.
5. according to the melt-spinning preparation method of each described doughnut perforated membrane of claim 1-4, it is characterized in that adding water-soluble pore-foaming agent component in the film forming system, addition is 1-10% of a film forming system gross mass; Described water-soluble pore component is meant polyethylene glycol, polyoxyethylene, or particle diameter is not more than 10 microns hydrochloride particulate.
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| CNA2008101531854A CN101417213A (en) | 2008-11-21 | 2008-11-21 | Hollow fiber porous film melt-spinning preparation method |
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| CN102080277A (en) * | 2010-12-09 | 2011-06-01 | 武汉纺织大学 | Compound elastic fiber and preparation method thereof |
| CN103078074A (en) * | 2012-11-19 | 2013-05-01 | 深圳中兴创新材料技术有限公司 | Composite membrane having porous active layer and preparation method |
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| CN103752178A (en) * | 2014-01-08 | 2014-04-30 | 宁波恺谱瑞膜科技有限公司 | Hollow fibre membrane and preparation method thereof |
| CN103877869A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Porous membrane made of polytetrafluoroethylene hollow fibers, preparation method and application thereof in membrane contactor |
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| CN106365254A (en) * | 2016-09-23 | 2017-02-01 | 广州仕瀚环保科技有限公司 | Titanium oxide film yarn |
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| CN102080277A (en) * | 2010-12-09 | 2011-06-01 | 武汉纺织大学 | Compound elastic fiber and preparation method thereof |
| CN102080277B (en) * | 2010-12-09 | 2013-09-04 | 武汉纺织大学 | Compound elastic fiber and preparation method thereof |
| CN103078074A (en) * | 2012-11-19 | 2013-05-01 | 深圳中兴创新材料技术有限公司 | Composite membrane having porous active layer and preparation method |
| CN103877869A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Porous membrane made of polytetrafluoroethylene hollow fibers, preparation method and application thereof in membrane contactor |
| CN103464003A (en) * | 2013-09-24 | 2013-12-25 | 清华大学 | Method for preparing polypropylene hollow-fiber porous membranes |
| CN103464003B (en) * | 2013-09-24 | 2016-08-10 | 清华大学 | A kind of method preparing polypropylene hollow fiber perforated membrane |
| CN103752178A (en) * | 2014-01-08 | 2014-04-30 | 宁波恺谱瑞膜科技有限公司 | Hollow fibre membrane and preparation method thereof |
| CN105498555A (en) * | 2014-09-24 | 2016-04-20 | 中国石油化工股份有限公司 | Production method of thermoplastic high-molecular material hollow fiber micro-pore membrane |
| CN106268353A (en) * | 2016-09-23 | 2017-01-04 | 广州仕瀚环保科技有限公司 | Bacteriostatic activated carbon film silk |
| CN106310969A (en) * | 2016-09-23 | 2017-01-11 | 广州仕瀚环保科技有限公司 | Activated-carbon membrane filament |
| CN106365254A (en) * | 2016-09-23 | 2017-02-01 | 广州仕瀚环保科技有限公司 | Titanium oxide film yarn |
| CN106693719A (en) * | 2016-12-02 | 2017-05-24 | 湖北硅金凝节能减排科技有限公司 | Hollow fibrous membrane and preparation method thereof |
| CN106693719B (en) * | 2016-12-02 | 2018-05-11 | 湖北硅金凝节能减排科技有限公司 | A kind of hollow-fibre membrane and preparation method thereof |
| CN109346655A (en) * | 2018-09-21 | 2019-02-15 | 江苏微能电子科技有限公司 | Over capacity stablizes lithium battery and preparation method thereof |
| CN110112005A (en) * | 2019-05-15 | 2019-08-09 | 宁波石墨烯创新中心有限公司 | A kind of combination electrode and preparation method thereof and application |
| CN110112005B (en) * | 2019-05-15 | 2021-02-09 | 宁波石墨烯创新中心有限公司 | Composite electrode and manufacturing method and application thereof |
| CN110396771A (en) * | 2019-07-05 | 2019-11-01 | 武汉纺织大学 | A kind of preparation method of nano fiber non-woven fabric |
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Open date: 20090429 |