CN104353369B - A kind of method that hot pressing incipient fusion method prepares nanofiber-based composite filter membrane - Google Patents
A kind of method that hot pressing incipient fusion method prepares nanofiber-based composite filter membrane Download PDFInfo
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Abstract
The present invention relates to a kind of method that hot pressing incipient fusion method prepares nanofiber-based composite filter membrane, comprising: function equipment macromolecule spinning solution carries out electrostatic spinning, using the nano fiber non-woven fabric that obtains as the supporting layer of composite filter membrane；Another kind functional polymer is configured to solution, is sprayed on the barrier layer as composite membrane for the above-mentioned non-woven fabrics membrane surface by electrostatic spraying processes；Use to the barrier layer of composite membrane the hot pressing incipient fusion method giving suitable temperature, pressure and hot pressing time to obtain complete barrier layer, finally carry out post processing to barrier layer and prepare required nanofiber-based composite membrane for separation.The present invention provides a kind of simple method preparing composite filter membrane, can facilitate and be accurately controlled thickness and the uniformity of function barrier layer, easily accomplish scale production；Obtained nanofiber group compound film has broad prospects in fields such as ultrafiltration, nanofiltration, counter-infiltrations.
Description
Technical field
The invention belongs to the preparation field of composite membrane for separation, particularly relate to a kind of method that hot pressing incipient fusion method prepares nanofiber-based composite filter membrane.
Background technology
Shortage of water resources, water environment degradation are world today's common problems, and membrane separation technique as a novel high score from, concentrate, purify and purification techniques, have selective height, simple to operate, energy consumption is low, take up an area less, the advantage such as pollution-free, it is used widely [slowly another in fields such as desalinization, Industrial Wastewater Treatment, environmental pollution improvements, Xu Zhikang, macromolecule member material, Chemical Industry Press, 2005；S.Judd, B.Jefferson, membrane technology and industrial effluent reusing, Chemical Industry Press, 2006], it is to solve the serious lack of water crisis of China, sewage discharge, the guarantee of raising drinking water quality.One of the preparation of current composite separating film and the application main development direction having become technical field of membrane separation.
Composite membrane is a kind of Novel separation film developed in recent years, it is to be composited by the basement membrane of very thin and dense barrier layer and high porosity, this makes composite membrane can choose different materials and preparation technology produces basement membrane and barrier layer, makes their performance respectively reach optimization.Therefore the preparation of composite filter membrane mainly includes that micropore basal membrane prepares the preparation with ultra-thin top layer and compound two parts, and wherein basement membrane is used as supporting layer, and the character of ultra-thin cortex determines separation characteristic and the separating property of composite membrane.
Method of electrostatic spinning is one simple effective method the most [Reneker D H, the Chun I 1996Nanotechnology 7:216 currently preparing the super-fine materials such as continuous nano-fibre；Li D, Xia Y 2004Adv.Mater 16:1151], the nano fiber non-woven fabric prepared has that fibre number is thin, surface-to-volume is than the Morphological Features big, porosity is high, pore structure is interconnected etc., and there is good mechanical strength and lightweight light weight and absorption property, it is extraordinary filtering material and filtration support material [Zhang H Y, Zheng J F, Zhao Z G, Han C C, 2013J.Membr.Sci.442:124；Zhao Z G,Zheng J F,Wang M J,Zhang H Y,Han C C,2012J.Membr.Sci.394-395:209；Park S J,Cheedrala R K,Diallo M S,Kim C,Kim I S,Goddard III W A,2012J.Nanopart.Res.14:884].
The method preparing ultra-thin cortex at present has a lot, mainly has coating process, spraying process, infusion process, interfacial polymerization, chemical vapour sedimentation method, situ aggregation method etc., and the method for most common of which is cladding process.But porosity and the open-celled structure being interconnected due to nanofiber porous basement membrane so that preparing, following two problem easily occurs during composite membrane: the phenomenon oozed under casting solution easily occurs when being function barrier layer in coating procedure；Two is in the unmanageable problem of Motor cortex thickness.These technical problems seriously hinder the commercial Application of nanofiber group compound film scale.
Electrostatic Spraying technique is to produce, based on high-pressure electrostatic conductor fluid after the match, the technology that the principle of high velocity jet develops, its experimentation can be sketched: under normal pressure, the solution of analyte carries high-tension capillary by one, under the high electric field action of about several kilovolts, produce the misty liquid droplets of altitudinal belt electric charge, in transition process, drop due to solvent evaporation or COULOMB EXPLOSION and volume is gradually reduced, finally produce the ion of complete desolventizing.Utilize the colloidal particle preparing nano-scale that electrostatic spraying method can be simple and efficient.On this basis for solving above-mentioned two problems, Wang et al. proposes nanofiber molten method of hanging down and prepares composite filter membrane new technology, the method of electrostatic spinning or electrostatic spray will be used to be deposited on nanofiber porous membrane surface by function of surface membrane material, then surface functional layer is fumigated film forming by solvent vapo(u)r or the melt into film that hangs down in the mixed solution of solvent and non-solvent obtains method [the Wang X F of very thin barrier layer, Zhang K, Y.Yang, Wang L, Zhou Z, .Zhu M F, Hsiao B S, Chu B, 2010J.Membr.Sci.356:110；You H,Yang Y,Li X,Zhang K,Wang X F,Zhu M F,Hsiao B S,2012J.Membr.Sci.394-395:241；You H, Li X, Yang Y, Wang B Y, Li Z X, Wang X F, Zhu M F, Hsiao B S, 2013Sep.Purif.Technol.108:143], well solve and under the casting solution occurring during film, ooze problem and skin thickness problem rambunctious.But solution hangs down, the dissolution method masking time is longer, the more difficult control of molten condition and steam hangs down；And loosening in the composite membrane top layer that these methods are prepared, is only used for retaining larger-size material (such as emulsion), thus is in a disadvantageous position in industrialized production, in terms of its promotion and application, there is limitation.
Content of the invention
The technical problem to be solved is to provide a kind of method that hot pressing incipient fusion method prepares nanofiber-based composite filter membrane; this preparation method is more simple; can facilitate and be accurately controlled thickness and the uniformity that surface selects layer, and be easier to the operation accomplished scale production；Obtained nanofiber-based composite membrane for separation can be used widely in fields such as ultrafiltration, nanofiltration, counter-infiltrations.
The method that a kind of hot pressing incipient fusion method of the present invention prepares nanofiber-based composite filter membrane, comprising:
(1) it is dissolved in functional polymer membrane material in solvent and is configured to the macromolecule spinning solution A that mass fraction is 8～30% and carries out electrostatic spinning, using the nano fiber non-woven fabric that obtains as the supporting layer of composite membrane, the average diameter of supporting layer nanofiber is 100～1000nm, thickness is 40～200 μm, and porosity is 60%～95%；
(2) will differ from the another kind of functional polymer membrane material of step (1) and be dissolved in solvent that to be configured to concentration be 0.1-10% macromolecule spinning solution B, then the function barrier layer as composite membrane for the nonwoven surface prepared in (1) is sprayed by the method for electrostatic spray, the average diameter of the barrier layer particle prepared is 20～2000nm, and thickness is 0.05～20 μm.
(3) carry out hot pressing incipient fusion process to the composite membrane of preparation in (2), i.e. use to the barrier layer containing appropriate solvent heating plate to give suitable temperature, pressure and hot pressing time and be processed to obtain complete barrier layer；Then required nanofiber-based composite membrane for separation is prepared by last handling processes such as chemical crosslinkings；The function barrier layer thickness being formed is 200-2000nm.
Functional polymer membrane material in described step (1) and (2) is PVAC polyvinylalcohol, polyvinyl phenol PVP, Kynoar PVDF, polyvinylchloride, cellulose acetate CA, polycaprolactone (PCL), polymetylmethacrylate, polycarbonate, 3-hydroxybutyrate and 3-hydroxypentanoic acid copolyesters PHBV, polyaniline PANI, polyacrylonitrile (PAN), polylactic acid PLA, polysulfones PSU, polyether sulfone PES, polystyrene PS, polyvinylcarbazole PVK, polyethylene terephtalate, one or several in shitosan CS or polyamic acid PAA.
Solvent in described step (1) and (2) be water, ethanol, n-butanol, isopropanol, acetone, 1-METHYLPYRROLIDONE, dichloromethane, chloroform, oxolane, 1,4-dioxane, formamide, N, dinethylformamide, N, N-dimethylacetylamide, concentration are the acetone N that the aqueous acetone solution of 10～95wt%, concentration are 30～95wt%, dinethylformamide solution or concentration are the dichloromethane DMF solution of 20～95wt%.
Electrostatic spinning process parameter in described step (1) is voltage 8～50kV, spout aperture 0.2～3mm, solution flow rate 5～100 μ L/min, and spinning environment temperature is 10～60 DEG C, and the relative humidity of spinning environment is 30～60%.
Electrostatic spray technological parameter in described step (2) is voltage 15～50kV, spout aperture 0.1～1mm, solution flow rate 5～40 μ L/min, and electrostatic spray environment temperature is 10～60 DEG C, and the relative humidity of electrostatic spray environment is 40～60%.
Hot pressing incipient fusion technological parameter in described step (3) is hot pressing incipient fusion temperature 20～500 DEG C, and hot pressing incipient fusion pressure is 0～50MPa, and the hot pressing incipient fusion process time is 1～100min.
Last handling process in described step (3) is for being immersed in the product after hot pressing incipient fusion in the coagulating bath containing crosslinking agent, and soak time is 0.5～24h.
Described crosslinking agent is formaldehyde, toluene di-isocyanate(TDI), pyromellitic trimethylsilyl chloride, glutaraldehyde, glycerine, acrylic acid, ethylene glycol or oxalic acid.
Described coagulating bath is water, formamide, N, dinethylformamide, N, N-dimethylacetylamide, oxolane, ethanol, isopropanol, n-butanol, 1,4-dioxane, acetone, 1-METHYLPYRROLIDONE, dichloromethane, chloroform, concentration be the aqueous acetone solution of 1～80wt%, concentration be the dichloromethane DMA solution of 10～95wt% or the formamide aqueous solution that concentration is 25～60wt%.
Beneficial effect
(1) preparation method is simple, can fast and easy and the thickness and the uniformity that are accurately controlled function of surface barrier layer, and be easier to the operation accomplished scale production；
(2) can accurately control the variable (temperature, pressure and time etc.) during hot pressing incipient fusion, hot pressing incipient fusion process simple possible, composite filter membrane can be prepared easily and effectively, it is easy to extension produces；Obtained nanofiber-based composite membrane for separation can be used widely in fields such as micro-filtration, ultrafiltration, nanofiltration, counter-infiltrations.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
L polyether sulfone (PES) 24g is dissolved in DMA (DMAC) solvent 76g by (), it is thus achieved that transparent homogeneous electrostatic spinning solution；
(2) it is dissolved in shitosan (CS) 1.0g in 99g deionized water, the water-bath of 50 DEG C carries out magnetic agitation, it is thus achieved that transparent homogeneous electrostatic spray solution；
(3) electrostatic spinning raw material solution in (1) is joined in syringe, by micro-injection pump control extrusion, spout connects high-voltage positive electrode, and electrospinning parameters controls at voltage 20kV, spout aperture 0.7mm, solution flow rate 30 μ L/min, environment temperature 35 DEG C, relative air humidity 35%, carry out electrostatic spinning, the average diameter of the PES electrostatic spinning nano fiber being obtained is 600nm, and deposit thickness is 400 μm, and porosity is 78%；
(4) electrostatic spray stoste in (2) is joined in syringe, by micro-injection pump control extrusion, spout connects high-voltage positive electrode, and electrostatic spray numerical control system is at voltage 35kV, spout aperture 0.7mm, solution flow rate 14 μ L/min, environment temperature 25 DEG C, relative air humidity is 50%, carries out electrostatic spray, the CS electrostatic spray deposit thickness being obtained is 1.5 μm, average diameter 200nm；
(5) before hot pressing, the composite membrane in (4) is placed in acetic acid atmosphere 2min, roughness Ra is used to be that two flat boards of 0.4 carry out hot pressing incipient fusion process to it subsequently, pressure is 1MPa, hold time as 4min, upper plate contact basement membrane (PES), temperature is set to room temperature, lower plate contact composite membrane cortex (CS), temperature is set to 80 DEG C, obtains nanofiber composite filter membrane, and skin thickness is about 400nm.
(6) within 2 hours, nanofiber-based composite membrane for separation is i.e. obtained by crosslinked in the ethanol solution of epoxychloropropane for prepared film.
This composite membrane can be used for nanofiltration, use Liu M H, Zheng Y P, Shuai S, Zhou Q, Yu S C, Gao C J, 2012, desalination, NF membrane performance is estimated by 288:98 cross-current mode, and operating the filtration flux that pressure is the metabisulfite solution to 1000ppm under 0.5MPa is 43L/m2H, rejection is 92%.
Embodiment 2
L polyacrylonitrile (PAN) 10g is dissolved in DMF (DMF) solvent 90g by (), it is thus achieved that transparent homogeneous electrostatic spinning solution；
(2) it is dissolved in polyvinyl alcohol (PVA) 4.0g in 96g deionized water, the water-bath of 90 DEG C carries out magnetic agitation, it is thus achieved that transparent homogeneous electrostatic spray solution；
(3) electrostatic spinning raw material solution in (1) is joined in container, by micro-injection pump control extrusion, spout connects high-voltage positive electrode, and Static Spinning state modulator is at voltage 20kV, spout aperture 0.7mm, solution flow rate 20 μ L/min, environment temperature 55 DEG C, relative air humidity is 35%, carry out electrostatic spinning, the average diameter of the PAN electrostatic spinning nano fiber being obtained is 500nm, and deposit thickness is 800 μm, and porosity is 86%；
(4) electrostatic spray stoste in (2) is joined in container, by micro-injection pump control extrusion, spout connects high-voltage positive electrode, and Static Spinning state modulator is at voltage 30kV, spout aperture 0.7mm, solution flow rate 16 μ L/min, environment temperature 25 DEG C, relative air humidity 45%, carry out electrostatic spray, the average diameter of the colloidal particle of the PVA electrostatic spray being obtained is 300nm, and deposit thickness is 2 μm；
(5) before hot pressing, the composite membrane in (4) is placed in the environment that humidity is 90% 90s, two flat boards using roughness Ra to be 0.4 subsequently carry out hot pressing to it, pressure is 0MPa, hold time as 2min, upper plate contact basement membrane (PAN), temperature is set to room temperature, lower plate contact composite membrane cortex (PVA), temperature is set to 60 DEG C, obtains nanofiber composite filter membrane, and skin thickness is about 300nm.
(6) it is 40% with acetone weight concentration in the mixed solvent of acetone that prepared film is immersed in the water containing glutaraldehyde, soaks crosslinking and i.e. obtains nanofiber-based composite membrane for separation in 1 hour.
This composite membrane can be used for nanofiltration, is estimated film properties in cross-current mode (with embodiment 1), and operating the filtration flux that pressure is the vitamin B12 solution to 100ppm for the 0.5MPa is 58L/m2H, rejection is 98%.
Embodiment 3
L polysulfones (PSU) 25g is dissolved in N by (), in mixed solvent (7:3) 75g of N-dimethylacetylamide (DMAC) and 1-METHYLPYRROLIDONE (NMP), at 60 DEG C, magnetic agitation obtains transparent homogeneous spinning solution；
(2) cellulose diacetate (CDA) 8.0g is dissolved in DMF (DMF) solvent 92g, it is thus achieved that transparent homogeneous electrostatic spray solution；
(3) spinning solution in (1) is joined in container, by micro-injection pump control extrusion, spout connects high-voltage positive electrode, and Static Spinning state modulator is at voltage 28kV, spout aperture 0.5mm, solution flow rate 18 μ L/min, environment temperature 45 DEG C, relative air humidity 25%, carry out electrostatic spinning, the average diameter of the PSU electrostatic spinning nano fiber being obtained is 500nm, and deposit thickness is 400 μm, and porosity is 83%；
(4) electrostatic spray stoste in (2) is joined in container, by micro-injection pump control extrusion, spout connects high-voltage positive electrode, and electrostatic spray state modulator is at voltage 20kV, spout aperture 0.7mm, solution flow rate 18 μ L/min, environment temperature 25 DEG C, relative air humidity 35%, carry out electrostatic spray, the CDA electrostatic spray deposit thickness being obtained is 2 μm, average diameter 2000nm；
(5) before hot pressing, the composite membrane in (4) is placed in DMF solvent atmosphere 60s, two flat boards using roughness Ra to be 0.2 immediately carry out hot pressing to it, pressure is 2MPa, hold time as 5min, upper plate contact basement membrane (PAN), temperature is set to room temperature, lower plate contact composite membrane cortex (CDA), temperature is set to 100 DEG C, obtains nanofiber composite filter membrane, and skin thickness is about 650nm.
This composite membrane can be used for ultrafiltration, with Zhao Z G, Zheng J F, Wang M J, Zhang H Y, Han C C, 2012J.Membr.Sci.394-395:209 film properties is estimated by the mode of report in document, the filtration flux to 1g/L bovine serum albumen solution is 66L/m2H, rejection is 99%.
Claims (6)
1. the method that a hot pressing incipient fusion method prepares nanofiber-based composite filter membrane, comprising:
(1) it is dissolved in functional polymer membrane material in solvent and is configured to the macromolecule spinning solution A that mass fraction is 8～30wt% and enters
Row electrostatic spinning, using the nano fiber non-woven fabric that obtains as the supporting layer of composite membrane, supporting layer nanofiber average
A diameter of 100～1000nm, thickness is 40～200 μm, and porosity is 60%～95%；
(2) will differ from the functional polymer membrane material of step (1) and be dissolved in solvent that to be configured to concentration be that 0.1-10wt% macromolecule is molten
Liquid B, the nonwoven surface then prepared in (1) by the method spraying of electrostatic spray is hindered as the function of composite membrane
Interlayer, the average diameter of the barrier layer particle prepared is 10～1000nm, and thickness is 0.04～20 μm；Described step
(1) the functional polymer membrane material and in (2) is PVAC polyvinylalcohol, polyvinyl phenol PVP, Kynoar
PVDF, polyvinylchloride, cellulose acetate CA, polycaprolactone (PCL), polymetylmethacrylate,
Polycarbonate, 3-hydroxybutyrate and 3-hydroxypentanoic acid copolyesters PHBV, polyaniline PANI, polyacrylonitrile (PAN),
Polylactic acid PLA, polysulfones PSU, polyether sulfone PES, polystyrene PS, polyvinylcarbazole PVK, poly-terephthaldehyde
Acid glycol ester PET, one or several in shitosan CS or polyamic acid PAA；
(3) hot pressing incipient fusion process is carried out to the composite membrane of preparation in (2), then prepare required nanofiber-based point by post processing
From composite membrane；The function barrier layer thickness being formed is 200-2000nm；Wherein, before hot pressing composite membrane at cortex material
Placing in the appropriate solvent atmosphere of material, described appropriate solvent is water, acetic acid or DMF；Hot pressing incipient fusion technological parameter is
Temperature 20～200 DEG C, pressure is 0～50MPa, and the hot pressing incipient fusion time is 1～100min；Last handling process is for by hot pressing
Product after incipient fusion is immersed in the coagulating bath containing crosslinking agent, and soak time is 0.5～24h.
2. the method that a kind of hot pressing incipient fusion method according to claim 1 prepares nanofiber-based composite filter membrane, it is characterised in that: institute
State the solvent in step (1) and (2) be water, ethanol, n-butanol, isopropanol, acetone, 1-METHYLPYRROLIDONE, two
Chloromethanes, chloroform, oxolane, Isosorbide-5-Nitrae-dioxane, formamide, DMF, N, N-
Dimethylacetylamide, concentration are the acetone N that the aqueous acetone solution of 10～95wt%, concentration are 30～95wt%, N-dimethyl
Formamide solution or concentration are the dichloromethane DMF solution of 20～95wt%.
3. the method that a kind of hot pressing incipient fusion method according to claim 1 prepares nanofiber-based composite filter membrane, it is characterised in that: institute
Stating the electrostatic spinning process parameter in step (1) is voltage 8～50kV, spout aperture 0.2～3mm, solution flow rate 5～100
μ L/min, spinning environment temperature is 10～60 DEG C, and the relative humidity of spinning environment is 10～60%.
4. the method that a kind of hot pressing incipient fusion method according to claim 1 prepares nanofiber-based composite filter membrane, it is characterised in that: institute
Stating the electrostatic spray technological parameter in step (2) is voltage 15～50kV, spout aperture 0.1～3mm, solution flow rate 5～40
μ L/min, electrostatic spray environment temperature is 10～60 DEG C, and the relative humidity of electrostatic spray environment is 20～60%.
5. the method that a kind of hot pressing incipient fusion method according to claim 1 prepares nanofiber-based composite filter membrane, it is characterised in that: institute
State crosslinking agent be formaldehyde, toluene di-isocyanate(TDI), pyromellitic trimethylsilyl chloride, glutaraldehyde, glycerine, acrylic acid, ethylene glycol or
Oxalic acid.
6. the method that a kind of hot pressing incipient fusion method according to claim 1 prepares nanofiber-based composite filter membrane, it is characterised in that: institute
State coagulating bath be water, formamide, DMF, DMA, oxolane, ethanol,
Isopropanol, n-butanol, Isosorbide-5-Nitrae-dioxane, acetone, 1-METHYLPYRROLIDONE, dichloromethane, chloroform, concentration
It is the dichloromethane DMA solution or dense that the aqueous acetone solution of 1～80wt%, concentration are 10～95wt%
Degree is the formamide aqueous solution of 25～60wt%.
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