CN104353369A - Method for preparing nanofiber-based composite filter membrane by hot-pressing incipient fusion method - Google Patents
Method for preparing nanofiber-based composite filter membrane by hot-pressing incipient fusion method Download PDFInfo
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Abstract
The invention relates to a method for preparing a nanofiber-based composite filter membrane by a hot-pressing incipient fusion method. The method comprises the following steps: preparing a spinning solution from functional macromolecules to carry out electrostatic spinning and using an obtained nanofiber non-woven fabric as a supporting layer of the composite filter membrane; preparing a solution from another functional macromolecules and spraying the solution to the surface of a base membrane of the non-woven fabric by an electrostatic spraying method to form a barrier layer of the composite membrane; carrying out processing on the barrier layer of the composite membrane by adopting the hot-pressing incipient fusion method which gives suitable temperature, pressure and hot-pressing time so as to obtain the complete barrier layer; finally, carrying out post processing on the barrier layer to obtain the required nanofiber-based separation composite membrane. The method for preparing the composite filter membrane, which is provided by the invention and is simple and easy to operate, can conveniently and accurately control the thickness and uniformity of the functional barrier layer and is easy to implement scale production; the obtained nanofiber-base composite membrane has a wide prospect in the fields of ultrafiltration, nanofiltration, reverse osmosis and the like.
Description
Technical field
The invention belongs to the preparation field of composite membrane for separation, particularly relate to the method for a kind of hot pressing incipient fusion legal system for nanofiber-based composite filter membrane.
Background technology
Shortage of water resources, water environment degradation are the ubiquitous problems in the world today, and membrane separation technique as a novel high score from, concentrated, purify and purification techniques, advantages such as there is selective height, simple to operate, energy consumption is low, take up an area less, be pollution-free, being used widely in fields such as desalinization, Industrial Wastewater Treatment, environmental pollution improvements, [Xu is another, Xu Zhikang, macromolecule member material, Chemical Industry Press, 2005; S.Judd, B.Jefferson, membrane technology and industrial effluent reusing, Chemical Industry Press, 2006], be the guarantee solving the serious lack of water crisis of China, sewage discharge, raising drinking water quality.One of Synthesis and applications main development direction having become technical field of membrane separation of current composite separating film.
Composite membrane is a kind of Novel separation film developed in recent years, it is composited by very thin and the barrier layer of densification and high porosity basement membrane, this makes composite membrane can choose different materials and preparation technology produces basement membrane and barrier layer, makes their performance reach optimization respectively.Therefore the preparation of composite filter membrane mainly comprises preparation and the compound two parts on micropore basal membrane preparation and ultra-thin top layer, 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 current one simple effective method [RenekerD H, the Chun I1996Nanotechnology7:216 the most preparing the super-fine materials such as continuous nano-fibre; Li D, Xia Y2004Adv.Mater16:1151], the nano fiber non-woven fabric prepared has that fibre number is thin, surface-to-volume is than the Morphological Features large, porosity is high, pore structure is interconnected etc., and there is good mechanical strength and lightweight light weight and absorption property, that 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 JF, 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 of the ultra-thin cortex of current preparation has a lot, mainly contains coating process, spraying process, infusion process, interfacial polymerization, chemical vapour sedimentation method, situ aggregation method etc., and wherein the most frequently used method is cladding process.But due to high porosity and the open-celled structure that is interconnected of nanofiber porous basement membrane, make easily to occur following two problems in the process preparing composite membrane: one easily there is casting solution when being function barrier layer in coating procedure under the phenomenon of oozing; 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 the technology developed based on the high-pressure electrostatic principle that conductor fluid produces high velocity jet after the match, its experimentation can be sketched and be: under normal pressure, analyze the solution of thing by the high-tension capillary of a band, under the about high electric field action of 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 reduces gradually, finally produces 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, the people such as Wang propose nanofiber and hang down molten legal system for composite filter membrane new technology, the method of electrostatic spinning or electrostatic spray is adopted 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, WangX F, Zhu M F, Hsiao B S, 2012J.Membr.Sci.394-395:241; You H, Li X, Yang Y, Wang B Y, LiZ X, Wang X F, Zhu M F, Hsiao B S, 2013Sep.Purif.Technol.108:143], ooze problem and skin thickness problem rambunctious under well solving the casting solution occurred in painting membrane process.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, can only be used for retaining larger-size material (such as emulsion), thus be in a disadvantageous position in suitability for industrialized production, there is limitation in its promotion and application.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for a kind of hot pressing incipient fusion legal system for nanofiber-based composite filter membrane, this preparation method is more simple, can to facilitate and accurate control surface selects thickness and the uniformity of layer, and the operation of more easily accomplishing scale production; The nanofiber-based composite membrane for separation obtained can be used widely in fields such as ultrafiltration, nanofiltration, counter-infiltrations.
A kind of hot pressing incipient fusion legal system of the present invention, for the method for nanofiber-based composite filter membrane, comprising:
(1) functional polymer membrane material is dissolved in solvent be mixed with mass fraction be 8 ~ 30% macromolecule spinning solution A carry out electrostatic spinning, using the supporting layer of the nano fiber non-woven fabric of acquisition as composite membrane, the average diameter of supporting layer nanofiber is 100 ~ 1000nm, thickness is 40 ~ 200 μm, and porosity is 60% ~ 95%;
(2) the another kind of functional polymer membrane material being different from step (1) is dissolved in solvent to be mixed with concentration be 0.1-10% macromolecule spinning solution B, then the nonwoven surface prepared the in (1) function barrier layer as composite membrane 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) process of hot pressing incipient fusion is carried out to composite membrane of preparation in (2), namely give suitable temperature, pressure and hot pressing time to the barrier layer employing heating plate containing appropriate solvent and process and obtain complete barrier layer; Then required nanofiber-based composite membrane for separation is obtained by last handling processes such as chemical crosslinkings; The function barrier layer thickness 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) is water, ethanol, n-butanol, isopropyl alcohol, acetone, 1-METHYLPYRROLIDONE, carrene, chloroform, oxolane, 1,4-dioxane, formamide, N, dinethylformamide, N, the acetone N that the aqueous acetone solution that N-dimethylacetylamide, concentration are 10 ~ 95wt%, concentration are 30 ~ 95wt%, dinethylformamide solution or concentration are the carrene 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 1/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 processing time is 1 ~ 100min.
Last handling process in described step (3) be by hot pressing incipient fusion after product be immersed in the coagulating bath containing crosslinking agent, 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, isopropyl alcohol, n-butanol, 1, the carrene N that the water acetone soln that 4-dioxane, acetone, 1-METHYLPYRROLIDONE, carrene, chloroform, concentration are 1 ~ 80wt%, concentration are 10 ~ 95wt%, N-dimethyl second phthalein amine aqueous solution or concentration are the formamide aqueous solution of 25 ~ 60wt%.
beneficial effect
(1) preparation method is simple, can the thickness of fast and easy and accurate control surface function barrier layer and uniformity, and the operation of more easily accomplishing scale production;
(2) accurately can control the variable (temperature, pressure and time etc.) in hot pressing incipient fusion process, hot pressing incipient fusion process simple possible, can prepare composite filter membrane easily and effectively, is easy to extension and produces; The nanofiber-based composite membrane for separation obtained 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, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
L polyether sulfone (PES) 24g is dissolved in N by (), in N-dimethyl methyl acetamide (DMAc) solvent 76g, obtain transparent homogeneous electrostatic spinning solution;
(2) shitosan (CS) 1.0g is dissolved in 99g deionized water, in the water-bath of 50 DEG C, carries out magnetic agitation, obtain transparent homogeneous electrostatic spray solution;
(3) electrostatic spinning raw material solution in (1) is joined in syringe, controlled to extrude by micro-injection pump, 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 obtained is 600nm, and deposit thickness is 400 μm, and porosity is 78%;
(4) electrostatic spray stoste in (2) is joined in syringe, controlled to extrude by micro-injection pump, spout connects high-voltage positive electrode, electrostatic spray numerical control built in 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 obtained is 1.5 μm, average diameter 200nm;
(5) before hot pressing, the composite membrane in (4) is placed 2min in acetic acid atmosphere, subsequently adopt roughness Ra be 0.4 two flat boards the process of hot pressing incipient fusion is carried out to it, 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, and obtain nanofiber composite filter membrane, skin thickness is about 400nm.
(6) within 2 hours, nanofiber-based composite membrane for separation is namely obtained by crosslinked in the ethanolic solution of epoxychloropropane for obtained film.
This composite membrane can be used for nanofiltration, adopt Liu M H, Zheng Y P, Shuai S, Zhou Q, Yu S C, Gao C J, 2012, desalination, 288:98 cross-current mode is assessed NF membrane performance, and operating pressure is under 0.5MPa be 43L/m to the filtration flux of the metabisulfite solution of 1000ppm
2h, rejection is 92%.
Embodiment 2
L polyacrylonitrile (PAN) 10g is dissolved in DMF (DMF) solvent 90g by (), obtain transparent homogeneous electrostatic spinning solution;
(2) polyvinyl alcohol (PVA) 4.0g is dissolved in 96g deionized water, in the water-bath of 90 DEG C, carries out magnetic agitation, obtain transparent homogeneous electrostatic spray solution;
(3) electrostatic spinning raw material solution in (1) is joined in container, controlled to extrude by micro-injection pump, 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 obtained is 500nm, and deposit thickness is 800 μm, and porosity is 86%;
(4) electrostatic spray stoste in (2) is joined in container, controlled to extrude by micro-injection pump, spout connects high-voltage positive electrode, Static Spinning state modulator at voltage 30kv, spout aperture 0.7mm, solution flow rate 16 μ l/mln, environment temperature 25 DEG C, relative air humidity 45%, carries out electrostatic spray, the average diameter of the colloidal particle of the PVA electrostatic spray obtained is 300nm, and deposit thickness is 2 μm;
(5) before hot pressing by the composite membrane in (4) in humidity be 90% environment in place 90s, subsequently adopt roughness Ra be 0.4 two flat boards hot pressing is carried out 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, and obtain nanofiber composite filter membrane, skin thickness is about 300nm.
(6) obtained film being immersed in acetone weight concentration in the mixed solvent of water containing glutaraldehyde and acetone is 40%, soaks crosslinkedly within 1 hour, namely to obtain nanofiber-based composite membrane for separation.
This composite membrane can be used for nanofiltration, assesses film properties in cross-current mode (with embodiment 1), and operating pressure is the filtration flux of 0.5MPa to the vitamin B12 solution of 100ppm is 58L/m
2h, 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), stir at 60 DEG C of lower magnetic forces and obtain transparent homogeneous spinning solution;
(2) cellulose diacetate (CDA) 8.0g is dissolved in DMF (DMF) solvent 92g, obtains transparent homogeneous electrostatic spray solution;
(3) spinning solution in (1) is joined in container, controlled to extrude by micro-injection pump, 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 obtained is 500nm, and deposit thickness is 400 μm, and porosity is 83%;
(4) electrostatic spray stoste in (2) is joined in container, controlled to extrude by micro-injection pump, spout connects high-voltage positive electrode, electrostatic spray state modulator at voltage 20kv, spout aperture 0.7mm, solution flow rate 18 μ l/min, environment temperature 25 DEG C, relative air humidity 35%, carries out electrostatic spray, the CDA electrostatic spray deposit thickness obtained is 2 μm, average diameter 2000nm;
(5) before hot pressing, the composite membrane in (4) is placed 60s in DMF solvent atmosphere, immediately adopt roughness Ra be 0.2 two flat boards hot pressing is carried out 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, and obtain nanofiber composite filter membrane, 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 the mode reported in document is assessed film properties, be 66L/m to the filtration flux of 1g/L bovine serum albumen solution
2h, rejection is 99%.
Claims (9)
1. hot pressing incipient fusion legal system is for a method for nanofiber-based composite filter membrane, comprising:
(1) functional polymer membrane material is dissolved in solvent to be mixed with mass fraction be that the macromolecule spinning solution A of 8 ~ 30wt% carries out electrostatic spinning, using the supporting layer of the nano fiber non-woven fabric of acquisition as composite membrane, the average diameter of supporting layer nanofiber is 100 ~ 1000nm, thickness is 40 ~ 200 μm, and porosity is 60% ~ 95%;
(2) the functional polymer membrane material being different from step (1) is dissolved in solvent to be mixed with concentration be 0.1-10wt% Polymer Solution B, then the nonwoven surface prepared the in (1) function barrier layer as composite membrane is sprayed by the method for electrostatic spray, the average diameter of the barrier layer particle prepared is 10 ~ 1000nm, and thickness is 0.04 ~ 20 μm;
(3) process of hot pressing incipient fusion is carried out to the composite membrane of preparation in (2), then obtain required nanofiber-based composite membrane for separation by post processing; The function barrier layer thickness formed is 200-2000nm.
2. a kind of hot pressing incipient fusion legal system according to claim 1 is for the method for nanofiber-based composite filter membrane, it is characterized in that: the 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.
3. a kind of hot pressing incipient fusion legal system according to claim 1 is for the method for nanofiber-based composite filter membrane, it is characterized in that: the solvent in described step (1) and (2) is water, ethanol, n-butanol, isopropyl alcohol, acetone, 1-METHYLPYRROLIDONE, carrene, chloroform, oxolane, 1, 4-dioxane, formamide, N, dinethylformamide, N, N-dimethylacetylamide, concentration is the aqueous acetone solution of 10 ~ 95wt%, concentration is the acetone N of 30 ~ 95wt%, dinethylformamide solution or concentration are the carrene N of 20 ~ 95wt%, dinethylformamide solution.
4. a kind of hot pressing incipient fusion legal system according to claim 1 is for the method for nanofiber-based composite filter membrane, it is characterized in that: the 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, spinning environment temperature is 10 ~ 60 DEG C, and the relative humidity of spinning environment is 10 ~ 60%.
5. a kind of hot pressing incipient fusion legal system according to claim 1 is for the method for nanofiber-based composite filter membrane, it is characterized in that: the electrostatic spray technological parameter in described step (2) is voltage 15 ~ 50kV, spout aperture 0.1 ~ 3mm, solution flow rate 5 ~ 40 μ 1/min, electrostatic spray environment temperature is 10 ~ 60 DEG C, and the relative humidity of electrostatic spray environment is 20 ~ 60%.
6. a kind of hot pressing incipient fusion legal system according to claim 1 is for the method for nanofiber-based composite filter membrane, it is characterized in that: the hot pressing incipient fusion technological parameter in described step (3) is temperature 20 ~ 200 DEG C, pressure is 0 ~ 50MPa, and the hot pressing incipient fusion time is 1 ~ 100min.
7. a kind of hot pressing incipient fusion legal system according to claim 1 is for the method for nanofiber-based composite filter membrane, it is characterized in that: the last handling process in described step (3) be by hot pressing incipient fusion after product be immersed in the coagulating bath containing crosslinking agent, soak time is 0.5 ~ 24h.
8. a kind of hot pressing incipient fusion legal system according to claim 7 is for the method for nanofiber-based composite filter membrane, it is characterized in that: described crosslinking agent is formaldehyde, toluene di-isocyanate(TDI), pyromellitic trimethylsilyl chloride, glutaraldehyde, glycerine, acrylic acid, ethylene glycol or oxalic acid.
9. a kind of hot pressing incipient fusion legal system according to claim 7 is for the method for nanofiber-based composite filter membrane, it is characterized in that: described coagulating bath is water, formamide, N, dinethylformamide, N, N-dimethylacetylamide, oxolane, ethanol, isopropyl alcohol, n-butanol, 1, the carrene N that the water acetone soln that 4-dioxane, acetone, 1-METHYLPYRROLIDONE, carrene, chloroform, concentration are 1 ~ 80wt%, concentration are 10 ~ 95wt%, N-dimethyl second phthalein amine aqueous solution or concentration are the formamide aqueous solution of 25 ~ 60wt%.
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