EP3077090A1 - Procédé de production de membranes de polymère à base de poly-(méth)acrylonitrile, membranes de polymère et solutions pour la production d'une membrane de polymère - Google Patents

Procédé de production de membranes de polymère à base de poly-(méth)acrylonitrile, membranes de polymère et solutions pour la production d'une membrane de polymère

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Publication number
EP3077090A1
EP3077090A1 EP14809354.5A EP14809354A EP3077090A1 EP 3077090 A1 EP3077090 A1 EP 3077090A1 EP 14809354 A EP14809354 A EP 14809354A EP 3077090 A1 EP3077090 A1 EP 3077090A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylonitrile
membrane
solvent
poly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14809354.5A
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German (de)
English (en)
Inventor
Detlev Fritsch
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Filing date
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Publication of EP3077090A1 publication Critical patent/EP3077090A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0095—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/06—Specific viscosities of materials involved
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/22—Specific non-solvents or non-solvent system

Definitions

  • the present invention relates to a process for producing a polymer membrane based on poly (meth) acrylonitrile, in which a poly (meth) acrylonitrile-containing solution is used.
  • the solution includes a solvent for poly (meth) acrylonitrile as well as a non-solvent. All of the components of the solution used are non-toxic and do not represent water-polluting chemicals.
  • a solution is described which contains a solvent for poly (meth) acrylonitrile and a non-solvent. The solution is particularly suitable for carrying out the method according to the invention.
  • Polymer membranes for substance separation are generally stable only to a few organic solvents. The best stability is possessed by membranes made of polyvinylidene fluoride (PVDF) or polyacrylonitrile (PAN). These membranes are usually characterized by a phase inversion Onsvon of high-boiling solvents such as dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC) or N-methylpyrrolidone (NMP) produced.
  • the phase inversion process typically produces membranes having an integrally asymmetric structure. This means from the top (feed side) of the membrane ago seen an increasing porosity to the bottom (permeate side).
  • Non-porous membranes can be used for gas separation or nanofiltration, with increasing pore size membranes are obtained for ultrafiltration, microfiltration. These membranes can be used directly for substance separation.
  • the membranes are also suitable as a support (support membrane) of composite membranes.
  • Composite membranes are understood here to mean thin-film composite membranes which consist of this carrier and a subsequently applied layer, generally a further polymer. This layer is the actual separation layer that enables the separation of substances.
  • gas or liquid separation For use in gas separation, a flow of the support membrane of at least 10 times greater than the final flow of the composite membranes is required. As a rule, gas flows greater than 100 m 3 / m 2 hbar are required here. For liquid applications such as ultrafiltration or nanofiltration, water flows of> 50 L / m 2 hbar are generally sufficient. In principle, higher flows mean a higher porosity for small average pore sizes and are desirable.
  • Composite membranes consist of a porous support membrane onto which the actual release layer is applied by known methods such as spraying, printing, roll coating, die coating or spraying or dipping.
  • This release layer usually consists of a second polymer which provides the selectivity.
  • this separating layer In order to achieve sufficient throughput for the technical application, this separating layer must be applied as thinly as possible and without defects.
  • the typical thickness is between 50 and 1000 nm, depending on the application and the material. Be made by suitable methods, such as crosslinking techniques solvent resistant or aging resistant.
  • nanoporous membranes are produced from polyimides, which show a cut-off value below 500 g / mol and are suitable in principle as a carrier material for composite membranes.
  • the pores of these membranes must be protected from collapsing.
  • the membranes are impregnated with hygroscopic substances such as glycerol or low molecular weight polyethylene glycols. This usually prevents use as a carrier material for composite membranes because this treatment prevents a flawless coating.
  • Polysulfone is a very suitable polymer to adjust the pore size, porosity and thus the separation properties.
  • EP 0 362 588 A1 discloses casting solutions which lead to porous membranes.
  • NMP is used as the basic solvent, which is classified as questionable under the REACH process.
  • the specified pore sizes are in the range 100-220 nm and the bubble point is 2-3 bar.
  • the membrane pores are also protected with glycerol from collapsing. By varying the manufacturing conditions, smaller pores are likely to be possible and the bubble point can be raised to improve coatability.
  • polysulfone, especially the finely porous top layer of the membrane has poor resistance to commonly used coating solvents. Thus, polysulfone is less suitable as a base polymer for composite membranes.
  • Polyvinylidene fluoride has good resistance to many low-boiling solvents, and porous membranes which are also suitable for producing composite membranes have been extensively studied [F. Liu, NA Hashim, Y. Liu, MRM Abed, K. Li, Progress in the production and modification of PVDF membranes, J. Membr. Sci., 375 (2011) 1-27].
  • membranes with relatively large pores are produced here, or the casting solutions contain salts such as LiCl or the precipitation bath, solvents such as 1-octanol are added.
  • membranes are made out unmodified PVDF strongly hydrophobic, which is why coatings of many membrane polymers adhere poorly and are not useful as a permanent release membrane.
  • polyacrylonitriles are used with higher comonomer content.
  • the casting or extrusion solution for the preparation of the membranes according to the invention using NMP, NMP mixtures, DMAc / DMF mixtures or DMSO / DMF mixtures is prepared as a solvent.
  • NMP can be used here as such or as a mixed solvent with a content of at least 50% by weight of NMP.
  • DMSO Dimethyl sulfoxide
  • DMAc Dimethyl sulfoxide
  • NC 2 -C 4 alkyl or N-hydroxy-Ci-C 4 -alkylpyrrolidone be used alone or in turn as a mixture.
  • These solvents are to be avoided except for DMSO after the REACH process DE 698 31 305 are prepared from PAN hollow filaments for filtration, which have a complete foam structure.
  • the solvent DMSO is added to the solvent propylene carbonate and mixed with low molecular weight polyethylene glycol as non-solvent in order to come close to the precipitation limit.
  • a high-molecular-weight PAN is used, which results in a very high viscosity, which can be used to produce hollow fibers
  • a pourable solution is usually required
  • Propylene carbonate is an important constituent of the casting solution in DE 69831305. Without this substance it becomes difficult to obtain a membrane with the desired properties Composition of the casting solution is not suitable for flat membranes because of the high viscosity. Thus, other swelling agents or non-solvents must be found.
  • membranes made from the pure solvents DMF, DMAC or DMSO without the addition of swelling or non-solvent agents produce membranes. However, these have very large caverns, which occur just below the separating layer. Thus, the risk of defects is greatly increased and the entire membrane is not suitable for high pressure applications.
  • polyacrylonitrile membranes are described in the literature [N.
  • the object of the invention is therefore in particular a porous carrier. germembrane with the properties
  • This membrane should be in a dry or wet state with polymers of solvents that polyacrylonitrile not swell noticeable or even dissolve coat.
  • claim 7 provides a polymer membrane according to the invention
  • claim 13 relates to a solution for the preparation of a polymer membrane.
  • Copolymer based on poly (meth) acrylonitrile is cast as a film or spun into a hollow fiber, the poly (meth) acrylonitrile, copolymer based on (meth) acrylonitrile or the mixture thereof by a Phaseninversi- onsrea precipitated and the poly (meth ) acrylonitrile, copolymer based on (meth) acrylonitrile or the mixture thereof is stabilized by thermal treatment at elevated temperatures relative to room temperature.
  • solutions which contain only solvents or non-solvents are also available. which are harmless, polymer membranes based on poly (meth) acrylonitrile, make excellent membranes can be produced, which have an optimal distribution of the cavities within the membrane and a high gas flow rate.
  • the membrane can thus be produced after the phase inversion process. Surprisingly, it has been found that excellent results can be achieved even when using only solvents which are not or only to a small extent water polluting and can be readily biodegraded. Solvents classified as unproblematic according to the European Chemicals Ordinance REACH were used in the choice of solvents for the phase inversion process only.
  • the precipitation bath in which the phase inversion is carried out can preferably consist exclusively of water, which is optionally tempered.
  • the membrane should be precipitated exclusively in water without additives, the water temperature during the precipitation process in the range of 15 - 25 ° C should be.
  • the properties of the membrane of the invention are intended to allow use as a support membrane for composite membranes, wherein the support membrane can be coated in a dry or wet state. Impregnating agents to protect the pore structure from changing during drying need not be used.
  • poly (meth) acrylonitrile stands for polyacrylonitriles, which may be added to the
  • Vinyl group can be substituted by a methyl group and thus includes both polyacrylonitrile and polymethacrylonitrile.
  • Copolymers based on (meth) acrylonitrile are essentially derived from the monomeric (meth) acrylonitrile, i. Preferably, these polymers are at least 80 mol% of (meth) acrylonitrile derived. Particular preference is given
  • the solution used according to the invention is free from crosslinkers of poly (meth) acrylonitrile, ie in particular free of amino-containing polymers, which may be selected, for example, from the group consisting of polyethyleneimine (PEI), polyvinylamine, polyallylamine and / or mixtures or Combinations thereof, wherein the polyethyleneimine (PEI), polyvinylamine or polyallylamine preferably has a number average molecular weight Mw of 25,000 to 750,000 g / mol.
  • PEI polyethyleneimine
  • polyvinylamine or polyallylamine preferably has a number average molecular weight Mw of 25,000 to 750,000 g / mol.
  • the solution is cast as a film.
  • the solution is spun through an annular die. In principle, it is conceivable that an air spinning takes place, ie, that before being introduced into the precipitation bath
  • Hollow thread which is produced by the annular nozzle, is transported via an air gap in the direction of the precipitation bath, it is also possible that a direct spinning of the hollow filament takes place in the spinning solution itself.
  • the hollow fiber is already introduced into a hot precipitation bath, in this case, the precipitation bath, for example, temperatures of 80 to 99 ° C, preferably 90 to 97 ° C, especially about 95 ° C have. In this case, precipitation of the precipitate already takes place when the hollow thread enters the precipitation bath
  • the stabilization is achieved by temperature treatment of the film or hollow thread obtained, according to the invention is achieved that a completely homogeneously formed film or hollow fibers is achieved.
  • the film is cast on a substrate.
  • a nonwoven of a polymeric material preferably polyester.
  • Composite membrane can be made.
  • the film or hollow fiber obtained after the phase inversion process can be washed with water.
  • the temperature treatment used for the stabilization is advantageously carried out at temperatures of 50 to 150 ° C, preferably from 70 to 120 ° C, particularly preferably from 85 to 99 ° C. It is particularly preferred and according to the invention in this case, immediately after the precipitation step and / or to the optionally carried out washing step and the temperature treatment is carried out.
  • a water bath is used which has a temperature of more than 50 ° C, preferably 50 to 99 ° C, more preferably 70 to 99 ° C, in particular 85 to 95 ° C.
  • the continuously generated films or hollow fibers are discharged from the precipitation bath and introduced into a tempered water bath.
  • the precipitation, stabilization / washing, drying steps can be done in one machine and a dry membrane according to the invention is obtained. It can also be given, for example, that the films or hollow fibers produced are first removed from the precipitation bath and rolled up to a corresponding stocking roll and the roll itself is tempered, for example, in a water bath. In addition, it is particularly advantageous when carrying out the tempering step in the water bath that any solvent still present in the polymer membrane produced is completely washed out.
  • the temperature treatment is advantageously carried out over a period of 5 minutes to 24 hours, preferably 15 minutes to 12 hours, more preferably from 20 minutes to 60 minutes.
  • a drying of the membrane can be carried out, preferably in an air stream having a temperature between 60 and 150 ° C, preferably between 60 and 120 ° C, more preferably between 80 and 110 ° C or between 110 and 130 ° C.
  • the stabilization step is carried out during the drying step, preferably as described above.
  • the present invention relates to a polymer membrane which can be prepared as described above.
  • the membrane may in principle be formed as a film, it is also conceivable that the membrane has the shape of a hollow thread.
  • the thickness of the membrane without any existing substrate from 20 to 200 ⁇ , preferably from 40 to 90 ⁇ .
  • the thickness of the membrane in this case refers either to the layer thickness of the film or to the thickness of the wall of the hollow thread.
  • this is preferably a nonwoven, in particular a polyester nonwoven.
  • a substrate for example a fleece, in particular a polyester fleece, is particularly preferred in the case of film membranes.
  • the membrane preferably has pores, the pore size at the Bubble point being from 15 to 100 nm, preferably from 20 to 100 nm, particularly preferably from 30 to 50 nm or from 20 to 40 nm.
  • the bubble point of the membranes is in the range of 6 to 32 bar, preferably 6 to 20 bar or 16 to 32 bar, more preferably 15 to 20 bar. For example, this corresponds to a pore size at the bubble point of 40 nm (at 16 bar) to 20 nm (at 32 bar).
  • a porometer Porolux ® 500
  • the bubble point is given at the first measurable flow and corresponds to the largest pore, the pore at the bubble point.
  • the mean pore size is determined as the pore size at 50% of the total flux.
  • the bubble point in conjunction with the average pore size, is a measure of the quality of the membrane obtained. For example, an average pore size of 30 nm at the bubble point with an average pore size of 20 nm represents a very good membrane A pore size at the bubble point of 150 nm at average pore size of 20 nm represents a rather poor membrane.
  • the pore size always corresponds to a pressure with which the membrane is subjected to the measurement. In this respect, it is also possible to define the pore size directly above the bubble point as a function of a pressure. A preferred pore size can thus be defined via the bubble point test.
  • the pressure is preferably> 6 bar (which corresponds to a pore size of about 100 nm), preferably greater than 10 bar (which corresponds to a pore size of about 60 nm) or particularly preferably> 20 bar (which corresponds to a pore size of ⁇ 32 nm corresponds).
  • the bubble point describes the largest pore and thus a measure of imperfections of the membrane.
  • the quality of the membrane thus has two characteristics:
  • defects are measured rather, according to the second criterion, the actual porosity of the membrane.
  • the flow rate of the membrane for gases at the bubble point is typically ⁇ 0.01% of the mean pore size flow.
  • Preferred average or average pore sizes of the membrane according to the invention are from 15 to 30 nm, preferably from 18 to 25 nm.
  • the pores are thereby generated automatically in the precipitation step or in a subsequent washing step and consolidated by the stabilization step.
  • the nitrogen permeability J N2 of the polymer membrane according to the invention is preferably from 10 to 1000 m 3 / (m 2 .h.bar).
  • the determination of the nitrogen permeability is carried out with a gas burette.
  • the gas flow per unit time is measured and related to the area and the pressure.
  • a gas meter such as Definer 220 from BIOS for determining the gas flow is also suitable. It is also possible to determine the determination of the gas flow at 3 bar with a porometer (eg Porolux ® 500).
  • the pores are preferably arranged asymmetrically with increasing pore size in a foam structure from the top to the bottom of the membrane.
  • the membrane may also have caverns in the lower area.
  • the foam structure is formed at least in a thickness of 2 ⁇ .
  • the foam structure is 10 -40 ⁇ up to the caverns, or the membrane is free of caverns.
  • the membrane structure is examined with microelectronic images.
  • the present invention relates to a solution for producing a polymer membrane containing or consisting of
  • Copolymer based on poly (meth) acrylonitrile Copolymer based on poly (meth) acrylonitrile.
  • the non-solvent is selected from the group consisting of acetone, diacetone alcohol, ethyl lactate, 1,3-dioxolane, polyalkylene glycol, in particular polyethylene glycol, tetraalkylene glycol, in particular tetraethylene glycol, alcohols, in particular isopropanol, ethanol, water and mixtures thereof.
  • the content of the non-solvent based on the content of the solvent or the mixture of at least two solvents is preferably 10 to 60 wt .-%, preferably 15 to 45 wt .-%.
  • the polymer used is polyacrylonitrile.
  • Preferred copolymers are obtainable by copolymerization of (meth) acrylonitrile with at least one copolymer selected from the group consisting of (meth) allylsulfonic acid or salts thereof.
  • the solution has a preferred viscosity of 1.5 to 20 Pa.s, preferably 4 to 12 Pa.s or 2 to 10 Pa.s.
  • Fig. La cross section membrane D Table 3 (DMSO / acetone 4/1).
  • Fig. Lb Surface membrane D, Table 3 (DMSO / acetone 4/1).
  • Fig. 2a Cross-section membrane H, Table 3 (DMSO / acetone 7/3).
  • Fig. 2b Surface membrane H, Table 3 (DMSO / acetone 7/3).
  • FIG. 3a shows a cross-section of the membrane 2 from Example 2 (DMSO / diacetone alcohol).
  • Fig. 3b surface of the membrane 2 of Example 2 (DMSO / diacetone alcohol).
  • Fig. 4a Cross-section of the membrane of Example 3 (DMSO / ethyl lactate).
  • Fig. 4b Surface of the membrane of Example 3 (DMSO / ethyl lactate). 5a cross-section of the membrane B from Example 4, Tab. 5, 6 (DMSO / 1.3-
  • FIG. 5b Cross-section of the membrane D from Example 4, Tab. 5, 6 (DMSO / 1,3-dioxolane).
  • Fig. 6a cross section of the membrane F from Example 4, Tab. 5, 6 (DMSO / 1,3-dioxolane).
  • Fig. 7a Cross-section of the membrane I from Example 4, Tab. 5, 6 (DMSO / 1,3-dioxolane).
  • Fig. 7b Surface of the membrane I from Example 4, Tab. 5, 6 (DMSO / 1,3-dioxolane).
  • Polyacrylonitrile is a polymer that is well-suited for polymer membranes. As a homopolymer it has good solvent stability and can nevertheless be processed from some high-boiling solvents into fibers or membranes by the phase inversion process.
  • Commonly used solvents for PANs are, for example, dimethylacetamide (DMAC), dimethylformamide (DMF),
  • GBL ⁇ -butyrolactone
  • NMP N-methylpyrrolidone
  • aqueous solutions of salts such as sodium thiocyanate (NaSCN) and zinc chloride or nitric acid are also used.
  • Dimethyl sulfoxide (DMSO) is used to a lesser extent in the
  • Fiber spiders [see A. Nogaj, C. Süling, M. Schweizer, Fibers, 8.
  • Membranes are usually based on the solvents DMF and NMP. Rarely, DMAC is used.
  • the membrane to be produced should have the largest possible foam structure in order to ensure high pressure stability. Pressures up to 80 bar are common in reverse osmosis and may also be required for an economical process in nanofiltration as well as in gas or vapor separation.
  • DMSO dimethyl methacrylate
  • these substances should show a high to complete water miscibility, be non-toxic and readily biodegradable.
  • membranes were prepared from the pure solvents DMF, DMAC and DMSO by the usual methods. From all these pure solvents, only a thin top layer is formed at the top of the membrane with large caverns close underneath.
  • PAN-1 acrylonitrile (93.5%) - methacrylate (6%) - sodium methallylsulfonate
  • PAN-2 polyacrylonitrile homopolymer (99.5% acrylonitrile).
  • Polyethylene glycol 200 (PEG) and ethyl lactate are examples of polyethylene glycol 200 (PEG) and ethyl lactate.
  • Rotational Viscometer DIN / ISO Viscometer 550 (by Thermo Haake). The value at a speed of 100 rpm is given in Pa * s.
  • REM grid electronic recording. Breakage in liquid nitrogen or surface, both sputtered with Au.
  • Porometers It used 500 a porometers Porolux ®. The bubble point is given at the first measurable flow and corresponds to the largest pore. The mean pore size is the pore size at 50% of the total flux.
  • Nitrogen flow From the porometer measurements of the dry curve, the gas flow is interpolated at 3 bar and given in m 3 / (m 2 * h * bar). Mean values from 3 to 5 test pieces are given.
  • polyester fleece As backing on the membrane drawing machine for the continuous production process, a polyester fleece (PET) was used with a basis weight of about 100 g / m 2 and a thickness of 160 ⁇ .
  • Solvent or solvent mixtures will give a 8-15% Polymer solution prepared. If necessary, the solution is made up to approx.
  • Membrane drawing machine applied via a squeegee to a polyester fleece
  • the membrane is in one
  • the pre-fabricated membrane is storable and ready for use without further treatment.
  • Example 1 membranes of DMSO with acetone as non-solvent.
  • the pull rate was A, B at 2 m / min and B - L at 1
  • nm and a bubble point (BP) should be ⁇ 50 nm.
  • the gas flow in membranes C - L is two to four times greater than the target size of 100
  • the MFP is well within the targeted range at 25 to 20.5 nm.
  • the BP is sometimes greater than 50 nm.
  • the foam structure should comprise more than 10% of the membrane thickness, better 20% or complete foam structure without cavities or voids in the membrane.
  • Membranes H - K achieve 20% foam structure with an absolute thickness of the foam of about 10 ⁇ m.
  • Membrane D is completely free of caverns.
  • the gap height see Tab. 3 Membrane K, L
  • the absolute membrane thickness and the foam content can be controlled.
  • Figure la, b the structure of the membrane D from Tab. 3 in cross section (Fig. La) and the surface (Fig. Lb) is shown.
  • the membrane is completely free of caverns.
  • Figure 2a, b the structure of the membrane H in cross-section (Fig. 2a) and the surface (Fig. 2b) is shown.
  • Approximately 80% of the membrane thickness is formed by caverns.
  • the foam structure is sufficiently strong to avoid defects in the membrane production and to ensure adequate pressure stability.
  • Example 2 DMSO membrane with diacetone alcohol as non-solvent.
  • a 10% polymer solution is prepared using a mixture of DMSO with diacetone alcohol (ratio 3/1).
  • the solution with a dynamic viscosity of 10.9 Pa * s is allowed to stand for degassing overnight and applied to a membrane drawing machine with a gap of 200 ⁇ on a PET nonwoven and precipitated in water of 24 ° C. It will be 80 min. washed at 40 ° C and another 50 min. at 95 ° C.
  • the membrane is dried at 105 ° C for 3 h.
  • the membrane had an N2 flux of 340 m 3 / [m 2 * h * bar], a mean pore size at the bubble point of 42 nm (+/- 2 nm) and an average pore size of 26 nm (+/- 1 nm ).
  • the ratio of DMSO / diacetone alcohol was set to 4/1 and a 10% polymer solution of PAN-2 was used.
  • the dynamic viscosity was 10
  • a membrane was pulled on the membrane drawing machine at a gap of 220 ⁇ m and treated as described above.
  • the dried membrane had an N2 flux of 230 m 3 / [m 2 * h * bar], a mean pore size at the bubble point of 108 nm (+/- 60 nm) and a mean pore size of 31 nm (+/- 4 nm).
  • FIG. 3 a, b shows the SEM image of membrane 2 from example 2.
  • Example 3 membranes with ethyl lactate as non-solvent
  • a 10% polymer solution is prepared from a mixture of DMSO / ethyl lactate (ratio 84/16).
  • the dynamic viscosity of the solution was 10.9 Pa * s.
  • a membrane was produced as in Example 2 on a membrane drawing machine at a gap of 200 ⁇ m.
  • the dry membrane had an N 2 flux of 270
  • Example 4 membranes with 1,3-dioxolane and other additives as non-solvent
  • 1,3-dioxolane was tested. A similar effect is achieved as by the addition of acetone (Example 1), diacetone alcohol (Example 2) and ethyl lactate (Example 3). However, a higher amount of non-solvent is required. With 50% addition of 1,3-dioxolane foam structure is largely achieved without caverns. If a part of the non-solvent 1,3-dioxolane is replaced by TEG or PEG 200 (Table 4 GL No. 5-7, 11), the viscosity of the casting solution increases greatly by 2.8 Pa * s (GL No. 3 , Table 4) to 8 - 9 Pa * s (GL No. 5 - 7, Tab.4).
  • MFP medium pore size
  • BP low bubble point
  • the N 2 fluxes of the membranes of Example 4, prepared according to the general procedure, are in the range of 250-400 m 3 / (m 2 * h * bar).
  • the MFP is at membranes of PAN-2 at 21 to 24.5 nm and the BP is usually around 30 nm with little scattering apparent from the standard deviation of the BP from Table 5. Due to the extensive foam structure is a good compressive strength of the membrane given , Thus, these membranes are very well suited as a substrate for composite membranes.
  • Example 5 membranes of DMSO and 1,3-dioxolane reproducibility
  • Membrane was determined with the bubble point, mean pore size and N 2 flow.
  • Porometer data namely bubble point, pore size and N2 flow of the dried membranes.
  • the membranes can be tempered at 90-95 ° C for half an hour to increase the pressure stability.
  • the pore size, bubble point and gas permeability do not change.
  • FIG. 8 A high-resolution scanning electron micrograph of the membrane from GL No. 3, Table 9 is shown in FIG. 8. Regular pores are found whose mean size is found between 7.7 and 13.8 nm, depending on the model used.
  • membranes with an average pore size of 18-19 nm are obtained which show a bubble point of 22-23 nm.
  • the gas permeability is about 300 m 3 / m 2 * h * bar and stands for high porosity.
  • Membranes of this type are very good as support membranes for

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Artificial Filaments (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé de production d'une membrane de polymère à base de poly-(méth)acrylonitrile, dans lequel une solution contenant du poly-(méth)acrylonitrile est utilisée. La solution comporte un solvant de poly-(méth)acrylonitrile et un non solvant. Tous les composants de la solution utilisés sont non toxiques et ne constituent pas de produits chimiques polluant l'eau. En outre, l'invention décrit une solution, qui contient un solvant du poly-(méth)acrylonitrile et un nom solvant. La solution est appropriée en particulier pour la réalisation du procédé selon l'invention.
EP14809354.5A 2013-12-04 2014-12-03 Procédé de production de membranes de polymère à base de poly-(méth)acrylonitrile, membranes de polymère et solutions pour la production d'une membrane de polymère Withdrawn EP3077090A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013224926.8A DE102013224926A1 (de) 2013-12-04 2013-12-04 Verfahren zur Herstellung von Poly-(meth)acrylnitril-basierten Polymermembranen, Polymermembranen sowie Lösungen zur Herstellung einer Polymermembran
PCT/EP2014/076414 WO2015082546A1 (fr) 2013-12-04 2014-12-03 Procédé de production de membranes de polymère à base de poly-(méth)acrylonitrile, membranes de polymère et solutions pour la production d'une membrane de polymère

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EP3077090A1 true EP3077090A1 (fr) 2016-10-12

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US (1) US20160354730A1 (fr)
EP (1) EP3077090A1 (fr)
JP (1) JP2017504470A (fr)
DE (1) DE102013224926A1 (fr)
WO (1) WO2015082546A1 (fr)

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US11980627B2 (en) 2019-06-14 2024-05-14 Joshua O. Atiba Triple pharmaceutical composition for proteinaceous infection

Citations (2)

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DE69831305T2 (de) * 1997-06-20 2006-06-29 Asahi Kasei Kabushiki Kaisha Hohlfaser-filtrationsmembran auf polyacrylnitrilbasis
JP2012055790A (ja) * 2010-09-06 2012-03-22 Toray Ind Inc 複合中空糸膜の欠陥検出方法

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US4970034A (en) 1988-09-23 1990-11-13 W. R. Grace & Co.-Conn. Process for preparing isotropic microporous polysulfone membranes
JP3171947B2 (ja) * 1991-09-03 2001-06-04 ダイセル化学工業株式会社 ポリアクリロニトリル共重合体選択透過膜およびその製造方法
DE4308150A1 (de) * 1993-03-15 1994-09-22 Miles Inc Semipermeable Membranen aus strukturviskosen Gießlösungen
DE4325650C1 (de) 1993-07-30 1994-09-22 Bayer Ag Membranen aus Acrylnitril-Copolymeren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19546837C1 (de) 1995-12-15 1997-05-28 Geesthacht Gkss Forschung Polyacrylnitril-Membran
DE19546836C1 (de) 1995-12-15 1997-05-28 Fraunhofer Ges Forschung PAN-Kapillarmembran
JP3318251B2 (ja) * 1998-01-14 2002-08-26 旭化成株式会社 ポリアクリロニトリル系中空糸状濾過膜の製造方法
JP2000024475A (ja) * 1998-07-13 2000-01-25 Asahi Chem Ind Co Ltd 熱処理方法
JP2000262873A (ja) * 1999-03-16 2000-09-26 Nitto Denko Corp ポリアクリロニトリル系多孔質膜
GB2437519B (en) 2006-04-28 2010-04-21 Imp Innovations Ltd Method for separation
EP2177603A1 (fr) * 2008-09-25 2010-04-21 Gambro Lundia AB Dispositif pour expansion cellulaire rénale
KR20120083695A (ko) * 2011-01-18 2012-07-26 삼성전자주식회사 폴리아크릴로니트릴계 공중합체, 이를 포함하는 분리막 제조 방법, 이를 포함하는 분리막 및 이를 이용한 수처리 모듈
JP6222625B2 (ja) * 2012-02-16 2017-11-01 富士フイルム株式会社 複合型分離膜、それを用いた分離膜モジュール

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Publication number Priority date Publication date Assignee Title
DE69831305T2 (de) * 1997-06-20 2006-06-29 Asahi Kasei Kabushiki Kaisha Hohlfaser-filtrationsmembran auf polyacrylnitrilbasis
JP2012055790A (ja) * 2010-09-06 2012-03-22 Toray Ind Inc 複合中空糸膜の欠陥検出方法

Non-Patent Citations (1)

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Title
See also references of WO2015082546A1 *

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DE102013224926A1 (de) 2015-06-11
US20160354730A1 (en) 2016-12-08
WO2015082546A1 (fr) 2015-06-11
JP2017504470A (ja) 2017-02-09

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