EP3600634A1 - Filtre servant à séparer des fluides hydrophiles et des fluides hydrophobes, ainsi que procédé servant à la fabrication dudit filtre - Google Patents

Filtre servant à séparer des fluides hydrophiles et des fluides hydrophobes, ainsi que procédé servant à la fabrication dudit filtre

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Publication number
EP3600634A1
EP3600634A1 EP18727213.3A EP18727213A EP3600634A1 EP 3600634 A1 EP3600634 A1 EP 3600634A1 EP 18727213 A EP18727213 A EP 18727213A EP 3600634 A1 EP3600634 A1 EP 3600634A1
Authority
EP
European Patent Office
Prior art keywords
group
filter
polymer
fluorine
filter according
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Withdrawn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
EP18727213.3A
Other languages
German (de)
English (en)
Inventor
Benjamin Naier
Herwig Schottenberger
Rania Bakry
Gabriel PARTL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hwk Kronbichler GmbH
Original Assignee
Universitaet Innsbruck
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Filing date
Publication date
Application filed by Universitaet Innsbruck filed Critical Universitaet Innsbruck
Publication of EP3600634A1 publication Critical patent/EP3600634A1/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Withdrawn legal-status Critical Current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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B01D71/281—Polystyrene
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes

Definitions

  • the invention relates to a filter for separating hydrophilic and hydrophobic fluids, wherein the filter comprises, consists of, or is coated with an oleophobic polymer, and wherein the filter exhibits hydrophilic and oleophobic properties.
  • the invention further relates to a method for producing such a filter.
  • hydrophilic and hydrophobic fluids such as water and oil are usually separated from each other industrially mostly by means of water separators.
  • Such apparatuses are usually large, expensive and not very mobile.
  • Filter membranes with hydrophilic and oleophobic coatings are also known from the prior art, with which also a separation of water and oil can take place. However, there are often problems with the technical solutions.
  • US 2015/136712 A1 discloses a composition comprising a hydrophilic and oleophobic co-polymer of an uncharged fluoro (meth) acrylate and a non-fluorinated betaine as co-monomers. Furthermore, membranes are described which have a coating of such a polymer in order to separate water and oil from each other.
  • the linear fluorine chains can be mixed or applied directly with a membrane solution and thus come as a retrofit existing filters in question.
  • the long-chain fluoroacrylates are limited in their solubility and the reaction requires the use of often expensive and toxic fluorine solvents. The synthesis of these polymers also requires the use of environmentally harmful surfactants.
  • US 9,186,631 B2 discloses a hydrophilic membrane with a contact angle for water below 5 ° and a contact angle for oil of over 90 ° C.
  • This membrane consists of a polyethylene diacrylate, 1 / - /, 1 / - /, 2 / - /, 2 / - / - heptadecafluorodecyl polyhedral oligomeric silsesquioxane (F-POSS) and 2-hydroxy-2-methylpropiophenone.
  • F-POSS heptadecafluorodecyl polyhedral oligomeric silsesquioxane
  • the membrane is mechanically stable due to the crosslinker and the technical characteristics are satisfactory.
  • a perfluoroalkyl chain length of CsFi 7 is used and the applications are therefore limited due to the aforementioned legal regulations.
  • polyhedral oligomeric siloxanes represent a very expensive class of substances.
  • Another disadvantage
  • US 2014/0048478 A1 describes a coating for a membrane which contains hydrophilic ethylene glycol segments and oleophobic vinylidene fluoride segments and, by combining these segments, has a contact angle for water of 0 to 60 ° and a contact angle for oil of 40 ° to 100 °.
  • a disadvantage of this technology is that the different membrane segments are often not intermixable with each other or only to a limited extent.
  • no charged monomers or polymers can be used. This causes the membranes to be susceptible to possible contamination.
  • a cross-linked structure can be achieved with these membranes only in a very complex manner.
  • WO 2015/075446 A2 discloses the use of a dip-coating method for filters, in which alternately charged non-fluorine-containing polymers and fluorine-containing surfactants are applied.
  • a disadvantage here is to observe that the fluorosurfactants adhere to one another only because of electrostatic interactions. Therefore, the coating is easily washable and is only durable for a short time. There is also the risk that fluorosurfactants are released into the environment.
  • US 2005/02871 11 A1 discloses the use of cationic fluorosurfactants in polymeric systems and their applications in various fields.
  • hydrophilic and oleophobic membranes with charged fluorosurfactants have been thought to require a mobile fluorine group.
  • “Recent advances in oil-repellent surfaces” International Materials Reviews, 61: 2, 101-126, 2016, “Surface and solid-state properties of a fluorinated polyelectrolyte-surfactant complex", Langmuir, 1999, 15, 4867-4874, as well as “Nano-structured materials with low surface energies formed by polyelectrolytes and fluorinated amphiphiles (PEFA)", Polym. Int., 2000, 49, 636-644).
  • the object of the invention is to provide a hydrophilic and oleophobic filter which is simple and inexpensive to produce and exhibits excellent separation properties of hydrophilic fluids.
  • the invention relates to filters having hydrophilic and at the same time oleophobic properties which comprise, consist of or are coated with an oleophobic polymer.
  • at least a part of the repeating units of the oleophobic polymer is based on a fluorine-containing monomer which is an ionic organic molecule that has an ionic group and a crosslinkable group and a fluorine-containing group in a covalent bond.
  • the filter according to the invention can be used, for example, in the separation of aqueous and oily phases of an emulsion. The aqueous phase may pass through the filter while the oily phase is retained.
  • the filter according to the invention can also be used in the separation of gases or in the separation of gases and liquids with different polarities.
  • the filter can be a fluid-permeable and preferably layer-shaped body, for example a filter membrane, or a fluid-permeable and preferably encapsulated bed.
  • the filter may comprise a substrate such as a membrane which is at least partially coated with a coating comprising or consisting of the oleophobic polymer.
  • suitable substrates include textile materials such as nonwovens or webs of organic or inorganic fibers (eg silk, cotton, lyocell, polyamide or the like), paper, metal nets (eg of stainless steel or bronze), plastic membranes or porous metal or ceramic bodies such as glass frits.
  • Organic fibers include, for example, polyolefin fibers.
  • Porous metal or ceramic bodies include, for example, sintered bodies.
  • suitable coatable materials for plastic membranes include polyurethanes, PVDF (polyvinylidene difluoride), PTFE (polytetrafluoroethylene), expanded PTFE, PSF (polysulfone), polyethersulfone, PAN (polyacrylonitrile), polypropylene, polyethylene, polyamide, polystyrene, polyethylene, metal nets, cellulose-based materials, and combinations it.
  • the filter comprises the oleophobic, partially fluorinated and ion-containing polymer, is made entirely of this or at least partially coated with this.
  • a granular material of a bed, the fibers of a nonwoven, embroidered fibers or a plastic membrane can be made of the described polymer.
  • granular materials of a bed or each of the above-mentioned filter bodies may be at least partially coated with the described oleophobic, partially fluorinated and ion-containing polymer.
  • the average pore size to achieve optimum separation between aqueous and oily phases may be between 0.001 and 1000 ⁇ and preferably between 0.01 and 500 ⁇ .
  • the fluorine-containing group is a perfluorocarbon group.
  • the perfluorinated hydrocarbon group is to be understood as meaning a hydrocarbon group in which all hydrogen atoms have been replaced by fluorine atoms.
  • the fluorine-containing functional group is a group of the type - (CF 2 ) n -F, where n is between 1 and 20 and is preferably 5, 6 or 7.
  • the chain length of 5 to 7 is particularly advantageous because the oleophobic properties are already very pronounced in this chain length, but at the same time there is still a good environmental compatibility.
  • Particularly preferred is the use of a perfluorohexyl group having the structural formula - (CF 2 ) 6-F.
  • fluoro ethers are also conceivable as fluorine-containing groups. These are preferably of the type (CF 2 ) n -O- (CF 2 ) m, where n and m independently of one another can be between 1 and 6.
  • fluorinated benzene derivatives are also conceivable, it being possible for 2 to 5 fluorine atoms or trifluoromethyl groups to be bonded to the aromatic.
  • the crosslinkable group comprises a reactive double bond.
  • allyl groups, (meth) acrylate groups or (meth) acrylamide groups are also suitable in one embodiment.
  • the crosslinkable group comprises an isocyanate, an anhydride, an amine, an acid group, an azide, a diazonium salt or a hydroxyl group.
  • the crosslinkable group is reacted in the oleophobic polymer of the filter according to the invention and forms part of the covalent bond between adjacent repeat units.
  • An unsubstituted vinyl group of the fluorine-containing monomer has in the polymer, for example, the incorporated partial structure of a divalent ethylene group.
  • the ionic group is an ionic heterocyclic and especially heteroaromatic group.
  • the charge is delocalized over several atoms of the ionic group.
  • the ionic group or fluorine-containing monomer is positively charged overall.
  • the ionic group or the fluorine-containing monomer as a whole are simply positively charged.
  • the ionic group is an ionic heterocyclic and especially heteroaromatic group at least one ring-forming nitrogen atom which assumes a positive charge by additional substitution.
  • examples include N, N-disubstituted imidazolium group, NN-disubstituted benzimidazolium group, N-substituted vinylpyridinium group or quaternary ammonium compound.
  • Particularly preferred are N-alkylated groups such as N, N-dialkylated imidazolium groups.
  • the substituent on the nitrogen atom may be, for example, the crosslinkable or fluorinated group which is bonded directly or indirectly, i.e. by means of an intermediate, preferably aliphatic, spacer to the nitrogen atom.
  • the ionic group is located between the crosslinkable and the fluorine-containing group.
  • the structure of the fluorine-containing monomer is such that the crosslinkable and fluorine-containing groups are located radially from the ionic group and preferably the ionic heterocycle.
  • a spacer is arranged between the ionic and the fluorine-containing group and / or between the ionic and the crosslinkable group.
  • the fluorine-containing or crosslinkable group in this embodiment is thus covalently bound to the ionic group by means of an intermediate spacer.
  • Suitable spacers include uncharged and unfluorinated organyl groups.
  • Preferred examples preferably include linear alkylene groups of 1 to 10, and preferably 1 to 5, more preferably 1, 2 or 3 carbon atoms. Especially preferred is ethylene.
  • the spacer comprises an ether bridge (-O-) or thioether bridge (-S-).
  • the fluorine-containing group can be bonded to the spacer via an ether bridge.
  • the spacer can be bonded to the ionic group via a thioether bridge, for example.
  • the fluorine-containing monomer has between 8 and 50, and preferably between 10 and 30, heavy atoms. In the present case, a heavy atom is understood to mean all atoms except hydrogen.
  • the molar mass of the fluorine-containing monomer is between 100 and 3500 g / mol, preferably between 130 and 1000 g / mol.
  • the fluorine-containing monomer is an ionic liquid.
  • the fluorine-containing monomer comprises exactly one ionic, fluorine-containing, and crosslinkable group.
  • the fluorine-containing monomer may also have a plurality of ionic groups and / or a plurality of fluorine-containing groups and / or crosslinkable groups.
  • the fluorine-containing monomer preferably comprises at least two identical or different centers, each of which comprises a charged and preferably also a fluorine-containing group.
  • the centers may be linked by a linker, which preferably connects the ionic groups of the two centers.
  • the linkers may be such groups as described above as spacers.
  • the functionalized monomer has an organosulfanyl group, which is preferably additionally substituted and represents an anionic group.
  • Suitable fluorine-containing cationic monomers include, for example, the compounds shown below:
  • Y represents a crosslinkable group as defined above
  • R f represents a fluorine-containing group as defined above
  • R represents a hydrogen or a C 1-6 alkane.
  • the oleophobic polymer is a co-polymer and at least another portion of the repeat units is based on a hydrophilic co-monomer.
  • the hydrophilic co-monomer has a polymerizable group and an ionic or uncharged hydrophilic group. These co-monomers can increase the hydrophilicity of the co-polymer. Charged such co-monomers can also improve the anti-fouling properties.
  • the additional co-monomer preferably has no fluorine-containing groups. This is preferable from an ecological point of view and, in the given embodiment, facilitates the coordination between hydrophilic and oleophobic properties of the coating.
  • hydrophilic co-monomers include charged or uncharged (meth) acrylate or (meth) acrylamide monomers or
  • (Meth) Acrylamidmonomerderivate Suitable examples of uncharged hydrophilic monomers include those having ethylene glycol or hydroxyl groups as side chains. Other examples include betainic monomers.
  • hydrophilic co-monomer hydrophilic and oleophobic properties of the polymer and thus filter can be matched against each other.
  • the oleophobic properties of the polymer or filter are generally due to the fluorine-containing groups of the fluorine-containing monomer.
  • the higher the content of the fluorine-containing monomers in one of the present embodiments the more oleophobic but also more hydrophobic the polymer is normally.
  • the higher the content of the hydrophilic co-monomer in the present embodiment the more hydrophilic the coating becomes. However, if the proportion of hydrophilic co-monomers becomes too large, the simultaneous oleophobic character is lost.
  • the proportion of repeating units of the co-polymer based on the fluorine-containing monomer is between 0.1 and 50 mol%, preferably between 0.5 and 15 mol%, and more preferably between 1 and 10 mol .-%. In these areas, a sufficient, technically usable oleophobia is achieved and at the same time a too high fluorine concentration is avoided, which is desirable for economic and environmental reasons.
  • the hydrophilic group is a polar or ionic group, for example, an acidic anion. Suitable examples include sulfonates or phosphonates.
  • the co-polymer may also be based on other co-monomers, for example unfunctionalized co-monomers with only one crosslinkable but no otherwise functionalized group, strongly oleophobic monomers having a crosslinkable and fluorine-containing functional group, but no charged functional group or crosslinking comonomer.
  • Cross-linking co-monomers may have at least two crosslinkable but no otherwise functionalized groups.
  • a reactive group may also be present in order to be able to produce a preferably covalent bond to the surface of the substrate
  • Examples of potentially suitable additional comonomers include uncharged fluorine-containing monomers due to fluorine-containing (meth) acrylate monomers and (meth) acrylamide monomers, respectively. These co-monomers can increase the oleophobicity of the co-polymer. Preference may also be given to polymers, oligomers and prepolymers as co-constituents. These may be due to vinylidene difluoride, tetrafluoroethylene, vinyl fluoride, chlorotrifluoroethylene, ethylene-tetrafluoroethylene, perfluoro (ethylene-propylene) and perfluoroalkoxy compounds, as well as combinations of these as monomers.
  • additional co-monomers include reactive and latent monomers, respectively, which are due to reactive or latent (meth) acrylate monomers, (meth) acrylamide monomers, allyl or vinyl monomers. These monomers can increase the adhesion of the polymer to various substrates. Co-monomers which comprise an isocyanate group, a blocked isocyanate group, a polymerizable trialkoxysilyl group, a polymerizable epoxy functionality or a plurality of double bonds may be preferred.
  • hydrophobic monomers which are based on hydrophobic (meth) acrylate monomers or
  • (Meth) acrylamide monomers go back.
  • these monomers contain a branched or unbranched alkyl group.
  • additional co-monomers include (meth) acrylic acid and (meth) acrylic acid derivatives, including acrylic acid, methacrylic acid, 3-sulfopropyl acrylate, hydroxyethyl (meth) acrylate,
  • suitable additional monomers include (meth) acrylamide and (meth) acrylamide derivatives, including 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-acrylamido-2-methylpropanesulfonate, N, N-dimethylaminoethylacrylamide (DMAEAA), N, N- Dimethylaminopropylacrylamide (DMAPAA), trimethylammoniumethyl (meth) acrylate chloride, N-hydroxyethylacrylamide (HEAA), dimethylacrylamide (DMAA), N-isopropylacrylamide (NIPAM), diethylacrylamide (DEAA) and N-tert-butylacrylamide (t-BAA).
  • urethane acrylate, epoxy acrylate and derivatives of the epoxy acrylate can be used.
  • crosslinkable comonomers examples include methylene methyl bis (meth) acrylate, ethylenebis ethyl (meth) acrylate, bisglycidyl methacrylate, urethane dimethacrylate, hexanediol dimethacrylate,
  • Tetraethylene glycol dimethacrylate (poly) ethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dipentaerythritol hexaacrylate, dipentaerythritol penta- / hexaacrylate and
  • Trimethylolpropane ethoxylate triacrylate Trimethylolpropane ethoxylate triacrylate.
  • additional co-monomers include uncharged fluoro (meth) acrylates.
  • examples include ⁇ H, ⁇ H, 2H, 2H-perfluorooctyl (meth) acrylate, pentafluoropropyl (meth) acrylate, and generally branched and unbranched 1H, 1H, 2H, 2H-perfluoroalkyl methacrylates, and 1- (1H, 1H, 2 / - /, 2 / - / - perfluorooctyl) -3-vinyl-1,3-dihydro-2H-imidazole-2-thione.
  • Additional comonomers include uncharged reactive monomers.
  • Examples include glycidyl (meth) acrylate, trimethylvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, triacetoxy (vinyl) silane, Tris (trimethylsiloxy) (vinyl) silane, 3- (trimethoxysilyl) propylnethacrylate, 3- (trimethoxysilyl) propyl acrylate, 3-isopropenyl-a, a-dimethylbenzyl isocyanate, 2-isocyanatoethyl (meth) acrylate, 2- [3,5-dimethylpyrazole) carboxyamino] ethyl (meth) acrylate, 1,1-bis (bisacryloyloxymethyl) ethyl isocyanate, and 2-methyl-2- (2-isocyanatoethoxy) ethyl ester.
  • the above isocyanates are protected from reaction with a blocking agent.
  • Heat or catalyzers can be used to remove the blocking agents.
  • preferred blocking agents include 2-butanone oxime, 3,5-dimethylpyrazole, ⁇ -caprolactam, di-tert-butylamine and tert-butylbenzamine.
  • the additional monomers have a charge and preferably salts of 2-acrylamido-2-methylpropanesulfonic acid, salts of sulfopropyl (meth) acrylic acid, salts of (meth) acrylic acid, salts of [2- (methacryloyloxy ) ethyl] trimethylammonium compounds such as [2- (methacryloyloxy) ethyl] trimethylammonium chloride, (vinylbenzyl) benzyltrimethylammonium compounds, [3- (methacrylamino) propyl] dimethyl (3-sulfopropyl) ammonium hydroxide betaine, diallyldi-methylammonium compounds, salts of maleic acid , Maleic acid esters and combinations thereof.
  • 2-acrylamido-2-methylpropanesulfonic acid salts of sulfopropyl (meth) acrylic acid, salts of (meth) acrylic acid, salts of [2- (methacryloyloxy
  • the additional monomers have additional functionality that can interact with a substrate, and preferably vinyl silanes, (meth) acryl silanes, glycidyl (meth) acrylate, isocyanates, blocked isocyanates, blocked and unblocked 3-isopropenyl-a, a-dimethylbenzyl isocyanate, and combinations of these.
  • the additional monomers have an additional functionality which is neutral and preferably styrene, urethane (meth) acrylates, ester (meth) acrylates, polyethylene (meth) acrylates, linear and branched alkyl (meth) acrylates and fluoro (meth) acrylates or combinations thereof.
  • the fluorine-containing monomers and / or the hydrophilic co-monomers may also be provided that at least some of the fluorine-containing monomers and / or the hydrophilic co-monomers have at least two crosslinkable groups.
  • the proportion of the repolymer units of the co-polymer which are based on monomers or co-monomers having at least two crosslinkable groups, can in one embodiment be between 0.1 and 2 mol%.
  • a higher degree of crosslinking can improve the resistance of the polymer and, when used as a coating, its adhesion to a substrate.
  • Cross-linking may also allow the creation of systems that are recyclable. It can be provided that the monomers having at least two crosslinkable groups comprise two different types of crosslinkable groups, one of these groups containing a physically or chemically cleavable bond, for example by temperature or hydrolysis.
  • the crosslinkable groups of the co-monomers may be formed as described in connection with the crosslinkable groups of the fluorine-containing monomers.
  • the co-polymer is preferably a random co-polymer with randomly distributed repeat units.
  • the filter also includes counterions corresponding to the ionic groups of the fluorinated and optionally hydrophilic monomers, which are, for example, halide anions or alkali metal cations can act.
  • suitable anionic counterions include chloride, bromide, iodide, aryl sulfonate, alkyl sulfonate, perfluoroalkyl sulfonate, alkyl sulfate, sulfate, aryl phosphonate, alkyl phosphonate, monoalkyl phosphate, dialkyl phosphate, (di) hydrogen phosphate, phosphate, hexafluorophosphate, tetrafluoroborate, bicarbonate, carbonate, carbamate, alkyl carbonate, trifluoromethanesulfonate, Bis (trifluoromethylsulfonyl) imide, nonafiat, carboxylate, camphorsulfonate, vinylphosphonate, and
  • a further advantage of the filters according to the invention is that the ionic groups of the polymer inhibit the formation of a filter-blocking biofilm.
  • the filter or the polymer portion or the polymer coating of the filter additionally comprise micro- or nanoparticles in addition to the oleophobic polymer. These can serve to improve the scratch resistance and / or the hydrophobic and oleophobic properties of a coating resulting from the composition.
  • Conductive particles can also be used, for example, to reduce the electrostatic charge or to dissipate frictional heat.
  • suitable nanoparticles include silica particles, titania particles, alumina particles, zinc oxide particles, zirconia particles, silver particles, cellulose particles, carbon nanotubes, graphene, carbon particles, polytetrafluoroethylene (PTFE) particles, polyethylene particles , Polypropylene particles and combinations thereof.
  • a filter according to the invention is used for the separation of hydrophilic and oleophobic components.
  • the presence of pores is essential for the separation performance.
  • the pore size is preferably at 0.001 ⁇ to 1000 ⁇ , preferably at 0.005 ⁇ to 500 ⁇ and more preferably at 0.01 to 250 ⁇ .
  • the pores of a filter according to the invention may be distributed continuously or discontinuously.
  • a filter according to the invention is characterized in one embodiment by the fact that contact angles for water are less than 70 °, preferably less than 40 ° and particularly preferably less than 10 °.
  • the water may pass through the porous structure of the filter.
  • the contact angle for hexadecane or diiodomethane can be above 50 °, preferably above 70 ° and particularly preferably above 90 °.
  • hydrophobic components do not pass through the porous structure.
  • the invention further relates to a method for producing a filter according to the invention comprising the step of providing a solution of the fluorine-containing monomer and optionally the other comonomers, with the step of applying this solution to a substrate, and with the step of Crosslinking of the monomers to form the polymer.
  • the finished filter for example, a finished flow, a finished PTFE membrane or a finished textile
  • the finished filter serve as a substrate starting materials for the production of the filter (for example, the fibers for the production of the web) or textile (the textile fibers or yarns).
  • Suitable methods of crosslinking include thermal processes, radiation, chemical curing or combinations thereof.
  • UV-initiators, thermal radical initiators and / or chemical radical initiators such as peroxodisulfate salts are optionally added to the solution.
  • controlled free radical reactions and reversible deactivating radical polymerizations include atom-transfer-radical polymerization (ATPR), reversible deactivation polymerization, nitroxide mediated polymerization (NMP), reversible addition-fragmentation chain transfer (RAFT) or iodine transfer polymerization (ITP).
  • direct radiation-curing processes such as e-beam curing and polymerizations by means of gamma radiation are conceivable.
  • the ionic fluoromonomers are particularly flexible in the production of membranes for the separation of oil and water from a technical point of view.
  • the ionic fluoromonomers are brought to a porous surface with possible co-monomers in dissolved form, in solvents, in gaseous form, as ionic liquids or as eutectic, where they are directly cured.
  • porogenic pores are produced in a polymer or co-polymer according to the invention, which results in the polymer or co-polymer matrix being able to be used directly as a membrane and no substrate being required.
  • the ionic fluoromonomers are polymerized with possible co-monomers or co-polymers in a liquid, preferably water.
  • a polymer dispersion or copolymer dispersion is obtained.
  • the polymer particles thus obtained in the dispersion have a particle size distribution of 30 nm to 500 ⁇ m, preferably between 50 nm and 50 ⁇ m, and particularly preferably between 90 nm and 500 nm.
  • a described polymer or copolymer can be obtained as a solid. This solid can then be redissolved, thereby obtaining a membrane.
  • the solvent can serve here as a porogen or can be used additional porogens.
  • the preferred viscosity of the polymer solutions or co-polymer solutions for these applications is between 50 mPas and 10,000 mPas, preferably between 100 mPas and 5,000 mPas and particularly preferably between 200 mPas and 1,000 mPas at 20 ° C.
  • the solvent content of the solution in the process according to the invention may generally be between 0 and 99% by weight, preferably between 50 and 99% by weight and more preferably between 70 and 99% by weight.
  • the monomer content of the solution may be, for example, between 0.5 and 99% by weight, preferably 5 to 70% by weight, particularly preferably 10 to 40% by weight.
  • the invention relates to a method for producing a filter according to the invention, which comprises a step of providing a solution of the oleophobic polymer and optionally further polymeric or monomeric components, a step of applying this solution to a substrate and the step of chemical or physical curing of the Polymer solution, preferably a removal of the solvent comprises.
  • the application of the solution can be carried out in the context of this method, for example by spray application or a dipping process.
  • a chemical hardening of the solution of the already crosslinked polymer can be carried out, for example, by an additional cross-linking of the polymer chains.
  • the procedures and additives described above with the alternative method are conceivable.
  • Physical hardening can take place, for example, by simple drying.
  • the solvent content of the solution may generally be for example between 0 and 99% by weight, preferably between 50 and 99% by weight and more preferably between 70 and 99% by weight.
  • the polymer content of the solution may for example be between 0.5 and 99% by weight, preferably 5 to 70% by weight and more preferably 10 to 40% by weight.
  • a viscosity of 1 mPas to 1, 000 mPas, in particular 2 mPas to 500 mPas and further, in particular 3 mPas to 200 mPas at 20 ° C is preferred.
  • the invention thus encompasses spraying methods as well as a direct coating by direct polymerization on a wide variety of substrates.
  • the invention further relates to a process for producing a filter according to the invention, which comprises the step of providing a solution of the oleophobic polymer and optionally further polymeric or monomeric constituents, and the step of precipitation or phase extrusion with an antisolvent.
  • a fiber or membrane can be produced directly from a polymer solution or co-polymer solution by means of an antisolvent.
  • the polymer solution preferably has a viscosity of from 200 mPas to 50,000 mPas, preferably from 500 mPas to 30,000 mPas and particularly preferably from 1,000 mPas to 10,000 mPas at 20 ° C.
  • the solvent of both processes according to the invention may be water or a mixture of at least 30% by volume and preferably at least 50% by volume of water.
  • polar solvents such as water, ethanol or DMF may be suitable, from an ecological and economic point of view water or a solvent with the highest possible water content is to be preferred.
  • the monomers used in the present invention may all be soluble in sufficient concentrations in pure water.
  • the invention comprises the co-polymerization of the fluorine-containing monomer with at least one hydrophilic co-monomer on a permeable substrate.
  • preferred methods of membrane fabrication include thermally-induced phase separation, non-solvent-induced phase separation, evaporation induced phase separation, vapor phase induced
  • the invention relates to a process for the separation of hydrophilic and hydrophobic fluids using a filter according to the invention.
  • Filters according to the invention can generally be used for the separation of aqueous and oily phases. Exemplary applications include water treatment to the collection of spilled oil after oil spills. A removal of fluorine-containing surfactants from wastewater streams can be achieved with filters according to the invention.
  • the charge of the monomers allows a much better solubility in polar solvents. Therefore, the use of only water or alcohols as a solvent is conceivable. This significantly minimizes the emission of volatile organic compounds (VOCs) and leads to much greener processes.
  • VOCs volatile organic compounds
  • the charged fluoromonomers and fluoropolymers themselves are salts which have a non-measurable vapor pressure and thus no intrinsic liquid.
  • Another advantage is that charged fluorine groups have a significantly better anti-fouling behavior than uncharged fluorine groups.
  • Bacterial growth is one of the biggest problems in membrane technology. This can be handled more efficiently by the present invention.
  • Fluorosurfactant molecules are arranged in hydrophilic and fluorophilic segments.
  • the fluoro side chains are in a typical alkanes zig-zag arrangement and not in one for fluoride side chains usually typical helical arrangement in front.
  • the molecules arrange themselves into hydrophilic and oleophobic segments. This can lead to better crystallinity of the fluorine side chains. In simple terms, this means that owing to the ionic structure of the fluoro groups, the oleophobicity of the systems can be increased. These effects allow the use of shorter fluoro chains with consistently high oleophobic properties.
  • Figure 1 a comparison of the behavior of uncoated and coated with an oleophobic polymer substrates to aqueous and oily phases;
  • FIG. 2 shows a test setup for the separation of a water / oil mixture with a filter according to the invention.
  • Figure 1 shows a partially coated in accordance with the invention textile of cotton fibers.
  • the line separates the two halves, with the left half uncoated and the right half coated.
  • the points 1 a and 1 b show each sunflower oil, which was dyed red. The difference is clear.
  • an oil drop forms with a contact angle significantly above 90 °, while in the uncoated area of the drops is absorbed.
  • colored water drops are applied to both sides, which are absorbed by the textile in both cases.
  • the recipe used is described in Example 6 below.
  • FIG. 2 shows a commercially available filter according to the invention coated by Macherey-Nagel.
  • the filter used has the specification MN 616, a basis weight of 85g / m 2 , a thickness of 0.2 mm and an average retention of 4-12 ⁇ .
  • MN 616 a red colored hexadecane for 1 minute.
  • the hexadecane stayed in the filter back and did not pass through the filter, as is the case with an uncoated filter.
  • blue-colored water was added which easily passed through the filter.
  • FIG. 2a shows how water and oil separate after the addition of water in the filter.
  • Figure 2b shows how all water passes through the filter and the oil remains. This picture was taken after 2 hours.
  • the recipe used is described in Example 1 below.
  • the impregnated paper was then irradiated with a UV LED lamp at a wavelength of about 365nm for 3 minutes.
  • the filter obtained was now slightly yellowed at the coated sites (iodine / triiodide).
  • the contact angles of water and hexadecane were measured. Water is the hydrophilic component and hexane represents the hydrophobic component. Each value was measured 3 times and the average recorded.
  • the hexadecane drop remained unchanged for 2 minutes as drops on the filter paper.
  • Example 1 The formulation described in Example 1 was also applied to a commercially available paper towel from Tork. This was also irradiated with a UV LED lamp for 3 minutes. The resulting coating was also yellow. In the case of this substrate, the contact angle was additionally measured with diiodomethane.
  • Example 2 This example is very similar to Example 1, but in this case the more hydrophilic chloride salt of the fluorinated cation was used. The same filter material and process parameters were used as in Example 1. Amount of [mg] substance
  • Example 1 Although the chloride salt of the fluorosurfactant has the significantly higher water solubility, the water droplet on the substrate was absorbed much slower. If the water drop in Example 1 was still submerged under 5 seconds, this was only observed after approx. 15 seconds. The contact angle of water measured at the beginning was 1 15 ° ( ⁇ 4.5).
  • Example 3 The same formulation as in Example 3 was used to coat a cellulose fiber. Due to the many fibers that formed a very inhomogeneous surface, contact angle measurement was not exactly possible because the values fluctuated too much. However, it could be observed that water was absorbed after a few seconds while both hexadecane and diiodomethane remained on the cellulosic tissue for at least 2 minutes.
  • FIG. 1 shows a partially coated cotton textile with the recipe used.
  • Example 6 With the formulation of Example 6, a cotton textile was coated. Subsequently, the textile was cured for 30 minutes with a UV lamp. The resulting textile had hydrophilic and oleophobic properties.
  • Example 7 The formulation prepared in Example 7 was cured for 30 minutes with a UV lamp and showed a special behavior. On a cotton textile, the formulation behaved as a hydrophilic and oleophobic coating, on a glass carrier, however, this formulation showed in a remarkable way hydrophobic and oleophobic properties. This shows that the separation effects can be adapted to the respective surface texture and texture.
  • Example 8 was also cured with a UV lamp for 30 minutes and then applied to a textile. This also showed hydrophilic and oleophobic properties.
  • Example 9 was applied as a textile coating.
  • Example 10 was UV cured for both a textile and a glass support as a monolith for 30 minutes. These formulations showed hydrophilic and oleophobic properties both on glass and on the textile.
  • a commercial polyurethane foam with a pore size distribution between 1 ⁇ and 500 ⁇ was wetted with the two formulations and then cured in a glass jar for 4h at 65 ° C.
  • the resulting, still very flexible membrane was hydrophilic and oleophobic and was suitable for the separation of water and olive oil. Thereafter, the foam was washed more often with water and acetone. Subsequently, water and oil were again successfully separated by means of the membrane.
  • the dried homopolymer from example 15 could be dissolved in excess of 220 g / l in Novec HFE 7100 IPA (3M).
  • the viscosity obtained could be adjusted between 50 mPas and over 5,000 mPas at 20 ° C. Both films and direct membranes or fibers can be produced in this viscosity range.
  • the co-polymer of Example 16 was now partially soluble in organic solvents due to the increased proportion of butyl acrylate. In DMAC and DMF, the polymer was soluble above 20 g / L. This solubility thus allows incorporation into existing polymer membranes such as polysulfones, poly (vinylidene difluoride) or polyacrylonitrile.
  • a hydrophilic and oleophobic membrane can now be produced, for example, as a flat membrane or hollow-fiber membrane.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un filtre servant à séparer des fluides hydrophiles et des fluides hydrophobes. Le filtre comprend un polymère oléophobe, en est constitué ou en est revêtu. Le filtre affiche des propriétés hydrophiles ou oléophobes. Au moins une partie des motifs répétitifs du polymère oléophobe est liée à un monomère contenant du fluor qui est une molécule organique ionique qui présente un groupe ionique, un groupe réticulable ou un groupe contenant du fluor. L'invention concerne en outre un procédé servant à fabriquer un filtre de ce type, ainsi qu'un procédé servant à séparer des fluides hydrophiles et hydrophobes en utilisant un filtre de ce type.
EP18727213.3A 2017-05-18 2018-05-17 Filtre servant à séparer des fluides hydrophiles et des fluides hydrophobes, ainsi que procédé servant à la fabrication dudit filtre Withdrawn EP3600634A1 (fr)

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EP17171765.5A EP3403715A1 (fr) 2017-05-18 2017-05-18 Filtre destiné à séparer des fluides hydrophiles et hydrophobes et son procédé de fabrication
PCT/EP2018/062965 WO2018211025A1 (fr) 2017-05-18 2018-05-17 Filtre servant à séparer des fluides hydrophiles et des fluides hydrophobes, ainsi que procédé servant à la fabrication dudit filtre

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EP18727213.3A Withdrawn EP3600634A1 (fr) 2017-05-18 2018-05-17 Filtre servant à séparer des fluides hydrophiles et des fluides hydrophobes, ainsi que procédé servant à la fabrication dudit filtre

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CN112094107B (zh) * 2019-05-31 2023-08-11 圣戈班研发（上海）有限公司 一种滤器用分离介质、其制备方法以及包含该分离介质的滤器
CN110804462B (zh) * 2019-09-29 2021-07-06 河北金力新能源科技股份有限公司 一种锂离子电池隔膜生产设备流出白油的回收再生方法
CN112494997B (zh) * 2020-10-23 2022-03-25 浙江海洋大学 多孔超亲水疏油材料
CN114452838B (zh) * 2020-11-27 2023-05-05 北京服装学院 一种不对称亲/疏水性复合纤维膜及其制备方法
CN112982030B (zh) * 2021-02-04 2023-06-23 陕西鸿鑫耐斯环保科技有限公司 一种超亲水/水下超疏油滤纸的制备方法
CN116328551A (zh) * 2021-12-23 2023-06-27 江苏泷膜环境科技有限公司 一种stro反渗透膜及其制备方法
EP4616941A1 (fr) * 2024-03-15 2025-09-17 AIRplus GmbH Procédé d'élimination de substances per- et polyfluoroalkyliques

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US3567500A (en) 1968-04-18 1971-03-02 Us Agriculture Fluoroamide-amino polymers and process for imparting oleophobic yet hydrophilic properties to fibrous materials
US9056125B2 (en) 2004-05-17 2015-06-16 Florida State University Research Foundation, Inc. Films for controlled cell growth and adhesion
WO2011159699A2 (fr) 2010-06-14 2011-12-22 The Regents Of The University Of Michigan Matériaux poreux superhydrophiles et oléophobes et procédés pour fabriquer et utiliser ceux-ci
WO2012148359A1 (fr) 2011-04-28 2012-11-01 National University Of Singapore Membrane extrêmement hydrophile et oléophobe pour séparation huile-eau
US9517952B2 (en) 2013-11-15 2016-12-13 General Electric Company Hydrophilic-oleophobic copolymer composition and uses thereof
GB201320676D0 (en) 2013-11-22 2014-01-08 Univ Durham Ultra fast oleophobic-hydrophilic switching surfaces

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