DE102020122857B4 - Process for the production of an ultra-thin free-standing 2D membrane with pores and its application-related modification and use of the 2D membranes produced using this process - Google Patents

Abstract

A method of making an ultrathin 2D freestanding porous membrane (200) involving covalent or noncovalent bonding between monomers at a water-air interface, comprising:• taking the monomers into and mixing with a solvent such that a Monomer-solvent mixture (2) is formed • this monomer-solvent mixture (2) is applied individually to a water surface (3), the monomer-solvent mixture (2) arranging itself at the water-air interface (13) and the solvent evaporating , the monomers remain on the water surface (3) and the water is in an open pool (1) with walls, in which a directed movement of the water surface (3) can be generated between the two opposite pool walls (11 and 12), in which a drag roller (4) divides the pool (1) between the two pool walls (11 and 12) into two areas and with its cross-section partially below the water surface surface (3) is rotated about its longitudinal axis and the application of the monomer-solvent mixture (2) takes place between the first pool wall (11) and the drag roller (4),• the air-facing surface (41) of the drag roller (4) the absorbs monomers from the water surface (3) and releases them back onto the water surface (3) in the direction of the second pool wall (12) and thereby compresses them,• in the area behind the compression in the direction of movement of the water surface (3) towards the second pool wall (12 ) there is an energetic initiator (5) for covalent bonds between the monomers and energy (6) is introduced,• as a result of the effect of the covalent bond, a 2D membrane (8) made of the monomers at the water-air interface (13 ) is formed, • this formed 2D membrane (8) subsequently in the region of the water-air interface (13) by a, the porous carrier material (71) promoting roller (7) in the direction of movement of the water surface (3) towards second be back wall (12) is removed from the water surface (3), so that the porous carrier material (71) is coated on its side facing the water surface (3) in the air with the 2D membrane (8) as a free-standing 2D membrane,• and finally the carrier material (71) provided with the free-standing 2D membrane is dried, characterized in that a photoinitiator is used as the energetic initiator (5) and radiated UV light (6) is used as the energy (6) to polymerize the monomers the polymerization step being followed by a washing step in a solvent bath separated from the water tank and containing a solvent for non-polymerizable small molecules (300), in the first step of the entire process the non-polymerizable small molecules (300) are admixed with the monomers be so that a monomer-molecule-solvent mixture is formed in order to solve by the non-polymerizable small n molecules (300) to generate pores (200) in the ultra-thin free-standing 2D membrane.

Description

The invention relates to a method for producing an ultra-thin, free-standing 2D membrane with pores according to main claim 1 and its application-related modification and use of the membranes produced by this method.

The properties of membranes, such as diffusion throughput, permeability, permselectivity, electrical and optical characteristics, depend decisively on the thickness of the membrane used, which can reach into the nanometer range.

Particularly thin membranes are required for some applications [e.g. in electronics (here the electrical and optical membrane properties can also be influenced by the choice of monomers) or in filtration].

In addition, specific functions and properties of the membranes (e.g. polarization, change in interfacial tension, permeability or other properties) require a uniform orientation of the molecules embedded in the membrane or the molecules that make up the membrane and require the targeted adjustment of their supramolecular structure.

Examples of various membrane functions and the production of these are listed below under points 1 to 3.

1. Continuous production of polymer membranes

• • einen Muldenschieberbettförderer mit einem Endlosband,
• • ein Element zum Zuführen einer unterphasigen Flüssigkeit zur Flüssigkeitsextrusion-Öffnung mit einer zur Geschwindigkeit des Förderers proportionalen Geschwindigkeit, so dass die gewünschte Tiefe der Flüssigkeit ohne Strömung relativ zum Muldenband aufrechterhalten wird;
• • ein Element, das Langmuir-Film bildende Flüssigkeiten und Suspensionen mit einer zur Geschwindigkeit des Förderers proportionalen Geschwindigkeit auf die Oberfläche der Unterphasenflüssigkeit abgibt, so dass eine vorbestimmte Filmdicke beibehalten wird,

und

• • ein Element zum Übertragen des Films auf ein festes Substrat.

WO 1993/022 069 A1 discloses, for example, a system for continuously producing Langmuir and Langmuir-Blodgett film (film for an injection mold for manufacturing radio wave transmission parts for vehicles).

• • a troughing bed conveyor with an endless belt,
• • an element for supplying a subphase liquid to the liquid extrusion orifice at a rate proportional to the speed of the conveyor so that the desired depth of the liquid is maintained with no flow relative to the troughed belt;
• • an element that dispenses Langmuir film-forming liquids and suspensions onto the surface of the subphase liquid at a rate proportional to the speed of the conveyor so that a predetermined film thickness is maintained,

and

• • an element for transferring the film to a solid substrate.

2. Selective membrane for detecting small molecules

From the U.S. 2004/0072360 A1 For example, a semiconductor component for the detection of nitrogen oxide molecules (NO) in gas mixtures, in biological liquids and in aqueous solutions is known. The device is a molecularly controlled semiconductor resistor (MOCSER) with a multilayer GaAs structure with a layer of multifunctional NO-binding molecules adsorbed on the top layer. The sensitivity of the semiconductor device to NO is independent of the composition of the mixture. Nitrogen oxide concentrations as low as 10 ppb NO have been detected in mixtures with various contaminants.

the DE 10 2006 033 528 B3 discloses an arrangement for detecting air constituents, in particular for detecting air constituents in buildings and vehicles, in which several active layers sensitive to gas and a heater are arranged on a substrate, which can be connected to an evaluation unit, the heater being a temperature sensor at the same time and the Resistance of the heater and the resistances of the active layers are connected via electrodes with a total of n+1 electrical connections in such a way that the heater is connected to two connections and n-1 further connections with connection points of the active layers.

3. Free-standing, stable dye membranes to separate reaction spaces, charge and energy transfer

From the WO 2018/229765 A1 for example, a free-standing film based on aromatic materials in the form of a hybrid of organic crystalline materials and inorganic carbon nanomaterials is known. The film, composed of fibrous organic nanocrystals of an aromatic material, is mechanically and thermally stable. This film is optionally reinforced by hybridization with a reinforcing material such as carbon nanotubes, carbon material, a polysaccharide, a metal, a metal alloy, or an organic polymer. The hybrid film of organic nanocrystals and carbon nanotubes has high conductivity and high thermal stability. The films or hybrids of this technical solution are used as microfiltration membranes for various materials, in electrodes or perovskite solar cells.

• • das leitende Material ein Kohlenstoffmaterial enthält,
• • das Kohlenstoffmaterial amorphen Kohlenstoff in Form von Graphen, Graphit, eines einwandigen Kohlenstoffnanoröhrchen oder eines mehrwandigen Kohlenstoffnanoröhrchen enthält

und

• • das leitende Material ein leitendes Polymer ist.

WO 2019/074618 A2 discloses a sensor consisting of a conductive region in electrical communication with at least three electrodes, the conductive region containing a conductive material and a redox-active selector configured to more readily bind an analyte in a first redox state than in a second redox state, where:

• • the conductive material contains a carbon material,
• • the carbon material contains amorphous carbon in the form of graphene, graphite, a single-walled carbon nanotube or a multi-walled carbon nanotube

and

• • the conductive material is a conductive polymer.

WO 2010/005 738 A1 discloses a van der Pauw (VDP) sensor having an electronic circuit electrically coupled to a surface, the surface comprising a type III-V material and the electronic circuit measuring a sheet resistance of the surface using a VDP -Technique measures.

In particular, the VDP sensor may comprise a macromolecule such as a porphyrin, an oligonucleotide, a protein, a polymer or a combination thereof in contact with the surface. The VDP sensors can be arranged in an array of similar or different sensors. An electronic circuit electrically coupled to a two-dimensional electron gas type III-V material, such as InAs or InN, the electronic circuit measuring an electrical property of the two-dimensional electron gas type III-V material.

WO 2012/160 521 A1 teaches a color conversion film comprising at least one active layer, the layer comprising an organic fluorescent dye having a fluorescent core, wherein the dye is substituted with at least one polymeric segment.

The polymer segment is selected from the group consisting of poly(styrene), poly(methyl methacrylate), poly(butyl methacrylate), poly(butyl acrylate), poly(isoprene), poly(butadiene), hydrogenated poly(isoprene), poly(cyclooctene ), poly(tetrafluoroethylene) and its copolymers or poly(isobutylene) and the fluorescent core is selected from the group consisting of naphthalenes, perylenes, terrylenes, quaterrylenes, optionally monosubstituted or polysubstituted.

• a) eine Kammer (210) zur Aufnahme des Fluids und
• b) eine Vielzahl von Ionenaustausch-(IX)-Membranen, die in der Kammer so angeordnet sind, dass sie die Kammer in vier Kammerabteile unterteilen, wobei mindestens eine der iX-Membranen einen photoaktiven Farbstoff umfasst, der kovalent an die iX-Membran gebunden ist (Farbstoff-sensibilisierte iX-Membran), woraufhin Belichtung mit einer Photonenquelle der photoaktive Farbstoff so konfiguriert ist, dass er eine regenerative lichtgesteuerte Dissoziationsreaktion oder lichtgesteuerte Assoziationsreaktion durchläuft, um ein positiv geladenes bewegliches Ion und/oder ein negativ geladenes bewegliches Ion zu erzeugen oder zu entfernen, wobei Ionen in dem Fluid zwischen Kammerabteilen transportiert werden, um die Entionisierung des Fluids in mindestens einem der Abteile zu bewirken.

WO 2019/191 326 A1 discloses a photodialysis machine capable of desalting saline streams. This device can have a desalination rate that is significantly faster than current solar thermal desalination technology. Salt is removed from water by passing an ion current derived from sunlight through this water using dye-sensitized membranes. The device includes:

• a) a chamber (210) for receiving the fluid and
• b) a plurality of ion exchange (IX) membranes arranged in the chamber so as to divide the chamber into four chamber compartments, wherein at least one of the iX membranes comprises a photoactive dye covalently bound to the iX membrane (dye-sensitized iX membrane), upon exposure to a photon source, the photoactive dye is configured to undergo a regenerative light-triggered dissociation reaction or light-triggered association reaction to produce a positively charged mobile ion and/or a negatively charged mobile ion, or to remove ions in the fluid between chamber compartments to effect deionization of the fluid in at least one of the compartments.

U.S. 2019/092885 A1 discloses a method for modulating the interfacial wettability of a noncovalent nanoscopic monolayer or thin film. To this end, a method is taught for modulating the interfacial wettability of a two-dimensional (2D) material using a molecular layer made from a polymerizable amphiphilic monomer having a hydrophilic head and a hydrophobic tail, with improved or reduced wettability of the 2D material is achieved by appropriate assignment of the position of the polymerizable group relative to the hydrophilic head and the hydrophobic tail.

• • Herstellen eines amphiphilen Monomers, Zuweisen einer geeigneten Position für die polymerisierbare Gruppe, relativ zum hydrophilen Kopf und zum hydrophoben Schwanz des amphiphilen Monomers;
• • Zusammenfügen einer Monoschicht oder eines dünnen Films aus dem amphiphilen Monomer; und
• • Polymerisieren des amphiphilen Monomers, wodurch dem 2D-Material eine verbesserte oder verminderte Benetzbarkeit verliehen wird.
• • wobei sich die geeignete Position für die polymerisierbare Gruppe auf ihre Position relativ zu dem hydrophoben Schwanz und dem hydrophilen Kopf bezieht, was ein proximales Alkylkettensegment, das die polymerisierbare Gruppe und den hydrophilen Kopf verbindet, und ein terminales Kettensegment, das die polymerisierbare Gruppe und das Ende des hydrophoben Schwanzes verbindet, erzeugt.

Specifically, this procedure consists of the following steps:

• • preparing an amphiphilic monomer, assigning an appropriate position for the polymerizable group relative to the hydrophilic head and hydrophobic tail of the amphiphilic monomer;
• • assembly of a monolayer or thin film of the amphiphilic monomer; and
• • Polymerize the amphiphilic monomer, giving the 2D material improved or reduced wettability.
• • where the appropriate position for the polymerizable group refers to its position relative to the hydrophobic tail and the hydrophilic head, which is a proximal alkyl chain segment connecting the polymerizable group and the hydrophilic head, and a terminal chain segment connecting the polymerizable group and the connecting the end of the hydrophobic tail.

Polymer membranes are conventionally manufactured by continuous wet spinning, extrusion or racking processes, with the membrane thickness being limited to the micrometer range. The nanometer range is only accessible on a laboratory scale using discontinuous spin coating.

The following are examples of various continuous processes to produce nanometer scale thin films/film layers.

So reveals the DE 44 47 353 C1 for example a method for producing a film layer which reflects radiation of selective wavelengths and is transparent to the remaining wavelengths.

This film layer is produced from aqueous or organo-aqueous solutions of mixtures of gelatin and acrylates and/or methacrylates which are water-soluble or soluble in alcoholic solutions. Surfactants are added to this aqueous or organo-aqueous solution, and inducers and/or hardeners can also be admixed. A solution produced in this way is applied to a carrier material, e.g. PET film or panes of glass, dried and then irradiated with coherent rays in the UV to IR wavelength range.

Target of the irradiation according to the DE 44 47 353 C1 is the interference formation in the layer thus formed.

• • Herstellung eines kompakten Films aus festen Partikeln, die auf einer Trägerflüssigkeit schwimmen, wobei die festen Partikel gegebenenfalls Gegenstände zwischen sich halten;
• • Aufsprühen von Partikeln auf die Seite des kompakten Films, die derjenigen gegenüberliegt, die in die Trägerflüssigkeit eingetaucht ist, derart, dass eine Schicht erzeugt wird, die ein Substrat bildet, das an den festen Partikeln haftet und
• • Herausziehen der erhaltenen Anordnung aus der Trägerflüssigkeit.

the WO 2014/184 303 A1 discloses a method of making an array of particles connected by a substrate, comprising the following sequential steps:

• • producing a compact film of solid particles floating on a carrier liquid, the solid particles optionally holding objects between them;
• • spraying of particles on the face of the compact film opposite to that immersed in the carrier liquid in such a way as to create a layer constituting a substrate adhering to the solid particles and
• • Withdrawing the arrangement obtained from the carrier liquid.

From the WO 2013/117678 A1 a method is known for transferring items onto a preferably moving substrate, wherein the items to be transferred are placed in a transfer area containing a carrier liquid forming a conveyor, wherein a compact particle film keeps the items floating on the carrier liquid of the transfer area, within which the objects are moved with the particle film to be transferred to the substrate. In addition, the method comprises the production of at least one connector on at least one of the objects, the connector being produced using a substance containing a polymerizable compound by bringing it into contact with the object placed in the transfer zone and then the substance is polymerized.

From the WO 2011/050 232 A2 a method and an apparatus for producing a gradient nano-article, a gradient nano-coating and a gradient nano-coating with a low refractive index are known. The method includes providing a first solution of a polymerizable material in a solvent and providing a first environment proximate a first area of the coating and a different second environment proximate an adjacent area of the coating. The method further includes at least partially polymerizing the polymerizable material to form a composition containing an insoluble polymer matrix and a second solution. The insoluble polymer matrix contains a plurality of nanovessels that are filled with the second solution, removing a major portion of the solvent from the second solution. A first volume fraction of the plurality of nanovessels proximate the first region of the coating is less than a second volume fraction of the plurality of nanovessels proximate an adjacent region of the coating. The apparatus for this method includes a transport line, a coating section, a partial polymerization section, and a solvent removal section.

the WO 2003/095 108 A1 discloses a method and apparatus for producing thin layers of particles wherein the particles are deposited onto a carrier fluid which flows by gravity along a ramp leading to a dam. The particles are at the bottom retained at the end of the ramp, causing the particles to stack against each other in a monolayer array.

The apparatus for this method of making monolayers of particles includes a film-forming surface, a fluid delivery system to provide a film of moving fluid on the film-forming surface, a particle delivery system to deposit particles on the film while the fluid flows along the film-forming surface , the fluid film carrying the particles forward to a dam, the dam causing the incoming particles to gather side by side so that they gradually form a layer of particles.

Thereby, the fluid delivery system is arranged at a higher level than the dam to allow the moving fluid to flow by gravity on the film-forming surface, in that the film-forming surface has an inclined surface, the fluid delivery system and the particle delivery system being so arranged that the fluid and the particles are caused to move down the inclined surface towards the dam.

• • Einspritzen eines Flüssigkeitsfilms, der darin dispergierte Teilchen oder Moleküle enthält, auf die Außenfläche eines Drehelements;
• • Einstellen der chemischen Eigenschaften der Teilchen oder Moleküle, wobei ein solcher Einstellschritt die Teilchen oder Moleküle an die Oberfläche des dünnen Flüssigkeitsfilms trägt;
• • Tragen der an der Gas-Flüssigkeits-Grenzfläche des dünnen Flüssigkeitsfilms absorbierten Teilchen oder Moleküle in eine gleichförmige Monoschicht und
• • Übertragen der Monoschicht von der Oberfläche des dünnen Flüssigkeitsfilms auf ein festes Substrat.

WO 2001/089716 A2 discloses a method for preparing monolayers of particles or molecules, comprising the following steps

• • injecting a liquid film containing particles or molecules dispersed therein onto the outer surface of a rotary member;
• • adjusting the chemical properties of the particles or molecules, such adjusting step carrying the particles or molecules to the surface of the thin liquid film;
• • carrying the particles or molecules adsorbed at the gas-liquid interface of the thin liquid film into a uniform monolayer and
• • Transferring the monolayer from the surface of the thin liquid film to a solid substrate.

However, the individual technical solutions described above cannot be easily combined with one another and the disadvantages of these individual technologies are listed below.

In the photo-polymerization at the water-air interface according to the previously known prior art, special mercury vapor lamps are required for the free radical photo-polymerization, which can emit the wavelength of 254 nm required for initiating the polymerization.

The deposition / transfer technology has so far been possible on a laboratory scale as discontinuous deposition on porous / lattice-like carrier material (TEM lattice). As a result, these known discontinuous depositions have the disadvantage that they make the process and the scaling to large-scale processes more difficult.

In the previously described continuous depositions or transfers of films located at the water-air interface onto non-porous carrier materials (substrates), the carrier material always passes through the subphase (the water), which leads to the disadvantage that porous carrier materials due to capillary forces Can "pull" water, which affects the ability of the deposited film and substrate to interact with each other.

When generating pores by electron beam bombardment and phase inversion reactions, the pore size in the low nanometer range is hardly accessible, so that either solution-diffusion membranes or electrically charged pore membranes are used for nanofiltration (particles > 2 nm are retained).

In the case of films made from “Covalent Organic Frameworks” and calix[n]arenes, the pore size depends very much on the molecules used. A flexible control of the pore size, e.g. by simply changing the film formation parameters, is hardly possible. The "molecular building blocks" used must also fit together exactly in order to be able to produce flat 2D films at all.

DE 27 05 193 A1 discloses a method and apparatus for producing and applying a monomolecular layer of amphiphilic molecules to a substrate, in which, in a first step, the layer is formed from a solution of the molecules in a suitable solvent by applying the solution to a liquid surface and removing the solvent and in a second stage a certain surface pressure is applied to the layer thus formed and in a third stage the layer is applied to a substrate, working on a liquid surface which is divided into at least two areas, two adjacent areas of which are separated by a partially in rotating horizontal part immersed in the liquid, introducing the solution of the molecules into one of the zones, removing the solvent and transporting the molecules of the monomolecular layer and applying a specific one to the layer thus formed exerts surface pressure by it is transferred from one area to the adjacent area by rotating the part separating the areas, the two adjacent areas being separated by a horizontal cylinder rotating about its axis.

The production of an ultra-thin free-standing 2D membrane with pores is not possible with the disclosed method and the disclosed device.

EP 3 189 899 A1 discloses a device and a method for obtaining nanostructured coatings on solid surfaces, comprising a processing tank for filling with a working liquid, a drainage device, at least one automated device for spraying a surface solution onto the surface of the working liquid in the form of a monolayer, a device for moving substrates and their displacement through the monolayer at an angle to a horizontal plane, two linear barriers placed along opposite sides of the trough with the possibility of movement in a horizontal plane, and a rotary cylindrical barrier whose axis is parallel to the surface of the working liquid and the linear barriers mounted between said linear barriers, two surface tension sensors, a substrate surface activation unit and an electronic control unit, at least one additionally incorporated A real heat exchanger intended for cooling the working liquid directly below the monolayer, a system for cleaning the working liquid and maintaining its certain level, the two linear barriers being designed for cleaning the surface of the working liquid from the monolayer, and a device for introducing it a working liquid; wherein the cylindrical barrier with the possibility of its vertical movement is mounted in such a way that its axis is located below the level of the working liquid, the angle to a horizontal plane at which the substrates are extracted being in the range from 3 to 30 degrees, where the linear barriers and the cylindrical barrier divide the surface of the working liquid in the processing tank into a zone (A) for automatic loading of the substrates, a zone (B) for spraying the surface solution and a zone (C) for shaping and shifting the monolayer, where the device is designed for continuous processing of the substrate coating.

The production of an ultra-thin free-standing 2D membrane with pores is not possible with the disclosed device and the disclosed method.

The object of the present invention is to provide a method for producing an ultra-thin free-standing 2D membrane with pores, which avoids the disadvantages of the prior art and enables continuous, technically scalable, inexpensive and large-scale production of this with an optional application-related modification and which specify use of the membranes produced by this method.

An ultra-thin, free-standing 2D membrane is to be provided with pores in the range from Å to 10 nm and, if necessary, with dye molecules or sensor molecules through application-related modification.

According to the invention, this object is achieved by the features of claim 1. Further advantageous configuration options of the invention are specified in the subordinate patent claims.

The technical solution is that in the process of producing an ultra-thin free-standing 2D membrane with pores, the continuous, scalable, covalent, energetically initiated connection of monomers takes place at a water-air interface in a water basin, such as the UV Initiated polymerization of photoactivatable monomers (e.g. methyl acrylates) at the water-air interface, with the polymerization step being followed by a washing step in a solvent bath which is separated from the water tank and contains a solvent for non-polymerizable small molecules, with the monomers being Polymerization the non-polymerizable small molecules are admixed to form a monomer-molecule-solvent mixture to generate pores in the ultra-thin free-standing 2D membrane by dissolving out the non-polymerizable small molecules.

The monomers are preassembled before the energetically initiated connection at the water-air interface and are thus covalently connected to a 2D film from a certain order by adding an energetic initiator, such as by adding a photoinitiator as a radical initiator and that Turn on a UV LED (in the range of 300 - 400 nm, e.g. with 365 nm) to polymerize the monomers.

In order to ensure a continuous transfer of this 2D film from the water-air interface to a substrate, a 2D film is required, which is continuously extended along the water surface.

The approach of this technical solution is to divide the water surface into different areas.

The area for spreading the monomers contained in the organic solvent is spatially separated by a drag roller from the areas of monomer compression, the covalent connection of the compressed monomers to a 2D film and the 2D film transfer to a porous carrier material.

After the solvent has evaporated, the individual monomers are transferred to the other area of the water basin using a drag roller, where they are compressed into a continuous film.

As soon as the monomers are at an adequate distance from one another (certain compression conditions have been reached) and the preassembled monomer film has been advanced into the area of energetic initiation, the energetic initiator generates the covalent bonding of the monomers, e.g. by adding the photoinitiator and switching on the UV LED started the polymerization of the photosensitive radicalizable monomers.

The polymerisation initiation takes place at certain intervals or spatially locally and begins at the monomer-polymer boundary in order to promote a continuation of the 2D polymer in one direction of the 2D plane.

After the 2D film has left the area of energetic initiation (e.g. the 2D polymer film the polymerisation area) through further advance, the deposition process takes place. For this purpose, a roll, on which a porous / lattice-like carrier material is stretched and tracked almost endlessly, is placed on the 2D film (e.g. the 2D polymer film) on the water surface.

The direction and speed of rotation of the conveying “separator roller” are the same as the feed direction and feed speed of the 2D film.

A system of rollers continuously feeds the porous/mesh support material to the 2D film on the water surface, the 2D film contacts the support material, adheres to it, and then the support material is fed away again. This carrying of the support material away from the water surface lifts the 2D film from the water surface, so that a free-standing 2D membrane is generated on top of the porous/grid-like support material.

Since the porous / lattice-like carrier material on the conveying "separation roller" is only lowered to the level of the water surface after the 2D film has formed, the porous / lattice-like carrier material does not come into contact with the aqueous subphase. The dry support material can interact directly with the 2D film without first having to displace water that is stuck in the pores, which is a great advantage.

The porous or grid-like support material protects the free-standing 2D membrane, but only from one side. In order to ensure protection on both sides, good handling, transport and operational capability, the free-standing 2D membrane needs to be protected on both sides. For this purpose, the unprotected side of the free-standing 2D membrane is additionally laminated with a second porous/grid-like carrier material. The laminated 2D free-standing membrane can then be integrated into desired target applications.

For certain applications, it is desirable if the free-standing 2D membrane also contains pores and possibly dye or sensor molecules.

In the case of additional pores, according to the invention, a polymerization is carried out at the water-air interface of a mixture of polymerizable monomers and non-polymerizable small molecules. The latter can be added after or before passing through the transfer roller, in any case before the polymerization. Depending on the miscibility and mixing ratio of the monomer and the non-polymerizable small molecule, the cluster size of the non-polymerizable small molecule can be varied.

After polymerisation and transfer to the porous/grid-like carrier material, a washing step (continuous or discontinuous) is integrated, in which the non-polymerisable small molecules are detached from the free-standing 2D membrane, optionally with the aid of ultrasound. This is done according to the invention, in which the washing step is carried out in a solvent bath separated from the water basin, which contains a solvent for non-polymerizable small molecules, in order to generate pores in the ultra-thin free-standing 2D membrane by dissolving out the non-polymerizable small molecules.

The monomers can also be used mixed with chromophores for 2D film formation, which supramole cular structure, surface tension, electrochemical potentials and more.

It is also within the scope of the invention that the monomers for the 2D film formation are also used mixed with individual sensor molecules.

The crosslinking of the monomers with or without chromophore or sensor units does not have to be covalent, but can also take place through electrostatic or van der Waals interactions, in particular London dispersion, dipole and multipole interactions and hydrogen bonds.

• - kontinuierliche und damit leicht skalierbare und kostengünstige Herstellung; auch ohne Subphasenkontakt,
• - bis zu einen Nanometer dünn,
• - mechanisch stabil und damit frei-tragend durch Polymerisation und ggf. Quervernetzung; die Quervernetzung kann auch durch geeignete van der Waals-Wechselwirkungen, also ohne Polymerisation, realisiert werden,
• - einstellbare, einheitliche und wohldefinierte supramolekulare Struktur und molekulare Orientierung,
• - polarisierbar durch Einbau von geeigneten Farbstoffen bzw. Herstellung der Membran aus Farbstoffen,
• - photo-schaltbare Grenzflächenspannung / Adhäsion / Benetzbarkeit des Films,
• - Einstellung der Permeabilität der Membran durch Substanzwahl und Polymerisationsart,
• - gezieltes Einbringen von Nano- bis Mikroporen.

This technical solution enables the production of thin membranes / layers / films with the following combined properties, which are otherwise only achieved individually or dual:

• - continuous and therefore easily scalable and inexpensive production; even without subphase contact,
• - up to one nanometer thin,
• - Mechanically stable and thus self-supporting through polymerisation and, if necessary, cross-linking; the cross-linking can also be realized by suitable van der Waals interactions, i.e. without polymerization,
• - tunable, uniform and well-defined supramolecular structure and molecular orientation,
• - can be polarized by incorporating suitable dyes or by making the membrane from dyes,
• - photo-switchable interfacial tension / adhesion / wettability of the film,
• - adjustment of the permeability of the membrane through the choice of substance and type of polymerization,
• - Targeted introduction of nano to micropores.

The provided 2D free-standing membrane manufacturing process is designed in a scalable manner and delivers a 2D free-standing membrane of up to molecular-thin thickness (about 1 nm) in a protected form, which allows for hassle-free handling in terms of storage, transportation, integration and application guaranteed.

The generation of pores and the optional introduction of dyes or sensors take place during the process of manufacturing the 2D membrane in a fast and energetically favorable way, so that, for example, the permeability of the membranes can be varied in addition to controlling the membrane thickness by incorporating defined pores.

The free-standing 2D membrane with pores laminated with a porous carrier material is a high-performance material that can be produced cheaply and is suitable, among other things, for dead-end filtration and can then be thermally recycled.

In addition, filter membranes of molecular thickness produced in this way significantly increase the filtration performance and speed, since the back pressures that build up are significantly lower.

The well-known polymer chemistry (covalent bonds through light-induced polymerization) is used to produce the free-standing 2D membrane with pores, so that defined two-dimensional polymer films are produced from monomers at the water-air interface in a continuous manner and transferred to a porous carrier material. which enables a large-scale manufacturing process.

Since the polymerisation is started by using a photo-initiable free-radical initiator and, for example, UV LEDs (365 nm), the energy required to initiate the polymerisation is very low, which contributes to cost savings.

According to the invention, the pores are created by mixing in non-polymerizable molecules.

The invention is explained in more detail below with reference to the schematic drawings and the exemplary embodiments, without being restricted to these.

• 1: eine schematische Darstellung einer Ausführungsform einer Anordnung zur Durchführung eines kontinuierlichen Verfahrens zur Herstellung einer freistehenden 2D- Polymermembran und
• 2: eine schematische Darstellung eines kontinuierlichen Waschschritts als Bestandteil in einem Verfahren gemäß 1, welches erfindungsgemäß modifiziert ist, zur kontinuierlichen Herstellung einer freistehenden 2D- Polymermembran, die mit zusätzlichen Poren versehen ist.

show:

• 1 : a schematic representation of an embodiment of an arrangement for carrying out a continuous method for producing a free-standing 2D polymer membrane and
• 2 : a schematic representation of a continuous washing step as a component in a method according to 1 , which is modified according to the invention, for the continuous production of a free-standing 2D polymer membrane, which is provided with additional pores.

Example 1

A method known per se for producing an ultra-thin, free-standing 2D membrane in the form of a 2D polymer membrane, in which the continuous, scalable, and UV-initiated polymerization of photoactivatable monomers takes place at a water-air interface

The one in the 1 The arrangement shown for carrying out the method according to the invention comprises an open tank (1) with tank walls (11, 12) filled with water, so that a water surface (3) is formed with a water-air interface (13), a monomer-solvent mixture ( 2), a drag roller (4) with an air-facing surface (41), a photoinitiator (5), a source of UV light (6), a porous support material (71) conveying roller (7), said porous support material (71) can carry a 2D polymer film (8), and transport roller (10), it also being possible for at least one further conveying roller (9) to be provided.

The concept for this technical structure is that in the production of ultra-thin, free-standing 2D polymer membranes, the continuous, scalable and UV-initiated polymerization of photoactivatable monomers, such as methyl acrylates, takes place at a water-air interface, in which the monomers preassembled before the polymerization reaction at the water-air interface and thus polymerized out of a certain order by adding the photoinitiator as a radical initiator and switching on the UV LED (365 nm) to form a 2D polymer film, which continuously extends along the water surface and is continuously transferred from the water-air interface onto a carrier substrate, the water surface in the open pool (1) being divided into different areas.

The area for spreading the monomer-solvent mixture (2) is spatially separated by the drag roller (4) from the areas of monomer compression, polymerisation and 2D polymer film transfer onto the porous carrier material (71) (see 1 ).

After the solvent has evaporated from the monomer-solvent mixture (2), the isolated monomers are transferred to the other area of the tank (1) using a drag roller (4).

Once the monomers are at an adequate distance from each other (certain compression conditions are reached) and the preassembled monomer film has been advanced into the area of polymerization initiation, adding the photoinitiator (5) and switching on the UV LED as the source of UV light (6) polymerization started.
[Alternatively, the photoinitiator (5) can also be present in the monomer-solvent mixture (2) and is only activated upon UV absorption.]
[As an alternative to being switched on, the UV light (6) can also run permanently if the intensity is appropriate.]

The polymerization can be initiated at specific intervals or spatially locally and starts at the monomer-polymer boundary in order to promote a continuation of the 2D polymer film (8) in one direction of the 2D plane.

After the 2D polymer film (8) has left the polymerisation area through further advance, the deposition process takes place. For this purpose, the conveying roller (7), on which the porous carrier material (71) is stretched and conveyed, is placed on the 2D polymer film (8) on the water surface (3). The direction and speed of rotation of the conveying roller (7) (= "separator roller") are the same as the feed direction and feed speed of the 2D polymer film (8) in the polymerization area.

The feed is between 1 and 1000 nm/min.

Through a system of rollers (7, 9 and 10), the porous/grid-like carrier material (71) is continuously guided to the film on the water surface (3), the 2D polymer film (8) comes into contact with the carrier material (71), adheres to it, and then the carrier material (71) is carried away again.

This removal of the carrier material (71) from the water surface (3) lifts the 2D polymer film from the water surface (3) so that a free-standing 2D polymer membrane is generated on the porous/mesh-like carrier material (71).

Since the porous / grid-like carrier material (71) on the conveying roller (7) (= "separator roller") is only lowered to the level of the water surface (3) after the formation of the 2D polymer film (8), the porous / grid-like carrier material comes (71) advantageously not in contact with the aqueous subphase.

The dry carrier material can interact directly with the 2D polymer film (8) without first having to displace water adhering to the pores, which is a great advantage.

• Es werden Monomere in einem Lösungsmittel aufgenommen und mit diesem vermischt.

The process for the production of ultra-thin free-standing 2D polymer membranes in which the continuous, scalable and UV-initiated polymerization of photoactivatable monomers at a water-air interface takes place using the above arrangement comprises the following steps:

• Monomers are taken up in a solvent and mixed with it.

This monomer-solvent mixture (2) is isolated on a water surface (3). brought, e.g. Dropped on, with the droplets formed of the monomer-solvent mixture (2) arranging at the water-air interface (13), the solvent evaporates, the monomers remain on the water surface (3) and the water is in an open Pool (1) with walls is located, in which a directed movement of the water surface (3) can be generated between the two opposite pool walls (11 and 12), in which a drag roller (4) moves the pool (1) between the two pool walls (11 and 12) divides into two areas and is moved with its cross-section partially under the water surface (3) rotating about its longitudinal axis, the monomer-solvent mixture (2) being dropped between the first pool wall (11) and the drag roller (4),

The surface (41) of the drag roller (4) facing the air takes up the monomers of the monomer-solvent mixture (2) from the water surface (3) and releases them back onto the water surface (3) in the direction of the second pool wall (12). and is thereby compressed.

A photoinitiator (5) is located in the area behind this compression of the monomers of the monomer-solvent mixture (2) in the direction of movement of the water surface (3) towards the second pool wall (12). At the same time, UV light (6) is radiated into this area.

As a result of the effect of the photoinitiator (5) and the UV light (6), a 2D polymer film is formed from the monomers at the water-air interface (13).

This formed 2D polymer film (8) is then rolled in the area of the water-air interface (13) by a roller (7) that conveys the porous carrier material (71) in the direction of movement of the water surface (3) towards the second pool wall (12 ) removed from the water surface (3), so that the porous carrier material (71) is coated/applied on its side facing the water surface (3) in the air with the 2D polymer film (8) as a free-standing 2D polymer membrane,

Finally, the carrier material (71) provided with the free-standing 2D polymer membrane is dried.

Advantageously, between the step of coating the porous support material (71) on its side facing the water surface (3) in air with the 2D polymer film (8) and the step of drying the support material (71) provided with the free-standing 2D polymer membrane a further method step is added, in which a further, likewise porous carrier material (71) conveying roller (9) is arranged in the direction of movement of the water surface (3) towards the second pool wall (12) in the air, through which the carrier material (71) is brought into contact with the previously still carrier material (71)-free side of the 2D polymer film (8), so that a free-standing polymer membrane (81) protected on both sides by the carrier material is formed, which can be removed via a transport roller (10).

The advantage of this technical process is that it is carried out continuously, thereby enabling a cost-effective production of free-standing 2D polymer membranes, which are protected on one or both sides by a carrier material, in an industrial process flow, with subsequent to this process according to the prior art Technology, an application-related modification of these membranes is possible in order to use them, for example, in the field of nanofiltration, reverse osmosis, health technologies (e.g. dialysis and sensor technology) and energy technologies (storage and photovoltaic technologies).

Example 2

Process for producing an ultra-thin free-standing 2D membrane according to the invention in the form of a 2D polymer membrane with additional pores, in which the continuous, scalable and UV-initiated polymerization of photoactivatable monomers takes place at a water-air interface

In order to obtain a free-standing 2D polymer membrane (8) with additional pores (300), it is necessary in the method described in exemplary embodiment 1 that the polymerization at the water-air interface is carried out according to the invention with a mixture of polymerizable monomers (2) and not polymerizable small molecules (300).

The non-polymerizable small molecules (300) are added in the area of the basin (1) before or after the drag roller (4) (in any case before the polymerization).

Depending on the miscibility and mixing ratio of polymerizable monomer (2) and non-polymerizable small molecule (300), the cluster size of non-polymerizable small molecule (300) can be varied.

After polymerization and transfer to the porous/grid-like support material (71), a washing step (continuous or discontinuous) is integrated into the process known per se (see 2 , to the continuous Washing step (the discontinuous washing step in the form of immersion is not shown) in which the non-polymerizable small molecules (300) are detached from the free-standing 2D polymer membrane (8), advantageously with the aid of ultrasound.

For this purpose, during the continuous washing step, in the area after the conveying roller (7) and after the photopolymerization area, an area (100) separated from the water of the basin (1) is provided, in which the porous / lattice-like support material (71), which the free-standing 2D polymer membrane (8) carries, over the rollers (110 and 120) through a solvent bath containing a solvent for the non-polymerizable small molecules (300) and may be an ultrasonic bath out.

As a result, the non-polymerizable small molecules (300) are dissolved out of the 2D polymer membrane (8) to form the desired pores (200).

However, it is also within the scope of the invention that, as an alternative to the discontinuous washing step after the conveying roller (7), individual batches of porous/grid-like carrier material (71) with a free-standing 2D polymer membrane + non-polymerizable small molecules in this membrane are removed from the process and be treated in batches in the solvent bath, which can be an ultrasonic bath, in order to extract the non-polymerizable small molecules from the 2D polymer membrane and thereby form the desired pores.

The monomers can also contain chromophores known from the prior art or, in a novel way, fluorophores that cause light-controlled polarization of the 2D polymer membrane and light-controlled variation of other properties, such as permeability, supramolecular structure, surface tension, electrochemical potentials and enable further.

The free-standing 2D membranes produced by the continuous, technically scalable process with a continuous washing step can thus be provided with pores in the range from Å to 10 nm, with an application-related modification also following this process according to the prior art of these membranes is possible in order to use them, for example, in the field of nanofiltration, reverse osmosis, health technologies (e.g. dialysis and sensor technology) and energy technologies (storage and photovoltaic technologies).

Comparative example 3

Process for the production of an ultra-thin 2D photoswitchable membrane without pores (prior art)

For the production of a photoswitchable 2D membrane, which changes its surface properties, in particular surface tension / adhesion / wettability, but also supramolecular structures, polarity, permeability, electrical and optical membrane or layer properties, under illumination, so that the membrane / surface coating in the sensor or for the delamination of biofilms, for example an amphiphilic 4-hydroxy-1,3-thiazole is used.

Alternatively, however, other dyes that change surface polarity via electron density redistribution through absorption can also be used.

For the continuous production of the 2D membrane, the in 1 shown arrangement used, wherein the 4-hydroxy-1,3-thiazole with a concentration of 0.1 mmol / l (or in the range 0.01 - 1 mmol / l) with the solvent chloroform as a monomer solvent mixture (2) dropwise applied (batchwise or continuously) to the water surface at the water-air interface (13) [= in the spreading area], the (spreading) volume flow being 200 µl/s (or in the range 20 - 2000 gl/s), resulting in an average area per molecule of 120 Å ² (or in the range 90 - 200 Å ² ) on the available subphase surface.

A displacement speed of 60 mm/min or in the range of 1 - 3000 mm/min is generated via the drag roller (4), so that the monomers/molecules are transferred to the water surface (3) and their surface concentration there becomes a dense packing (corresponding to a condensed Phase which allows the switching of the interface properties) is increased, so that the 4-hydroxy-1,3-thiazole located at the water-air interface (13) are successively compressed to form a 2D membrane in the form of a Langmuir film.

This 2D membrane is immobilized by depositing the packed 4-hydroxy-1,3-thiazole film on all types of surfaces to be functionalized, e.g. foils, but also molded parts in the form of the carrier material (71).

The speed of the separation is selected in such a way that there is a constant boundary surface pressure in the separation basin (in the range 1 - 3000 mm/min, typically slightly lower than the speed of the transfer roller).

In order to switch the adhesion of analytes or contaminants to sensor surfaces, the membrane described above can be deposited on transistors, semiconductor or conductor layers or a transparent film in order to realize transistor- or resistance-based sensors or photometric sensors.

Comparative example 4

Process for manufacturing an ultra-thin vdW 2D membrane without pores (state of the art)

An amphiphilic protoporphyrin IX and methylene blue are used to produce an ultra-thin and asymmetrically polarizable 2D membrane (vdW 2D membrane), in which energy and charge transfer, in particular light-driven or electrically controlled, and, if necessary, diffusion through it is possible used as monomer-solvent mixture (2).

Alternatively, the combinations of fluorophore and ionic or non-ionic dye are also useful, as long as one molecular species is water soluble and one is water insoluble. The water-insoluble component forms the 2D membrane film at the water-air interface (13), with both components having to exert attractive intermolecular interactions on one another.

The molecules of the water-soluble component either exert attractive intermolecular forces on one another, have more than one functional group that exerts an intermolecular bond to the water-insoluble component, or meet both of the above criteria.

The continuous production of the polarizable 2D membrane (vdW 2D membrane) takes place with a device according to 1 , wherein the protoporphyrin IX with a concentration of 0.005 mmol/l (or in the range 0.006 - 0.0001 mmol/l) with the solvent chloroform as a monomer-solvent mixture (2), dropwise (batchwise or continuously) onto the water surface (3) is applied with a (spreading) volume flow of 200 µl/s (or in the range 20 - 2000 µl/s), so that an average area per molecule of 200 Å ² (or in the range 150 - 600 Å ² ) on the available Subphase surface results.

The molecules are transferred to the water surface (3) at a displacement speed of 60 mm/min (or in the range of 1 - 3000 mm/min) via a drag roller (4), with the methylene blue being dissolved in a concentration of 0.1 mmol /l (or in the range 1 - 0.01 mmol/l) and there its surface concentration increases to a dense packing (corresponding to a condensed phase) and thus the fluorophores located at the water-air interface (3) - ionic dye mixture can be successively compressed into a 2D membrane in the form of a Langmuir film.

This 2D membrane is immobilized by depositing the packed fluorophore-ionic dye mixture film on microgrids/networks as carrier material (71), which are continuously fed to the system described above.

Alternatively, the 2D membrane can also be deposited on semiconductor or conductor layers or a transparent film.

The speed of the deposition is chosen so that there is a constant boundary surface pressure in the open basin (1) (in the range 1 - 3000 mm/min, typically slightly lower than the speed of the transfer roller).

The D membranes manufactured in this way are universally applicable, so that they can be used in gaseous, liquid, gel-like, solid environments and combinations thereof and are chemically resistant.

Comparative example 5

Production of a sensor layer without pores for use in the detection of nitrogen monoxide (not the subject of the invention)

For the production of an ultra-thin and 2D membrane that changes its electronic and optical properties upon binding of nitric oxide (NO), an important biomarker, so that the binding of NO can be read out electronically, e.g. by means of transistors, or photonically/photometrically, an amphiphilic iron(III) corrol dye (hereinafter referred to as “corrol” for short) is used as the monomer/solvent mixture (2) in combination with tris base or tris(2-aminoethyl)amine. As an alternative to “corrol”, other (transition) metal complexes that can bind nitrogen monoxide, possibly reversibly, are suitable.

As an alternative to the tris base or tris(2-aminoethyl)amine crosslinker, other molecules having multiple Lewis base groups can be used.

The continuous production of the 2D membrane is carried out by mixing the corrol with a concentration of 0.1 mmol/l (or in the range 0.01 - 1 mmol/l) together with the solvent: chloroform:methanol (70:30, or in the range 90:10 to 60:40 or other suitable solvents or solvent quantities mix)] as a monomer-solvent mixture (2) dropwise (batchwise or continuously) onto the water surface (3) at the water-air interface (13) (= spreading area), the (spreading) volume flow being 200 μl/s (or in the range 20 - 2000 µl/s), resulting in an average area per molecule of 200 Å ² (or in the range 20 - 2000 Å ² ) on the available subphase surface.

The molecules in the basin (1) are attached to the water Air interface (13) transferred and there their surface concentration to a dense packing (corresponding to a condensed phase) increases and thus the at the water-air interface (13) located corrole successively compressed to a 3D membrane in the form of a Langmuir film .

During this compression, the above-mentioned cross-linking agent is fed into the subphase of the separating tank as an aqueous solution in the same mass flow rate as the corrol. This feed is adjusted during the process in such a way that a constant pH value is established. The amino groups of the crosslinker bind to the acid groups of the corrole and thus stabilize the 2D membrane film through crosslinking.

The immobilization of this 2D membrane (cross-linked corrol film) is deposited on transistors, which have been immobilized on a foil as a carrier material (71) and are continuously fed to the system described above.

Alternatively, the layer can also be deposited on semiconductor or conductor layers or a transparent film in order to implement a resistance-based or photometric sensor system instead of a transistor-based sensor system.

The speed of the separation is selected in such a way that there is a constant boundary surface pressure in the separation basin (in the range 1 - 3000 mm/min, typically slightly lower than the speed of the transfer roller).

To protect this 2D membrane and as a permselective functional layer, a 2D polymer membrane can also be applied to the corrole film in accordance with exemplary embodiment 1, with the monomer here as bisphenol A dimethacrylate, the radical initiator as azobis(isobutyronitrile) AIBN for short or phenylbis( 2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure 819) and the UV wavelength for polymerization initiation can be chosen as 365 nm (300-400 nm).

The 2D membranes produced in this way with additional sensor molecules in the form of NO sensor molecules, in which the energetic initiation of monomers takes place at a water-air interface, can be used universally for nitrogen monoxide measurements.

Reference List

1

open pool

11, 12

pool walls

13

water-air interface

2

monomer solvent mixture

3

water surface

4

drag roller

41

air-facing surface

5

energetic initiator

6

contributed energy

7

promoting role

71

porous carrier material

8th

2D membrane, e.g. 2D polymer film

9

second promotional role

10

transport roller

100

area separated from the water of the pool (1) (solvent bath

110, 120

Rollers for transport through the solvent bath

200

pore

300

non-polymerizable small molecules

Claims (9)

A method of making an ultrathin 2D freestanding porous membrane (200) involving covalent or noncovalent bonding between monomers at a water-air interface, comprising: • taking the monomers into and mixing with a solvent such that a Monomer-solvent mixture (2) is formed, • this monomer-solvent mixture (2) is applied individually to a water surface (3), the monomer-solvent mixture (2) arranging itself at the water-air interface (13), the solvent evaporates , the monomers remain on the water surface (3) and the water is in an open pool (1) with walls in which between the two opposing pool walls (11 and 12) a directed movement of the water surface (3) can be generated by a drag roller (4) dividing the pool (1) between the two pool walls (11 and 12) into two areas and with its cross section partially below the water surface (3) is rotated about its longitudinal axis and the application of the monomer-solvent mixture (2) takes place between the first pool wall (11) and the drag roller (4), • the air-facing surface (41) of the drag roller (4) the absorbs monomers from the water surface (3) and releases them back onto the water surface (3) in the direction of the second pool wall (12) and thereby compresses them, • in the area behind the compression in the direction of movement of the water surface (3) towards the second pool wall (12 ) there is an energetic initiator (5) for covalent bonds between the monomers and energy (6) is introduced, • as a result of the effect of the covalent bond, a 2D membrane (8) from the Mo nomeren is formed at the water-air interface (13), • this formed 2D membrane (8) subsequently in the area of the water-air interface (13) by a, the porous carrier material (71) promoting role (7) in Direction of movement of the water surface (3) toward the second pool wall (12) is removed from the water surface (3), so that the porous carrier material (71) on its water surface (3) facing side in the air with the 2D membrane ( 8) is coated as a free-standing 2D membrane, • and finally the support material (71) provided with the free-standing 2D membrane is dried, characterized in that a photoinitiator is used as the energetic initiator (5) and a photoinitiator is used as the energy (6) introduced UV light (6) is irradiated to polymerize the monomers, with the polymerization step being followed by a washing step in a solvent bath separated from the water tank, which contains a solvent for non-polymerizable small M contains molecules (300), the non-polymerizable small molecules (300) being admixed to the monomers in the first step of the entire process, so that a monomer-molecule-solvent mixture is formed in order to, by dissolving the non-polymerizable small molecules (300) Generate pores (200) in the ultrathin free-standing 2D membrane. procedure according to claim 1 , characterized in that between the step of coating the porous support material (71) on its side facing the water surface (3) in air with the 2D polymer film (8) and the step of drying the support material provided with the free-standing 2D membrane (71) a further process step takes place, in which a further roller (9), which also conveys porous carrier material (71), is arranged in the direction of movement of the water surface (3) towards the second pool wall (12) in the air, through which the carrier material (71) is brought into contact with the side of the 2D polymer film (8) that was previously free of carrier material, so that a free-standing polymer membrane (81) protected on both sides by the carrier material is formed, which can be removed via a transport roller (10). procedure according to claim 1 or 2 , characterized in that the monomers additionally contain dye molecules in the form of chromophores or fluorophores. procedure according to claim 1 ,2 or 3, characterized in that the monomers additionally contain sensor molecules. procedure according to claim 1 or 2 , characterized in that the solvent bath is an ultrasonic bath. Method according to one or more of Claims 1 until 5 , characterized in that the monomers are photoactivatable molecules. procedure according to claim 5 , characterized in that the photoactivatable molecules are methyl acrylates. Method according to one or more of Claims 1 until 6 , characterized in that the UV light (6) has a wavelength of 300-400 nm. Use of by the method according to one or more of Claims 1 until 8th manufactured free-standing 2D-membrane with pores (200) in the range of λ up to 10 nm for an application-related modification of this for use in the field of nanofiltration, reverse osmosis, dialysis or sensor technology in health technologies and the field of energy storage or photovoltaic technologies.

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