Composition and method of 3D printing a porous, substance-embossed material, porous, substance-embossed material, and uses thereof
Patent Information
- Application Number
- PCT/EP2024/076002
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-22
- Filing Date
- 2024-09-18
- Publication Date
- 2025-03-27
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Abstract
Description
[0001] Composition and method for 3D printing a porous, substance-imprinted material, porous, substance-imprinted material, and uses thereof. A composition and a method for 3D printing a porous, substance-imprinted material are provided. Furthermore, a porous, substance-imprinted material is provided, and uses thereof are proposed. With the composition according to the invention, it is possible to produce porous, substance-imprinted materials in a simple, cost-effective, controllable, and scalable manner via 3D printing.
[0002] The advantage of the composition is that it has a higher storage stability than known compositions. Furthermore, the composition ensures that porous, substance-embossed materials can be printed with consistent properties over long periods of time. The reproducibility achievable with the composition according to the invention in the
[0003] The production of porous, substance-imprinted materials is very complex. Porous, substance-imprinted materials (PSGMs for short) are highly cross-linked, partly polymeric adsorption media that bear a structural and functional imprint for a substance (i.e., a template) with which they were imprinted during production. This imprint enables the PSGMs to reversibly bind the substance (i.e., the template) according to the lock-and-key principle (via non-covalent or reversible covalent interactions) and thus represent synthetic receptors for the substance with which they were imprinted. Compared to their natural analogues (e.g., antibodies, enzymes, or hormone receptors), PGSMs are impressive due to, among other things, their large reactive surface structure and their high stability.
[0004] To date, PSGMs have been primarily produced using conventional wet-chemical synthesis strategies (e.g., bulk polymerization, emulsion synthesis, suspension synthesis, and spin coating). However, the disadvantage of these methods is that they have limitations regarding the shape of the PSGMs (limited design freedom). Furthermore, reproducibility with these methods requires improvement.
[0005] It is also known that PSGMs can be produced using microstereolithography (Conrad II, PG et al., Advanced Materials, 15(18):1541-1544) and two-photon stereolithography (Gomez, LPC et al., Advanced Materials, 28(28):5931-5937). However, with both stereolithographic approaches, the material properties (such as porosity) could not be specifically controlled. Furthermore, the production of larger PSGMs using these methods is very costly (costly scaling). Two-photon stereolithography also has the disadvantage that the porous polymers have a low binding capacity. Furthermore, the choice of the porogenic solvent is very limited in two-photon stereolithography due to the required high viscosity of the porogenic solvent.
[0006] In general, it is known in the prior art that porous polymers can be produced via 3D printing (Dong, Z. et al., Nature Communications, 12). In this case, a process is also known with which a porous, substance-imprinted material can be produced by 3D printing (Rezanavaz, R., 3D Printing and Additive Manufacturing, 0:1-9; DOI: 10.1089 / 3dp.2022.0107). However, in this known process, an emulsion is printed via 3D printing. In the emulsion, the porogenic solvent (water or methanol) is present in a first (liquid) phase, and the monomers and the photoinitiator for producing the polymer are present in a second (liquid) phase separate from the first phase.
[0007] The disadvantage of this approach is that the stability of this composition (emulsion) is low and inevitably leads to a spatial separation of the two liquid phases of the emulsion over time, i.e., an initially homogeneous distribution of the two phases is lost over time. This can lead to an inhomogeneous pore distribution in the porous, substance-embossed material printed with such a composition (emulsion). This inhomogeneous pore distribution can occur in a single printing process, producing an inhomogeneous product, or it can occur over time across multiple printing processes, resulting in inhomogeneity in the products produced one after the other. Therefore, the use of such a composition (emulsion) for printing a porous, substance-embossed material cannot guarantee that the printed, porous, substance-embossed materials will have consistent properties (e.g.in terms of their porosity).
[0008] The addition of an emulsifier (or surfactant) to said composition (emulsion) can mitigate this disadvantage, but cannot completely overcome it. Rezanavaz, R. (3D Printing and Additive Manufacturing, 0:1-9; DOI: 10.1089 / 3dp.2022.0107), for example, discloses the addition of the surfactant Pluronic L-81 to stabilize the composition (emulsion). This has the disadvantage that the printed, porous, substance-imprinted material necessarily contains said surfactant and can release it during use. A release of surfactant can be undesirable in certain applications, such as application of the material in the human or animal body (e.g., pose a health risk). Based on this, the object of the present invention was to provide a composition for 3D printing a porous, substance-imprinted material that overcomes at least one disadvantage known in the prior art.In particular, the composition should be suitable for 3D printing a porous, substance-imprinted material in a simple, cost-effective, controllable, and / or scalable manner, wherein the composition should exhibit higher storage stability and ensure that porous, substance-imprinted materials with consistent properties (e.g., consistent pore distribution) can be printed over long periods of time (high reproducibility). Furthermore, a method for 3D printing a porous, substance-imprinted material should be provided that overcomes at least one disadvantage known in the prior art and, in particular, has at least one of the aforementioned advantages. Furthermore, a porous, substance-imprinted material with improved properties (e.g., more homogeneous pore distribution) should be provided, and uses thereof should be proposed.
[0009] The object is achieved by the composition having the features of claim 1, the method having the features of claim 8, the porous, substance-embossed material having the features of claim 12 and the use having the features of claim 14.
[0010] According to the invention, a composition for 3D printing a porous, substance-imprinted material is provided, containing or consisting of a) at least one monomer which is suitable for polymerization; b) at least one initiator for initiating polymerization of the at least one monomer (e.g. at least one photoinitiator); and c) at least one porogenic solvent which is not suitable for polymerization; d) at least one substance (template) which does not polymerize upon polymerization of the composition and which differs from the porogenic solvent; wherein the at least one monomer, the at least one initiator and the at least one porogenic solvent are present in a single phase of the composition (iethe composition is not present as an emulsion), wherein the at least one porogenic solvent is suitable for forming a phase which is separate from the phase of the polymer during a polymerization of the at least one monomer to at least one polymer (ie the at least one porogenic solvent has the property that a phase separate from the porogenic solvent, namely a polymer phase, only forms during the polymerization of the composition), wherein the at least one porogenic solvent is present in the composition in an amount of 1 to 98 wt.%, based on the total weight of the composition.
[0011] The composition according to the invention makes it possible to produce porous, substance-embossed materials in a simple, cost-effective, controllable, and scalable manner via 3D printing. It has been found that the composition according to the invention can be used to print a porous, substance-embossed material that has a very high binding capacity for the at least one substance and very high thermal insulation. Furthermore, it has been found that the porous, substance-embossed material produced with the composition according to the invention has very high dimensional stability, i.e., a dimensional stability that is significantly higher than that of a comparable composition that does not contain the at least one substance for embossing.
[0012] A key advantage of the composition is that it has greater storage stability than known compositions in emulsion form. This can also ensure that porous, substance-embossed materials with consistent properties (e.g., consistent pore distribution) can be printed with the composition over long periods of time. In other words, the composition according to the invention can ensure consistent properties within the production of a single porous, substance-embossed material and also ensure consistent properties with respect to multiple porous, substance-embossed materials that are printed at a certain time interval from one another. The reproducibility achievable with the composition according to the invention in the production of the porous, substance-embossed materials is thus very high.In the composition according to the invention, the at least one porogenic solvent is present in an amount of 1 to 98 wt.%, based on the total weight of the composition. The higher the amount of porogenic solvent in the composition, the higher the porosity of the porous, substance-imprinted material produced with the composition.
[0013] In the composition, the at least one monomer can have at least one functional group that differs from a polymerizable group, preferably from all polymerizable groups, of the at least one monomer. The advantage here is that, via polymerization of the monomer, a polymer can be produced that exposes the functional group on its surface. Thus, the binding cavities for the at least one substance, which are imprinted into the surface of the polymer during the polymerization of the at least one monomer, also have the functional groups. As a result, the resulting porous, substance-imprinted material can have a higher binding affinity for the at least one substance.
[0014] The at least one monomer of the composition may further be selected from the group consisting of alkenes, wherein the at least one monomer is preferably selected from the group consisting of vinyl monomers, allyl monomers, acrylate monomers, methacrylate monomers and combinations thereof.
[0015] In addition, the at least one monomer can be selected from the group consisting of methacrylate, trifluoromethyl acrylate, acrylate, itaconate, styrenesulfonate, acrylamido-methylpropanesulfonate, 4-vinylphenylboronate, 4-vinylbenzoate, carboxyethyl acrylate, hydroxyethyl methacrylate phosphate, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 4(5)-vinylimidazole, 2-aminoethyl methacrylate, 2-(dimethylaminoethyl) methacrylate,
[0016] Aminoethyl acrylate, 4-vinylbenzyltrimethylammonium chloride,
[0017] Hydroxyethylmethacrylat, Glycidylmethacrylat, Acrylamid, Methacrylamid, Isopropylacrylamid, 4-Vinylbenzamidin, 4-Methacrylamidbenzamidin, Styrol, Phenylmethacrylat, Cyclohexylmethacrylat, Methylmethacrylat, Butylmethacrylat, Hexylmethacrylat, Octylmethacrylat,
[0018] Ethylenglykoldimethylacrylat, Hexandioldimethacrylat,
[0019] Trimethylolpropantrimethacrylat, Polyethylenglykoldi(meth)acrylat,
[0020] Triethylenglykoldi(meth)acrylat, Pentaerythrittri(meth)acrylat,
[0021] Pentaerythritoltetra(meth)acrylat, Dipentaerythritolpenta(meth)acrylat, Dipentaerythritolhexa(meth)acrylat, Divinylbenzol, Ethylenbisacrylamid, Methylenbisacrylamid, Bisacryloylpiperazin, N N'-Bisacryloylcystamin, N,N'- 1,2-Dihydroxyethylenbisacrylamid, N,O-Bismethacryloylethanolamin, und Kombinationen hiervon.
[0022] Furthermore, the at least one monomer can be selected from the group consisting of surfactants with a polymerizable group, cyclodextrins with a polymerizable group, or silanes with a polymerizable group, and combinations thereof. A surfactant with a polymerizable group (so-called "surfmer") has the advantage, firstly, that it serves as an emulsifier and functional monomer, thereby enhancing pore formation in the porous, substance-imprinted material during polymerization and allowing hydrophilic binding cavities to be created in the porous, substance-imprinted material. The surfactant with a polymerizable group can thus achieve a higher binding affinity for the substance. A further advantage over surfactants without a polymerizable group is that the surfactant with a polymerizable group is chemically covalently bonded to the polymer of the material, meaning it cannot be released from the produced material.This increases long-term stability and can minimize any health risk posed by the surfactant to a user of the material (e.g., if the material is used in an animal or human body).
[0023] The at least one monomer can be present in the composition in an amount of 0.25 to 98 wt.%, preferably 1 to 70 wt.%, particularly preferably 3 to 50 wt.%, most preferably 5 to 40 wt.%, in particular 10 to 25 wt.%, based on the total weight of the composition. Optionally, all monomers of the composition that are suitable for polymerization are present in the composition in this amount.
[0024] The at least one initiator of the composition can be a photoinitiator or a thermal initiator. Preferably, the initiator is a photoinitiator. The at least one initiator of the composition can be selected from the group consisting of free radical formers, cation formers, anion formers, and combinations thereof.
[0025] Furthermore, the at least one initiator can be selected from the group consisting of quinone compound, camphorquinone, azide compound, azo compound (e.g. azobisisobutyronitrile), peroxide compound (e.g. benzoyl peroxide), disulfide compound, bis-imidazole compound, alkyl halide, benzoylbenzoic acid, benzoyl benzoates, alkyl thiocyanate,
[0026] Phosphine oxide compound (e.g. bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide), phenylphosphinate compound, benzoylcyclohexanol (e.g. 1-hydroxycyclohexylphenyl ketone), substituted or unsubstituted thioxanthone, substituted or unsubstituted benzophenone, substituted or unsubstituted acetophenone, substituted or unsubstituted benzil, substituted or unsubstituted benzoin and combinations thereof.
[0027] Apart from that, the at least one initiator can be selected from the group consisting of ionic photoacid generators (cation generators), preferably selected from the group consisting of onium salts, triarylphosphonium salts containing complex halides as counterions, arene-metal complexes containing complex halides as counterions, dialkylphenacylsulfonium salts containing complex halides as counterions, and combinations thereof. The onium salts are optionally selected from the group consisting of aryldiazonium, diaryliodonium, triarylsulfonium, triarylselenonium, and combinations thereof.
[0028] In addition, the at least one initiator can be selected from the group consisting of non-ionic photoacid generators, wherein the non-ionic photoacid generator is preferably selected from the group consisting of 2-nitrobenzyl esters of carboxylic acids, 2-nitrobenzyl esters of sulfonic acids, sulfone compounds, triaryl phosphates, N-hydroxyimidesulfonates (e.g. N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-l-butanesulfonate), sulfonic acid esters of phenol, diazonaphthoquinones, iminosulfonates, trichloromethyl-l,3,5-triazines (e.g. 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine), and combinations thereof.
[0029] Furthermore, the at least one initiator can be selected from the group consisting of photobase formers (anion formers), wherein the photobase former is preferably selected from the group consisting of carbamates (preferably selected from the group consisting of m-nitrophenylcarbamate, methyl[l-(3,4-dimethoxyphenyl)ethyl]carbamate, o-nitrobenzylcarbamate and combinations thereof), o-acyloximes, ammonium salts, sulfonamides, formamides, nifedipines, aminimides, aminoketones, o-carbamoyloximes and / or combinations thereof.
[0030] The at least one initiator can be present in the composition in an amount of 0.001 to 25 wt.%, preferably 0.01 to 10 wt.%, particularly preferably 0.1 to 5 wt.%, most preferably 0.25 to 3 wt.%, in particular 0.5 to 2 wt.%, based on the total weight of the composition. Optionally, all initiators of the composition are present in the composition in this amount.
[0031] The at least one porogenic solvent of the composition may be selected from the group consisting of polar solvents, non-polar solvents and combinations thereof.
[0032] Furthermore, the at least one porogenic solvent can be selected from the group consisting of water, alcohol (e.g. methanol, ethanol, glycol, 1-propanol, 2-propanol, propylene glycol, 1-butanol, 2-butanol, isobutyl alcohol, butylene glycol, cyclohexanol or 1-decanol), ether (e.g. dimethyl ether, diethyl ether, tert-butyl methyl ether, 1,4-dioxane or tetrahydrofuran), ester (e.g. ethyl acetate), carbonate (e.g. dimethyl carbonate or diethyl carbonate), haloalkane (e.g. dichloromethane, trichloromethane, tetrachloromethane or 1,2-dichloroethane), nitrile (e.g. acetonitrile), aldehyde, ketone (e.g. acetone), amide (e.g. DMF), sulfoxide (e.g. DMSO), carboxylic acid (e.g. formic acid or acetic acid), aliphatic hydrocarbon (e.g. pentane, Cyclopentane, hexane, cyclohexane, heptane or octane), aromatic hydrocarbon (e.g., benzene or toluene), and combinations thereof. According to the invention, the at least one porogenic solvent is present in the composition in an amount of 1 to 98 wt.-%, preferably 5 to 95 wt.%, particularly preferably 30 to 80 wt.%, very particularly preferably 45 to 70 wt.%, in particular 50 to 64 wt.%, based on the total weight of the composition. Optionally, all porogenic solvents of the composition are present in this amount in the composition. The morphology (e.g. with regard to the porosity) of the produced porous, substance-imprinted material can be adjusted via the amount of porogenic solvent in the composition, with the porosity being higher the higher the amount of porogenic solvent in the composition. By establishing a specific morphology of the porous, substance-imprinted material, an uptake rate or release rate of the at least one substance by the porous, substance-imprinted material can be determined.
[0033] The at least one substance (template) does not polymerize upon polymerization of the composition (i.e., it is different from the at least one monomer of the composition). By selecting the size of the at least one substance, the pore size of the interconnected pores of the material produced with the composition can be adjusted (i.e., the larger the substance, the larger the interconnected pores in the produced material).
[0034] The at least one substance may be selected from the group consisting of monomers, oligomers, polymers and combinations thereof.
[0035] Furthermore, the at least one substance can be selected from the group consisting of carbohydrates, lipids, nucleosides, nucleotides, nucleic acids, ribonucleic acids, amino acids, peptides, proteins, enzymes, protein-based enzymes, riboenzymes, monosaccharides, oligosaccharides, polysaccharides and combinations thereof.
[0036] Apart from that, the at least one substance can be selected from the group consisting of therapeutic active ingredients with a molar mass of <500 Da, wherein the at least one substance is preferably selected from the group consisting of antibiotics, X-ray contrast media, steroids, narcotics, intoxicants and combinations thereof.
[0037] Furthermore, the at least one substance can be selected from the group consisting of flavorings, food supplements, vitamins, doping agents, and combinations thereof.
[0038] In addition, the at least one substance can be selected from the group consisting of animal cells, human cells, plant cells, bacterial cells, yeast cells, fungal cells, viruses, virus-like particles and combinations thereof.
[0039] Furthermore, the at least one substance can be selected from the group consisting of toxins, wherein the at least one substance is preferably selected from the group consisting of pesticides, insecticides, fungicides, herbicides, bacterial mycotoxins, endocrine disruptors and combinations thereof.
[0040] Apart from that, the at least one substance can be selected from the group consisting of explosive substances, wherein the at least one explosive substance is preferably selected from the group consisting of primary explosives, secondary explosives, tertiary explosives, plastic explosives, propulsion explosives and combinations thereof.
[0041] In addition, the at least one substance can have a material bound to the substance, optionally chemically covalently. The material bound to the substance can preferably be selected from the group consisting of microparticles, nanoparticles and combinations thereof. The material is particularly preferably fibers. “Microparticles” are understood to mean particles with a diameter in the range from 1 pm to 1000 pm. “Nanoparticles” are understood to mean particles with a diameter of 1 nm to <1 pm. The diameter of the particles can refer, for example, to a diameter determined by electron microscopy or dynamic light scattering. The at least one substance can be present in the composition in an amount of 0.0005 to 60 wt.%, preferably 0.001 to 40 wt.%, particularly preferably 0.05 to 10 wt.%, very particularly preferably 0.1 to 5 wt.%, in particular 0.5 to 3 wt.-%, based on the total weight of the composition. Optionally, all substances of the composition that do not polymerize upon polymerization of the composition and that differ from the porogenic solvent are present in the composition in this amount. The quantity of the substance preferably refers only to the substance itself, in particular not to a sum of an amount of the substance and a material bound to the substance (e.g., not to a sum of an amount of the substance and a fiber optionally chemically covalently bound to the substance).
[0042] In a preferred embodiment, the composition further contains one, optionally several, crosslinkers having at least two polymerizable groups. The advantage is that the porous, substance-embossed material produced using the composition exhibits greater mechanical stability (e.g., greater hardness).
[0043] The crosslinker(s) optionally have at least three polymerizable groups. The crosslinker(s) is / are particularly preferably selected from the group consisting of vinyl crosslinkers, allyl crosslinkers, acrylate crosslinkers, methacrylate crosslinkers, and combinations thereof.
[0044] Furthermore, the crosslinker or crosslinkers are preferably selected from the group consisting of pentaerythritol triacrylate, ethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate,
[0045] Polyethylene glycol di(meth)acrylate, phenylene di(meth)acrylate,
[0046] Alkylenediol di(meth)acrylate, methylenebis(meth)acrylamide,
[0047] Alkylenbis(meth)acrylamid, Piperazinbis(meth)acrylamid, Divinylbenzol, Divinylnaphthalin, Diisopropenylbenzol, 1,3-Phenylenbis(meth)acrylamid, 1,4- Phenylenbis(meth)acrylamid, N,N'-l,3-Phenylenbis(2-methyl-2-propenamid), N,N'-l,4-Phenylenbis(2-methyl-2-propenamid), 3,5-Bis(meth)acrylamido- benzoesäure, 2,6-Bis(meth)acryloylamidopyridin,
[0048] Anhydroerythritoldi(meth)acrylat, l,4;3,6-Dianhydro-psorbitol-2,5- di(meth)acrylat, lsopropenbis(l,4-phenylen)-di(meth)acrylat, 2,2- Bis(hydroxymethyl)butanol-tri(meth)acrylat, Trimethylolpropantrimethacrylat, Polyethylenglykoldi(meth)acrylat, Triethylenglykoldi(meth)acrylat,
[0049] Pentaerythrittri(meth)acrylat, Pentaerythritoltetra(meth)acrylat,
[0050] Dipentaerythritolpenta(meth)acrylat, Dipentaerythritolhexa(meth)acrylat,
[0051] N,O-Bis(meth)acryloyl-ethanolamin und Kombinationen hiervon.
[0052] In addition, the crosslinker or crosslinkers are preferably selected from the group consisting of surfactants with at least two polymerizable groups, cyclodextrins with at least two polymerizable groups, silanes with at least two polymerizable groups and combinations thereof.
[0053] In addition, the crosslinker can be present in the composition in an amount of
[0054] 0.25 to 98 wt.%, preferably 3 to 75 wt.%, particularly preferably 5 to 60 wt.%, very particularly preferably 10 to 45 wt.%, in particular 15 to 30 wt.%, based on the total weight of the composition. Optionally, all crosslinkers of the composition are present in the composition in this amount.
[0055] The composition may have a viscosity of at most 1000 mPa-s, preferably from 1 to 200 mPa-s, particularly preferably from 1.5 to 100 mPa-s, most preferably from 2 to 50 mPa-s, in particular from 2.5 to 40 mPa-s. The viscosity preferably refers to a viscosity determined at a temperature of 25°C and 1013 hPa using a rotational viscometer.
[0056] In a preferred embodiment, the composition does not contain a non-porogenic solvent. The advantage is that this enhances the formation of pores during polymerization of the composition and improves accessibility to the binding sites in the substance-imprinted material produced from the composition.
[0057] In a further preferred embodiment, the composition contains no non-polymerizable surfactant (e.g., no Pluronic L-81). The advantage is that the material produced with the composition contains no non-polymerizable surfactant, i.e., no surfactant that is bound to the material only via non-covalent interactions and can be released during application of the material. This can, for example, minimize a health risk (e.g., when the material is applied in the human or animal body).
[0058] According to the invention, a method for 3D printing a porous, substance-imprinted material is further provided, comprising or consisting of the following steps: a) providing a composition according to the invention and b) printing the composition in a 3D printing process to form a porous, substance-imprinted material (optionally under the action of electromagnetic radiation, e.g. if the composition contains a photoinitiator as initiator).
[0059] The process according to the invention makes it possible to achieve the advantages mentioned above in connection with the composition according to the invention. In the process according to the invention, the properties of the porous, substance-embossed material can be controlled and monitored through the selection of the specific, individual components of the composition according to the invention as well as through computer-aided design (CAD) of the structures to be printed. Using the process according to the invention, a porous, substance-embossed material can be produced in a customized, almost arbitrary, microscopic or macroscopic form, thus tailoring it precisely to its target application and "installation" at a "site of action." Due to the high precision, porosity, and design flexibility, complex structures can be integrated into objects (e.g., cylindrical filters), for example, to produce highly specific low-pressure filter materials.
[0060] In the process, in step b), the composition can be printed using a 3D stereolithography printing process, preferably DLP 3D printing or LCD 3D printing. LCD 3D printing has the advantage of being cost-effective and allowing the printing of large objects as well as the simultaneous printing of multiple structures to be carried out independently of time. As a result, LCD 3D printing exhibits high scalability and reproducibility. Furthermore, LCD 3D printing enables the production of porous, substance-imprinted materials in virtually unlimited dimensions. Furthermore, LCD 3D printing—unlike two-photon stereolithography—allows the use of printable compositions with low viscosity.
[0061] In a preferred embodiment, the composition in step b) of the process is printed such that the porous, substance-embossed material has interconnected pores with a pore diameter per pore in the range of 1 nm to 20 pm, preferably 2 nm to 10 pm, particularly preferably 5 nm to 5 pm, most particularly preferably 10 nm to 2 pm (first type of pores).
[0062] Furthermore, the composition in step b) of the method can be printed such that the porous, substance-embossed material has a second type of pores that have a larger pore diameter than the interconnected pores (i.e., than the first type of pores), wherein the pore diameter of the second type of pores per pore is preferably in the range of 20 μm to 250 μm, particularly preferably 50 μm to 30 μm, most preferably 100 μm to 20 μm, in particular 150 μm to 15 μm. Optionally, the second type of pores are non-interconnected pores or interconnected pores.
[0063] Furthermore, the composition in step b) of the process can be printed such that the porous, substance-embossed material has a width, depth and / or height in the range of at least 0.5 mm, preferably at least 1 mm, particularly preferably at least 3 mm, most preferably at least 6 mm, in particular at least 8 mm, optionally at least 10 mm.
[0064] In the process, after step b) of the process, the at least one substance and the at least one porogenic solvent can be removed from the porous, substance-imprinted material, preferably leaving pores that are free of the at least one substance and the at least one porogenic solvent and are particularly preferably connected to one another. The at least one substance and the at least one porogenic solvent are preferably removed from the porous, substance-imprinted material using a process selected from the group consisting of washing with a liquid (e.g., organic solvent, organic solvent mixture, aqueous acid, or aqueous base), treatment with ultrasound, treatment with electromagnetic radiation (e.g., microwave treatment), pressurization, temperature elevation, electrochemical treatment, and combinations thereof.After removal of the at least one substrate and the at least one porogenic solvent, the remaining binding cavity results in a binding pocket complementary to the substance, optionally with a specific arrangement of functional groups of the polymer of the porous, substance-imprinted material, whereby said material exhibits substance-specific binding properties. In other words, a reactive and specific surface structure is obtained in a porous 3D network. The advantage is that the resulting porous, substance-imprinted material can bind or absorb the at least one substance in a controlled manner (uptake function). The uptake rate can be controlled via the controllable porosity of the porous, substance-imprinted material.
[0065] In the process, after step b), the porous, substance-imprinted material can be post-cured by exposure to electromagnetic radiation. The at least one porogenic solvent and the at least one substance remain in the resulting pores, which are particularly preferably interconnected. The advantage is that the resulting porous, substance-imprinted material can release large amounts of the at least one substance in a controlled manner (release function). The release rate can be controlled via the controllable porosity of the porous, substance-imprinted material.
[0066] Furthermore, after step b) of the process, the porous, substance-imprinted material can be dried, preferably using a process selected from the group consisting of drying with supercritical CO2, freeze-drying, air drying, and combinations thereof. Air drying is preferably carried out under the influence of electromagnetic radiation.
[0067] According to the invention, a porous, substance-imprinted material is further provided, containing or consisting of a molecularly imprinted polymer, wherein the molecularly imprinted polymer consists of chemically covalently bonded monomers, wherein the surface of the molecularly imprinted polymer has, at least in regions, a shape which corresponds at least partially to an imprint of a three-dimensional structure of at least one substance which differs from a porogenic solvent, wherein the porous, substance-imprinted material has pores with a pore diameter per pore in the range from 1 nm to 20 pm (= first type of pores) and wherein the porous, substance-imprinted material is produced by the method according to the invention.
[0068] The porous, substance-embossed material has the advantages mentioned in connection with the composition according to the invention. Since the inventive method uses the inventive composition and the at least one porogenic solvent is present therein in an amount of 1 to 98 wt. %, based on the total weight of the composition, the porous, substance-embossed material according to the invention has a certain porosity. The higher the amount of porogenic solvent in the composition used to produce the porous, substance-embossed material according to the invention, the higher the porosity of the porous, substance-embossed material according to the invention.
[0069] The diameter of the pores of the porous, substance-imprinted material may refer to a diameter determined by mercury porosimetry, a gas sorption method, and / or microscopy (e.g., electron microscopy).
[0070] The pore diameter of the first type of pores can preferably be 2 nm to 10 pm, particularly preferably 5 nm to 5 pm, most preferably 10 nm to 2 pm, per pore.
[0071] The first type of pores of the porous, substance-embossed material can be at least partially interconnected pores. Furthermore, the porous, substance-embossed material can have a second type of pores that have a larger pore diameter than the first type of pores, wherein the pore diameter of the second type of pores per pore is preferably in the range of 20 μm to 250 μm, particularly preferably 50 μm to 30 μm, most preferably 100 μm to 20 μm, in particular 150 μm to 15 μm, wherein the second type of pores can optionally be non-interconnected pores or interconnected pores.
[0072] Apart from that, the porous, substance-embossed material can have a width, depth and / or height in the range of at least 0.5 mm, preferably at least 1 mm, particularly preferably at least 3 mm, most preferably at least 6 mm, in particular at least 8 mm, optionally at least 10 mm.
[0073] In an optional embodiment, the porous, substance-imprinted material does not contain a porogenic solvent.
[0074] Furthermore, the porous, substance-imprinted material can contain the at least one substance, preferably at least partially bound in a negative imprint of the three-dimensional structure of the at least one substance, in particular via non-covalent interactions. The advantage is that the porous, substance-imprinted material can release large amounts of the at least one substance (release function).
[0075] Furthermore, the porous, substance-embossed material may not contain the at least one substance. The advantage is that the porous, substance-embossed material can bind or absorb the at least one substance (absorption function).
[0076] The porous, substance-embossed material according to the invention can be characterized by not containing a non-polymerizable surfactant (i.e., a surfactant that is only bonded to the material via non-covalent interactions, such as Pluronic L-81). The advantage here is that the material cannot release any surfactant, which can minimize health risks for certain applications of the material (e.g., application in the human or animal body). According to the invention, the porous, substance-embossed material according to the invention is produced using the method according to the invention.
[0077] The use of the porous, substance-imprinted material according to the invention is proposed in an i) separation process for separating the at least one substance from other substances (e.g. at low pressure, ie 650 to 5000 hPa), wherein the separation process is preferably selected from the group consisting of liquid chromatography, solid phase extraction, filtration processes and combinations thereof, wherein the separation process is particularly preferably selected from the group consisting of liquid treatment processes, gas treatment processes and combinations thereof, in particular water treatment processes, beverage treatment processes, phage separation processes, air treatment processes; and / or ii) enrichment process for enriching the at least one substance; and / or iii) catalytic process;and / or iv) sensory methods for detecting the at least one substance, preferably sensory testing methods, wherein the sensory testing method is particularly preferably selected from the group consisting of pollutant detection methods in a liquid, pollutant detection methods in a gas, and combinations thereof; and / or v) release methods for releasing the at least one substance, wherein the at least one substance is preferably an active ingredient, particularly preferably a pheromone; and / or vi) cell cultivation methods for cultivating at least one cell in the porous, substance-imprinted material;
[0078] The subject matter of the invention will be explained in more detail with reference to the following figures and examples, without wishing to restrict it to the specific embodiments shown here.
[0079] Figure 1 schematically shows a method for 3D printing a porous, substance-embossed material 6. The composition 1 according to the invention (shown in dashed lines in Figure 1) is provided in a container 3 of a 3D printer. A printing platform 2 of a 3D printer then moves into the provided composition 1 according to the invention. In the container 3 of the 3D printer, the composition is solidified, i.e., hardened, into a porous, substance-embossed material 6 by the action of electromagnetic radiation from a light source 5 of the 3D printer and via an LCD screen 4 as a mask for exposing individual layers. Figure 1 also shows, in the right-hand outer part, an enlargement 7 of a section of the porous, substance-embossed material 6.
[0080] Figure 2 shows a micrograph of a first porous, substance-imprinted material according to the invention. The 3D-printed material is 18 mm high, has the shape of a rocket, and features interconnected pores with a pore size of approximately 0.030–0.130 pm.
[0081] Figure 3 shows a micrograph of a second porous, substance-imprinted material according to the invention. The 3D-printed material is 18 mm wide, has the shape of a perforated disc, and has, on the one hand, first, interconnected pores with a pore size of approximately 0.030–0.130 pm, and, on the other hand, a second type of pore whose diameter is larger than the diameter of the first, interconnected pores (diameter approximately 1.6 mm).
[0082] Figure 4 shows a micrograph of a third porous, substance-embossed material according to the invention. The 3D-printed material is 9.5 mm long, high, and wide, has the shape of a perforated cuboid, and has, on the one hand, first, connected pores with a pore size of approximately 0.030–0.130 pm, and, on the other hand, a second type of pore whose diameter is larger than the diameter of the first, connected pores (diameter approximately 1 mm).
[0083] Example 1 - Preparation of a porous, hormone-imprinted material
[0084] A photocurable composition consisting of 26.0 wt% of the crosslinking and binding monomer 2-hydroxyethyl methacrylate, 22 wt% of the crosslinking monomer ethylene glycol dimethacrylate, 9.5 wt% of the pore-forming solvent 1-decanol, 39.5 wt% of the pore-forming solvent cyclohexanol, 2 wt% of the photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 1.0 wt% of the substance (template) 17ß-estradiol was homogenized by ultrasonication for 15 minutes.
[0085] The Phrozen Sonic Mini 4K liquid crystal display (LCD) 3D printer was used to produce porous, hormone-imprinted materials. Matching the absorption spectrum of the selected photoinitiator, the printer uses a 405 nm UV LED array as the light source. The layer thickness was set to 50 pm with an exposure time per layer of 19 seconds.
[0086] Several macroscopic geometries of the porous, hormone-imprinted materials were created, some with at least one dimension larger than 1 cm (see Figures 2 to 4).
[0087] After 3D printing, the porous, hormone-imprinted materials were washed with acetone, isopropanol, and ethanol to remove the unreacted components. The porous, hormone-imprinted materials were then dried using CO2 in a Tousimis Samdri 795 critical point dryer to prevent the pore network from collapsing.
[0088] Example 2 - Preparation of a porous, cannabinoid-imprinted material
[0089] A photocurable composition consisting of 1.2 wt% of the crosslinking and binding monomer 2-hydroxyethyl methacrylate, 1.6 wt% of the crosslinking and binding monomer benzyl methacrylate, 45.2 wt% of the crosslinking monomer 1,6-hexanediol dimethacrylate, 9.5 wt% of the pore-forming solvent 1-decanol, 39.5 wt% of the pore-forming solvent cyclohexanol, 2 wt% of the photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 1.0 wt% of the substance (template) cannabidiol was homogenized by ultrasonication for 15 minutes.
[0090] The production and post-treatment after 3D printing were carried out with the composition described here as in Example 1.
[0091] Cylinders with a radius of approximately 28.5 mm and a height of approximately 8 mm were printed, with an internal gyroid structure to increase the flow velocity (not shown in the figures).
[0092] Example 3 - Preparation of a porous, pheromone-imprinted material
[0093] A photocurable composition consisting of 28.0 wt% of the crosslinking and binding monomer 2-hydroxyethyl methacrylate, 18.0 wt% of the crosslinking monomer ethylene glycol dimethacrylate, 2 wt% of the pore-forming solvent ethanol, 4.0 wt% of the photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 48.0 wt% of the substance (template) verbenone was homogenized by ultrasonication for 15 minutes.
[0094] The LCD-based Phrozen Sonic Mini 4K 3D printer was used to produce the porous, pheromone-releasing material. Matching the absorption spectrum of the selected photoinitiator, the printer uses a 405 nm ultraviolet (UV) light-emitting diode (LED) array as the light source. The layer thickness was set to 50 pm with an exposure time per layer of 27 seconds.
[0095] Macroscopic cubes (volume: 1.0 cm 3 ) (not shown in the figures).
[0096] After the porous, pheromone-imprinted materials were produced via 3D printing, they were post-cured using UV light (405 nm) for 15 min.
[0097] 1: composition according to the invention;
[0098] 2: Printing platform of a 3D printer;
[0099] 3: Container of a 3D printer in which the composition is cured;
[0100] 4: LCD screen as a mask for illuminating the individual layers; : light source of a 3D printer; : porous, substance-embossed material; : enlargement of a section of the porous, substance-embossed
[0101] Materials.
Claims
Patent claims (for PCT subsequent application) 1. A composition for 3D printing a porous, substance-imprinted material, containing or consisting of a) at least one monomer suitable for polymerization; b) at least one initiator for initiating polymerization of the at least one monomer; and c) at least one porogenic solvent that is not suitable for polymerization; d) at least one substance that does not polymerize upon polymerization of the composition and is different from the porogenic solvent;wherein the at least one monomer, the at least one initiator and the at least one porogenic solvent are present in a single phase of the composition, wherein the at least one porogenic solvent is suitable for forming a phase separate from the polymer phase during polymerization of the at least one monomer to at least one polymer, wherein the at least one porogenic solvent is present in the composition in an amount of 1 to 98 wt.%, based on the total weight of the composition; 2. Composition according to the preceding claim, characterized in that the at least one monomer i) has at least one functional group which is different from a polymerizable group, preferably all polymerizable groups of the at least one monomer; and / or ii) is selected from the group consisting of alkenes, wherein the at least one monomer is preferably selected from the group consisting of vinyl monomers, allyl monomers, acrylate monomers, methacrylate monomers, and combinations thereof; and / or iii) is selected from the group consisting of methacrylate, trifluoromethyl acrylate, acrylate, itaconate, styrene sulfonate, acrylamido-methylpropanesulfonate, 4-vinylphenylboronate, 4-vinylbenzoate, carboxyethyl acrylate, hydroxyethyl methacrylate phosphate, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 4(5)-vinylimidazole, 2-aminoethyl methacrylate, 2-(dimethylaminoethyl)methacrylate, aminoethyl acrylate, 4-vinylbenzyltrimethylammonium chloride, hydroxyethyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, isopropylacrylamide, 4-vinylbenzamidine, 4-methacrylamide- benzamidine, styrene, phenyl methacrylate, Cyclohexyl methacrylate, methyl methacrylate, butyl methacrylate,Hexyl methacrylate, octyl methacrylate, ethylene glycol dimethyl acrylate, hexanediol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, divinylbenzene, ethylenebisacrylamide, methylenebisacrylamide, bisacryloylpiperazine, N N'-bisacryloylcystamine, N,N'-1,2-dihydroxyethylene-bisacrylamide, N,O-bismethacryloylethanolamine, and combinations thereof; and / or iv) is selected from the group consisting of surfactant with polymerizable group, cyclodextrins with polymerizable group or silanes with polymerizable group and combinations thereof; and / or v) in the composition in an amount of 0.25 to 98 wt.%, preferably 1 to 70 wt.%, particularly preferably 3 to 50 wt.%, very particularly preferably 5 to 40 wt.%, in particular 10 to 25 wt.%, based on the total weight of the composition, wherein optionally all monomers of the composition which are suitable for polymerization are present in the composition in this amount.
3. Composition according to one of the preceding claims, characterized in that the at least one initiator is i) a photoinitiator or a thermal initiator; and / or ii) is selected from the group consisting of radical formers, cation formers, anion formers, and combinations thereof; and / or iii) is selected from the group consisting of quinone compound, camphorquinone, azide compound, azo compound, peroxide compound, disulfide compound, bis-imidazole compound, alkyl halide, benzoylbenzoic acid, benzoyl benzoates, alkyl thiocyanate, phosphine oxide compound, phenylphosphinate compound, substituted cider or unsubstituted thioxanthone, substituted or unsubstituted benzophenone, substituted or unsubstituted acetophenone, substituted or unsubstituted benzil, substituted or unsubstituted benzoin and combinations thereof;and / or iv) is selected from the group consisting of ionic photoacid generators, preferably selected from the group consisting of onium salts, triarylphosphonium salts containing complex halides as counterions, arene-metal complexes containing complex halides as counterions, dialkylphenacyl sulfonium salts containing complex halides as counterions, and combinations thereof, wherein the onium salts are optionally selected from the group consisting of aryldiazonium, diaryliodonium, triarylsulfonium, triarylselenonium and combinations thereof; and / or v) is selected from the group consisting of non-ionic photoacid generators, wherein the non-ionic photoacid generator is preferably selected from the group consisting of 2-nitrobenzyl esters; of carboxylic acids, 2-nitrobenzyl esters of sulfonic acids, sulfone compounds, triaryl phosphates, N-hydroxyimide sulfonates, sulfonic acid esters of phenol, diazonaphthoquinones, iminosulfonates, trichloromethyl-1,3,5-triazines, and combinations thereof; and / or vi) is selected from the group consisting of photobase formers, wherein the photobase former is preferably selected from the group consisting of carbamates, o-acyloximes, ammonium salts, sulfonamides, formamides, nifedipines, aminimides, aminoketones, o-carbamoyloximes and / or combinations thereof, wherein the carbamates are preferably selected from the group consisting of m-nitrophenyl carbamate, methyl [l-(3,4-dimethoxyphenyl)ethyl]carbamate, o-nitrobenzyl carbamate and combinations thereof; and / or vii) in the composition in an amount of 0.001 to 25 wt.%, preferably 0.01 to 10 wt.%, particularly preferably 0.1 to 5 wt.%, very particularly preferably 0.25 to 3 wt.%, in particular 0.5 to 2 wt.-%, based on the total weight of the composition, wherein optionally all initiators of the composition are present in the composition in this amount.
4. Composition according to one of the preceding claims, characterized in that the at least one porogenic solvent i) is selected from the group consisting of polar solvents, non-polar solvents and combinations thereof; and / or ii) is selected from the group consisting of water, alcohol, ether, ester, carbonate, haloalkane, nitrile, aldehyde, ketone, amide, sulfoxide, carboxylic acid, aliphatic hydrocarbon, aromatic hydrocarbon and combinations thereof; and / or iii) in the composition in an amount of 5 to 95 wt.%, particularly preferably 30 to 80 wt.%, most particularly preferably 45 to 70 wt.%, in particular 50 to 64 wt.%, based on the total weight of the composition, wherein optionally all porogenic solvents of the composition are present in the composition in this amount.
5. Composition according to one of the preceding claims, characterized in that the at least one substance i) is selected from the group consisting of monomers, oligomers, polymers and combinations thereof; and / or ii) is selected from the group consisting of carbohydrates, lipids, nucleosides, nucleotides, nucleic acids, ribonucleic acids, amino acids, peptides, proteins, enzymes, protein-based enzymes, ribosomes, monosaccharides, oligosaccharides, polysaccharides and combinations thereof; and / or iii) is selected from the group consisting of therapeutic active ingredients with a molar mass of <500 Da, wherein the at least one substance is preferably selected from the group consisting of antibiotics, X-ray contrast agents, steroids, narcotics, intoxicants and combinations thereof; and / or iv) is selected from the group consisting of flavorings, dietary supplements, vitamins, doping agents and combinations thereof;and / or v) is selected from the group consisting of animal cells, human cells, plant cells, bacterial cells, yeast cells, fungal cells, viruses, virus-like particles, and combinations thereof; and / or vi) is selected from the group consisting of toxins, wherein the at least one substance is preferably selected from the group consisting of pesticides, insecticides, fungicides, herbicides, bacterial mycotoxins, endocrine disruptors, and combinations thereof; and / or; vii) is selected from the group consisting of explosive substances, wherein the at least one explosive substance is preferably selected from the group consisting of primary explosives, secondary explosives, tertiary explosives, plastic explosives, propulsion explosives and combinations thereof; and / or viii) has a material bound to the substance, preferably chemically covalently, wherein the bound material is preferably selected from the group consisting of microparticles, nanoparticles and combinations thereof, wherein the material is particularly preferably fibers; and / or ix) in the composition in an amount of 0.0005 to 60 wt.%, preferably 0.001 to 40 wt.%, particularly preferably 0.05 to 10 wt.%, very particularly preferably 0.1 to 5 wt.%, in particular 0.5 to 3 wt.-%, based on the total weight of the composition, wherein optionally all substances of the composition which do not polymerize upon polymerization of the composition and which differ from the porogenic solvent are present in this amount in the composition, wherein the quantity of the substance preferably refers only to the substance itself, in particular not to a sum of an amount of the substance and a material bound to the substance.
6. Composition according to one of the preceding claims, characterized in that the composition further contains one, optionally several, cross-linkers which have at least two polymerizable groups, wherein the cross-linker(s) preferably i) has at least three polymerizable groups, wherein the cross-linker is particularly preferably selected from the group consisting of vinyl cross-linkers, allyl cross-linkers, acrylate cross-linkers, methacrylate cross-linkers and combinations thereof; and / or ii) is selected from the group consisting of pentaerythritol triacrylate, ethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, phenylene di(meth)acrylate, alkylenediol di(meth)acrylate, methylenebis(meth)acrylamide, alkylenebis(meth)acrylamide, piperazinebis(meth)acrylamide, divinylbenzene, divinylnaphthalene, diisopropenylbenzene, 1,3-phenylenebis(meth)acrylamide, 1,4-phenylenebis(meth)acrylamide, N,N'-1,3-phenylenebis(2-methyl-2-propenamide), N,N'-1,4-phenylenebis(2-methyl-2-propenamide), 3,5-bis(meth)acrylamidobenzoic acid, 2,6-Bis(meth)acryloylamidopyridine, anhydroerythritol di(meth)acrylate, 1,4;3,6-dianhydro-psorbitol-2,5-di(meth)acrylate, isopropenebis(1,4-phenylene)-di(meth)acrylate, 2,2-bis(hydroxymethyl)butanol-tri(meth)acrylate, trimethylolpropane trimethacrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, N,O-bis(meth)acryloylethanolamine and combinations thereof; and / or iii) is selected from the group consisting of surfactants having at least two polymerizable groups, cyclodextrins having at least two polymerizable groups, silanes having at least two polymerizable groups and combinations thereof;and / or iv) is / are present in the composition in an amount of 0.25 to 98 wt.%, preferably 3 to 75 wt.%, particularly preferably 5 to 60 wt.%, very particularly preferably 10 to 45 wt.%, in particular 15 to 30 wt.%, based on the total weight of the composition, wherein optionally all crosslinkers of the composition are present in the composition in this amount.; 7. Composition according to one of the preceding claims, characterized in that the composition i) has a viscosity of at most 1000 mPa-s, preferably from 1 to 200 mPa-s, particularly preferably from 1.5 to 100 mPa-s, very particularly preferably from 2 to 50 mPa-s, in particular from 2.5 to 40 mPa-s, wherein viscosity preferably refers to a viscosity determined at a temperature of 25 °C and 1013 hPa by means of a rotational viscometer; and / or ii) does not contain a non-porogenic solvent; and / or iii) does not contain a non-polymerizable surfactant.
8. A method for 3D printing a porous, substance-imprinted material, comprising or consisting of the following steps: a) providing a composition according to any one of the preceding claims; and b) printing the composition in a 3D printing process to form a porous, substance-imprinted material.
9. The method according to claim 8, characterized in that in step b) i) the composition is printed using a 3D stereolithography printing process, preferably DLP 3D printing or LCD 3D printing; and / or ii) due to polymerization of the composition, a porous substance-embossed material is formed which has interconnected pores with a pore diameter in the range of 1 nm to 20 pm, preferably 2 nm to 10 pm, particularly preferably 5 nm to 5 pm, most particularly preferably 10 nm to 2 pm;and / or iii) the composition is printed such that the porous, substance-embossed material has a second type of pores which have a larger pore diameter than the interconnected pores, wherein the pore diameter of the second type of pores per pore is preferably in the range from 20 μm to 250 μm, particularly preferably 50 μm to 30 μm, very particularly preferably 100 μm to 20 μm, in particular 150 μm to 15 μm, wherein the second type of pores are optionally non-interconnected pores or interconnected pores; and / or; iv) the composition is printed such that the porous, substance-embossed material has a width, depth and / or height in the range of at least 0.5 mm, preferably at least 1 mm, more preferably at least 3 mm, most preferably at least 6 mm, in particular at least 8 mm, optionally at least 10 mm.
10. The method according to one of claims 8 or 9, characterized in that after step b) the at least one substance and the at least one porogenic solvent are removed from the porous, substance-imprinted material, preferably leaving pores which are free of the at least one substance and the at least one porogenic solvent and are particularly preferably connected to one another, wherein the at least one substance and the at least one porogenic solvent are preferably removed from the porous, substance-imprinted material via a method selected from the group consisting of washing with a liquid, treatment with ultrasound, treatment with electromagnetic radiation, pressurization, increasing the temperature, electrochemical treatment and combinations thereof.
11. The method according to claim 8 or 9, characterized in that after step b) i) the porous, substance-imprinted material is post-cured by exposure to electromagnetic radiation, wherein the at least one porogenic solvent and the at least one substance remain in the resulting pores, wherein the pores are particularly preferably connected to one another; or ii) the porous, substance-imprinted material is dried, preferably by a method selected from the group consisting of drying with supercritical CO2, freeze-drying, air drying and combinations thereof, wherein the air drying preferably takes place under the action of electromagnetic radiation.
12. A porous, substance-imprinted material containing or consisting of a molecularly imprinted polymer, wherein the molecularly imprinted polymer consists of chemically covalently bonded monomers, wherein the surface of the molecularly imprinted polymer has, at least in regions, a shape which corresponds at least partially to an imprint of a three-dimensional structure of at least one substance which differs from a porogenic solvent, wherein the porous, substance-imprinted material has pores with a pore diameter per pore in the range from 1 nm to 20 pm, wherein the porous, substance-imprinted material is produced by a method according to any one of claims 1 to 11.
13. Porous, substance-embossed material according to claim 12, characterized in that the porous, substance-embossed material i) has pores with a pore diameter per pore in the range of 1 nm to 20 pm, preferably 2 nm to 10 pm, particularly preferably 5 nm to 5 pm, very particularly preferably 10 nm to 2 pm; and / or ii) has at least partially interconnected pores with a pore diameter per pore in the range of 1 nm to 20 pm, preferably 2 nm to 10 pm, particularly preferably 5 nm to 5 pm, very particularly preferably 10 nm to 2 pm;and / or iii) has a second type of pores which have a larger pore diameter than the pores with a pore diameter per pore in the range of 1 nm to 20 pm, wherein the pore diameter of the second type of pores per pore is preferably in the range of 20 pm to 250 mm, particularly preferably 50 pm to 30 mm, most preferably 100 pm to 20 mm, in particular 150 pm to 15 mm, wherein the second type of pores are optionally non-interconnected pores or are interconnected pores; and / or; iv) has a width, depth and / or height in the range of at least 0.5 mm, preferably at least 1 mm, more preferably at least 3 mm, most preferably at least 6 mm, in particular at least 8 mm, optionally at least 10 mm; and / or v) does not contain a porogenic solvent; and / or vi) which contains at least one substance, preferably at least partially bound in the negative imprint of the three-dimensional structure of the at least one substance, in particular via non-covalent interactions, or which does not contain at least one substance.
14. Use of the porous, substance-imprinted material according to one of claims 12 or 13 in a i) separation process for separating the at least one substance from other substances, wherein the separation process is preferably selected from the group consisting of liquid chromatography, solid-phase extraction, filtration processes and combinations thereof, wherein the separation process is particularly preferably selected from the group consisting of liquid treatment processes, gas treatment processes and combinations thereof, in particular water treatment processes, beverage treatment processes, phage separation processes, air treatment processes; and / or ii) enrichment processes for enriching the at least one substance; and / or iii) catalytic processes;and / or iv) sensory methods for detecting the at least one substance, preferably sensory testing methods, wherein the sensory testing method is particularly preferably selected from the group consisting of pollutant detection methods in a liquid, pollutant detection methods in a gas, and combinations thereof; and / or; v) release method for releasing the at least one substance, wherein the at least one substance is preferably an active ingredient, particularly preferably a pheromone; and / or vi) cell cultivation method for cultivating at least one cell in the porous, substance-imprinted material.
Citation Information
Patent Citations
Printing of inherently porous three-dimensional polymer objects
EP3848201A1
Cited By
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