Materials, processes, and methods for the adsorption of harmful compounds

Abstract

The invention relates to a polymeric mesh comprising a cross-linked polymer, wherein the cross-linked polymer comprises residues of a polyvalent carboxylic acid, a polyvalent amine, and a cross-linker. The polymeric mesh may be used for removing harmful compounds from an environment such as a gas or an aqueous environment.

Description

Materials, Processes, and Methods for the Adsorption of Harmful CompoundsField of the Invention

[0001] The invention relates to a polymeric mesh comprising a cross-linked polymer, a composite material comprising the cross-linked polymer and a support material, to processes for the synthesis of the composite material, to a method of removing harmful compounds from the environment, and to a method of using an acidic polymer.Background of the Invention

[0002] WO 2020 / 079233 A2 discloses methods of forming a polymeric mesh based on a cross-linked polyamine. Herein, poly(vinylamine) is used as an amino group-containing polymer comprising a dicarboxylic acid such as succinic acid as the preferred cross-linking agent. However, for formation of the polymeric mesh, a rather high reaction temperature from 185°C to 200°C is necessary. The related high energy consumption is not acceptable for many industrial processes.

[0003] Instead of dicarboxylic acid as the cross-linking agent, also bis-epoxide reagents may be employed. However, utilization of these highly reactive compounds in an aqueous medium is limited due to their poor solubility in water, thereby causing severe difficulties with respect to up-scaling to the manufacturing process, particularly when moving towards the multi-ton production.

[0004] The polymeric mesh defined in WO 2020 / 079233 A2 is capable of binding microorganisms as well as small molecules.Object of the Invention

[0005] It was the object of the present invention to provide polymeric meshes and composite materials comprising the polymeric meshes for removing harmful substances from the environment such as an aqueous or gaseous environment, in particular from an aqueous environment, and which can be prepared in an easier manner, in particular at lower temperatures than those used in the prior art. Moreover, the crosslinkers used for making the polymeric mesh should be at least partially soluble in water.Summary of the Invention

[0006] The invention relates to the following items:1. A polymeric mesh comprising a cross-linked polymer, wherein the cross-linked polymer comprises residues of a polyvalent carboxylic acid, a polyvalent amine, and a cross-linker.2. The polymeric mesh according to item 1 , wherein the cross-linked polymer is a gel.3. The polymeric mesh according to item 1 , wherein the cross-linked polymer is immobilized on a support material, thus forming a composite material.4. The polymeric mesh according to any of items 1 to 3, wherein the cross-linker is an oxirane compound or an organic dihalide; or wherein the polyvalent carboxylic acid is a dicarboxylic acid, and the polyvalent amine is a triamine, preferably wherein the dicarboxylic acid is adipic acid, the polyvalent amine is diethylenetriamine, and the cross-linker is epichlorohydrin, preferably wherein epichlorohydrin is attached via one functionality only to the polyvalent amine; or wherein the polyvalent carboxylic acid is a tricarboxylic acid and the polyvalent amine is a diamine, preferably wherein the tricarboxylic acid is citric acid, the polyvalent amine is hexamethylenediamine, and the cross-linker is epichlorohydrin.5. A composite material comprising a cross-linked polymer, the cross-linked polymer being defined in item 4, wherein the cross-linked polymer is immobilized on a support material.6. The composite material according to item 5, wherein the support material comprises particles, preferably wherein the particles comprise activated carbon or an ionexchanger; or wherein the support material is a tissue or a fabric; orwherein the support material comprises glass fibers, preferably combined with polyester fibers.7. A process for the synthesis of a composite material as defined in item 5 or 6, comprising steps (i) to (iv):(i) providing a support material,(ii) wetting the support material with a cross-linker and an amino group-containing polymer in a solvent, wherein the polymer comprises the residues of a polyvalent carboxylic acid and residues of a polyvalent amine;(iii) heating the wetted support material at a temperature in the range of from 80 °C to 195 °C or 80°C to 180°C, preferably 80 to 150°C, more preferred 80 to 110°, supplying thermal, oscillation, vibrational, or radiation energy, thus allowing the cross-linking, and(iv) optionally evaporating excess solvent.8. A process for the synthesis of a composite material as defined in item 5 or 6, comprising steps (i) to (iv):(i) providing a support material,(ii) wetting the support material with an amino group-containing polymer, wherein the amino group-containing polymer comprises the residues of a polyvalent carboxylic acid and residues of a polyvalent amine, and wherein a cross-linker is attached via one functionality only to the amino group-containing polymer, in a solvent;(iii) heating the wetted support material at a temperature in the range of from 80 °C to 195 °C or 80°C to 180°C, preferably 80 to 150°C, more preferred 80 to 110°, supplying thermal, oscillation, vibrational, or radiation energy, thus allowing the cross-linking, and(iv) optionally evaporating excess solvent.9. The process according to item 7 or 8, wherein the polyvalent carboxylic acid is adipic acid, the polyvalent amine is diethylenetriamine, and the cross-linker is epichlorohydrin; orwherein the polyvalent carboxylic acid is citric acid, the polyvalent amine is hexamethylenediamine, and the cross-linker is epichlorohydrin.10. The process according to anyone of items 7 to 9, wherein the solvent in step (ii) is water; or wherein the support material comprises activated carbon particles, preferably having a median pore diameter between 15 and 200 nm; preferably wherein the carbon particles are glued together by the epoxy-containing polymer, thus forming a solid piece / monolith; or wherein the support material comprises glass fibers combined with polyester fibers; or wherein the support material is a tissue or fabric.11. The process according to anyone of items 7 to 10, wherein prior to step (ii) or in step (ii) the support material is contacted with a detergent solution, preferably wherein the detergent is based on sodium dodecyl sulphate or a polyoxymethylene or a polysorbate.12. The process according to anyone of items 7 to 11 , wherein the polymer is derivatized by means of a derivatizing reagent, preferably wherein a reagent used for derivatisation is an anhydride or a lactone.13. A composite material as defined in item 5 or 6, obtainable by a process as defined in anyone of items 7 to 12.14. A method for removing harmful compounds from an environment selected from a gas, preferably air, or water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein the polymeric mesh as defined in anyone of items 1 to 4, or a mixture of the polymeric mesh with an adsorbent, or a composite material as defined in item 5 or 6 or 13 is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.The method according to item 14, wherein the harmful compound is an acidic or a neutral compound, such as a drug or a pesticide, and metabolites thereof, a fluorinated carboxylic and sulphonic acid, as well as a combination of two or more thereof; or wherein the support material comprises particles smaller than 500 pm, wherein undesired substances are first adsorbed by the composite material, and the aqueous solution or suspension is finally separated after the depletion of the target compounds, using a membrane; or wherein a combination of at least two composite materials is used, at least one of them comprising a basic polymer and at least one of them comprising an acidic polymer. A method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material as defined in item 5 or 6 or 13 comprising activated carbon or an ion exchanger, preferably used as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides. A method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material as defined in item 5 or 6 or 13 comprising glass fibers, polyester fibers, or any woven or non-woven support material, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides. A method for removing harmful compounds from an environment selected from a gas, preferably air, or water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in item 5 or 6 or 13 comprising activated carbon or an ion exchanger, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and theirdegradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.19. The method of item 18, wherein the bacteria are legionella, pseudomonas aeruginosa, staphylococcus aureus, or klebsiella pneumoniae.20. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in item 5 or 6 or 13 comprising activated carbon or an ion exchanger, is contacted with said harmful compounds, preferably selected from multi-resistant germs, preferably from bacteria and viruses and their DNA, or from oligonucleotides, containing the gene sequences responsible for the multi-resistance.21. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in item 5 or 6 or 13 comprising activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pesticides, drugs or their metabolites, more preferred from chlorothalonil metabolite R471811.22. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in item 5 or 6 or 13 comprising activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from polyfluorinated compounds, preferably carboxylic and sulphonic acids (PFAS), more preferred from short chain moieties like perfluoro octanoic acid (PFOA) or products from GenX processes.23. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueoussolution, most preferred a body fluid, wherein a composite material as defined in item 5 or 6 or 13 comprising a fabric, or a wound dressing material, also combined with activated carbon, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from endotoxins or lipoteichoic acid and other endogenic or exogenic pyrogenic substances.24. A method of using an acidic polymer for the binding of basic to neutral compounds, preferably drugs, pesticides, and their metabolites, fungi, and their spores; wherein the polymer is a cross-linked polymer comprising preferably residues of a polyvalent carboxylic acid selected from citric acid, residues of a polyvalent amine selected from hexamethylenediamine, and a cross-linker selected from epichlorohydrin.Detailed Description

[0007] As used herein, the term “polymeric mesh” of the present application is synonymously used with the term “polymeric mesh adsorbent”. A technical synonym for the term “polymeric mesh adsorbent” as used herein is the term “filter medium” when used in application.

[0008] A polymeric mesh is either a “porous polymeric gel”, also referred to as “gel”, or a composite material comprising the gel coated onto a support material, i.e., the gel is immobilized on the support material, thus forming an immobilized porous polymeric coating on the support material. Accordingly, a gel comprises at least one at least partially porous solid polymer without support material. The porosity of the polymer is preferably generated by the space available inside and between the immobilized coils and globules. Preferred materials are in both cases functional polymers and co-polymers, also comprising related derivatives, wherein at least one functional group bears a ligand or residue.

[0009] First aspect: Polymeric mesh

[0010] According to the first aspect, the invention relates to a polymeric mesh comprising a cross-linked polymer comprising residues of a polyvalent carboxylic acid, a polyvalent amine and a cross-linker.

[0011] The term “polyvalent” as used herein means that more than one functional group is present, i.e. more than one carboxylic group in the polyvalent carboxylic acid and more than one amino group in the polyvalent amine.

[0012] The term “amino groups” as used herein means that the polyvalent amine comprises primary amino groups or secondary or tertiary amino groups or quaternary ammonium groups. Additionally, in one embodiment, secondary or tertiary or secondary and tertiary amino groups or secondary, tertiary, and quaternary amino groups can be present.

[0013] The term “residue” as used herein defines the moiety of a polyvalent carboxylic acid being devoid of the OH-groups of the carboxylic groups, the moiety of a polyvalent amine being devoid of hydrogen-groups of amino groups, and the moiety of a cross-linker connecting two polymer strands of the polymer.

[0014] In one embodiment, the molar ratio of the residues of the polyvalent carboxylic acid to the polyvalent amine to the cross-linker, respectively the molar ratio of the polyvalent carboxylic acid to the polyvalent amine to the cross-linker, is in a range of from (0.8 to 1 .2) : (1.2 to 0.8) : (0.22 to 0.28), or from (0.9 to 1.1 ) : (1.1 to 0.9) : (0.23 to 0.27), or (0.95 to 1.05) : (1.05 to 0.95) : (0.24 to 0.26), or 1 : 1 : 0.25.

[0015] In one embodiment, the polymer comprises amido groups.

[0016] In one embodiment, the polymer comprises moieties of a polyamide. In one embodiment, the polymer is a polyamide.

[0017] In a preferred embodiment, the polymer comprises amido groups, amino groups and carboxylic groups.

[0018] In one embodiment, the polymer comprises free carboxylic groups in excess to amino groups. In this embodiment, the polymer may have acidic properties.

[0019] In still a further embodiment, the polymer comprises amido groups and additionally free carboxylic groups in excess to amino groups. In this embodiment, the polymer may have acidic properties.

[0020] In still a further embodiment, the polymer comprises free amino groups in excess to carboxylic groups. In this embodiment, the polymer may have basic properties.

[0021] In still another embodiment, the polymer comprises amido groups and additionally free amino groups in excess to carboxylic groups. In this embodiment, the polymer may have basic properties.

[0022] In one embodiment, the functionality of the polyvalent carboxylic acid and the functionality of the polyvalent amine are different.

[0023] The term “functionality” as used herein means the presence of functional groups in a molecule. A monofunctional molecule possesses one functional group, a bifunctional (or difunctional) two, a trifunctional three, and so forth.

[0024] In one embodiment, the functionality of the polyvalent carboxylic acid is higher than the functionality of the polyvalent amine, i.e. the number of carboxylic groups exceeds the number of amino groups. Accordingly, the formed polymer may have acidic properties. In one embodiment, the polyvalent carboxylic acid is a tricarboxylic acid, and the polyvalent amine is a diamine.

[0025] In one embodiment, the functionality of the polyvalent carboxylic acid is lower than the functionality of the polyvalent amine, i.e., the number of carboxylic groups is lower than the number of amino groups. Accordingly, the formed polymer may have basic properties. In one embodiment, the polyvalent carboxylic acid is a dicarboxylic acid, and the polyvalent amine is a triamine.

[0026] In one embodiment, a polymer where the functionality of the polycarboxylic acid and the functionality of the polyamine are the same is excluded. In one embodiment, a polymer where the polyvalent carboxylic acid is a dicarboxylic acid, and the polyvalent amine is a diamine is excluded.

[0027] The polymeric mesh is in the form of a porous polymeric gel.

[0028] Porosity

[0029] The porosity of the polymer is preferably generated by the space available inside and between the immobilized coils and globules. Preferred materials are in both cases functional polymers and co-polymers, also comprising related derivatives, wherein at least one functional group bears a ligand or residue. Immobilized means that the polymeric mesh is not soluble under the conditions of application, preferably achieved by means of non- covalent or covalent attachment to a surface of a support material, by means of crosslinking, by means of low solubility in the solvents applied, or by a combination of said procedures and properties. The fibrous substrate capable of binding or embedding said polymeric gels can be made from natural and / or synthetic fibres with woven and / or nonwoven structures.

[0030] Gel

[0031] The cross-linked polyamine is a gel.

[0032] As used herein, the term ”gel” encompasses a non-fluid colloidal network or polymer network that is expanded throughout its whole volume by a fluid. The gel contains a covalent polymer network, e.g., a network formed by crosslinking polymer chains or by nonlinear polymerization. The polymer network is formed through the physical aggregation of polymer chains, caused by hydrogen bonds, crystallization, helix formation, complexation, and covalent binding that results in regions of local order acting as the network junction points.

[0033] Polyvalent carboxylic acid

[0034] As used herein, the term “polyvalent carboxylic acid” encompasses any organic acid having at least two carboxylic groups.

[0035] The polyvalent carboxylic acid may bear further functional groups such as sulphonic or phosphonic groups. The further functional groups may be the same or may be different from one another.

[0036] In one embodiment, a polyvalent carboxylic group may have two, three or four carboxylic groups, preferably two or three carboxylic groups.

[0037] The term “carboxylic acid” encompasses aliphatic, cycloaliphatic and aromatic carboxylic acids.

[0038] Examples of aliphatic divalent carboxylic acids are oxalic acid, propanedioic acid, butanedioic acid, pentanedioic acid, and hexanedioic acid (adipic acid).

[0039] Examples of cycloaliphatic divalent carboxylic acids are 2,5- tetrahydrofurandicarboxylic acid and 1 ,4-cyclohexanedicarboxylic acid.

[0040] Examples of divalent aromatic dicarboxylic acid are phthalic acid, terephthalic acid, isophthalic acid, and 2,5-furandicarboxylic acid.

[0041] An example of an aliphatic tricarboxylic acid is citric acid.

[0042] An example of an aromatic tricarboxylic acid is mellitic acid,

[0043] Examples of tetracarboxylic acids are butanetetracarboxylic acids, 2,3,5- tricarboxycyclopentylacetic acid, 3,5,6-tricarboxynorbornane-2-acetic acid, 1 , 2,3,4- cyclobutanetetracarboxylic acid, 1 ,3-dimethyl-1 ,2,3,4-cyclobutanetetracarboxylic acid, 1 ,2,3,4-cyclopentanetetracarboxylic acid, 2,3,4,5-tetrahydrofuranetetracarboxylic acid, and bicyclo[2,2,2]-oct-7-en-2,3,5,6-tetracarboxylic acid.

[0044] In a preferred embodiment, the polyvalent acid is selected from an aliphatic dicarboxylic acid such as propanedioic acid, butanedioic acid, pentanedioic acid, and hexanedioic acid. Hexanedioic acid (adipic acid) is particularly preferred.

[0045] In another preferred embodiment, the polyvalent acid is citric acid.

[0046] Polyvalent amine

[0047] As used herein, the term “polyvalent amine” encompasses any amine having at least two amino groups.

[0048] The amino groups may be primary or secondary or tertiary. In one embodiment, the amino groups are primary or primary and secondary amino groups. Tertiary amino groups may also be present.

[0049] In one embodiment, the polyvalent amine contains both primary and secondary amino groups.

[0050] In one embodiment, a polyvalent amine may have two, three or four amino groups.

[0051] Suitable examples of a polyvalent amine encompass aromatic diamines such as p- and m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'- diaminodiphenylether, 4,4'-diaminodiphenylsufide, 4,4'-diaminodiphenylsulfone, 1 ,5- diaminonaththalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'aminophenyl)-1 ,3,3- trimethylindane, 6-amino-1-(4'-aminophenyl)-1 ,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluormethylbenzanilide, 3,5-diamino-4'trifluoromethylbenzanilide, 3,4'- diaminodiphenylether, 2,7-diaminofluorene, 2,2-bis(4-aminophenyl)hexafluorpropane, 4,4'- methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'- diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'- bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4- aminophenoxy)phenyl]hexafluoropropane, 1 ,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4- aminophenoxy)-biphenyl, 1 ,3'-bis(4-aminophenoxy)benzene, 9,9-bis(4- aminophenyl)fluorene, 4,4'(p-phenylenisopropylidene)bisaniline, 4,4'(m- phenyleneisopropylidene)bisaniline, 2,2'-bis[4-(4-amino-2)trifluormethylphenoxy)phenyl]hexafluoropropane, 4,4'-bis[4-(4-amino-2- trifluoromethyl)phenoxy]-octafluorobiphenyl, 4,4'-oxydianiline, and diaminotetraphenylthiophene.

[0052] Suitable examples of aliphatic diamines and alicyclic diamines are 1 ,2- ethanediamine, 1 ,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 ,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4, 7- methanoindanylendiamine, tricyclo[6,2,1 ,02.7]-undecylendimethyldiamine, and 4,4'- methylenebis(cyclohexylamine).

[0053] Further examples of polyvalent amines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and tripropylenetetramine.

[0054] In a preferred embodiment, the polyvalent amine is selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and tripropylenetetramine. In a particularly preferred embodiment, the polyvalent amine is diethylenetriamine.

[0055] In another preferred embodiment, the polyvalent amine is selected from tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine. In a particularly preferred embodiment, the polyvalent amine is hexamethylene diamine.

[0056] Further examples of polyvalent amines are selected from poly(vinylformamide-co- vinylamine), a linear or branched poly(vinylamine), a poly(allylamine), a poly(ethyleneimine), a poly-lysine, a poly(vinylimidazol), a polypyrrol, a polyaniline, and copolymers containing such amino polymers.

[0057] Cross-linker

[0058] As used herein, the term “cross-linker” encompasses any compound being suitable to link one polymer chain of a polymer to another polymer chain of the polymer or to connect two functional groups of the same polymer chain. These links may take the form of covalent bonds or ionic bonds.

[0059] In a preferred embodiment, the links take the form of covalent bonds.

[0060] In a preferred embodiment, the cross-linker comprises at least two functional groups being capable of linking one polymer chain of a polymer to another polymer chain of the polymer. These two functional groups may be the same or may be different from one another.

[0061] In a preferred embodiment, the cross-linker is an oxirane or comprises an oxirane.

[0062] As used herein, the term “oxirane” means that the crosslinker comprises at least one epoxy group and at least one further functional group being capable of reacting with a polymer chain. Preferably, this further functional group is not an epoxy group.

[0063] In a preferred embodiment, the further functional group of the oxirane may be a halide, preferably Cl or Br.

[0064] In a preferred embodiment, the cross-linker is epichlorohydrin.

[0065] In a further preferred embodiment, the cross-linker is an organic dihalide.

[0066] As used herein, in one embodiment, the term “organic dihalide” means an aliphatic or cyclic or cycloaliphatic organic dihalide.

[0067] In a preferred embodiment, the organic halide is a compoundX-(CH2)n-X, wherein n preferably ranges from 1 to 6, and X is independently Cl or Br.

[0068] In a preferred embodiment, n is two, and the dihalide is 1 ,2-dichloroethane.

[0069] In one embodiment, the cross-linker is attached via one functional group to the polymer before the final cross-linking is achieved.

[0070] In a preferred embodiment, the polymeric mesh is or comprises at least the crosslinked polymer comprising residues of a polyvalent carboxylic acid selected from an aliphatic dicarboxylic acid, wherein the polyvalent amine is an aliphatic triamine, and the cross-linker is an oxirane or an organic dihalide.

[0071] In a further preferred embodiment, the polymeric mesh is or comprises the crosslinked polymer comprising residues of a polyvalent aliphatic carboxylic acid, a polyvalent amine and a cross-linker, wherein the polyvalent organic acid is an aliphatic dicarboxylic acid selected from propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, or a tricarboxylic acid selected from citric acid, the polyvalent amine is an aliphatic amine selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, and the cross-linker is an oxirane selected from epichlorohydrin.

[0072] In a further preferred embodiment, the polymeric mesh is or comprises a crosslinked polymer comprising residues of a polyvalent carboxylic acid, a polyvalent amine and a cross-linker, wherein the polyvalent carboxylic acid is an aliphatic dicarboxylic acid selected from hexanedioic acid or a an aliphatic tricarboxylic acid selected from citric acid, the polyvalent amine is an aliphatic triamine selected from diethylenetriamine or an aliphatic diamine selected from hexamethylendiamine, and the cross-linker is an oxirane selected from epichlorohydrin.

[0073] In a further preferred embodiment, the polymeric mesh is or comprises a crosslinked polymer comprising residues of a polyvalent carboxylic acid, a polyvalent amine and a cross-linker, wherein the polyvalent carboxylic acid is an aliphatic dicarboxylic acid selected from hexanedioic acid, the polyvalent amine is an aliphatic triamine selected from diethylenetriamine, and the cross-linker is an oxirane selected from epichlorohydrin.

[0074] In a further preferred embodiment, the polymeric mesh is or comprises a crosslinked polymer comprising residues of a polyvalent carboxylic acid, a polyvalent amine and a cross-linker, wherein the polyvalent carboxylic acid is an aliphatic tricarboxylic acid selected from citric acid, the polyvalent amine is an aliphatic diamine selected from hexamethylenediamine, and the cross-linker is an oxirane selected from epichlorohydrin.

[0075] The polymeric mesh may be produced according to methods, the basic principles of which are known in the art, such as polycondensation reactions.

[0076] Support material

[0077] Although the polymeric mesh in the form of a porous polymeric gel may be used as such, for practical reasons, the combination with a rigid skeleton, namely a support material, is favorable. Herein, a composite material comprising the cross-linked polymer and the support material is formed.

[0078] If the polymeric mesh in the form of a porous polymeric gel as such is used, in one embodiment, the polymer is molten and extruded using a nozzle with preferably less than 1 mm diameter. The resultant string is cut into short pieces with preferably less than 1 mm length. These swellable particles may be used for any of the applications as listed in the fourth aspect.

[0079] In one other embodiment, the polymer is molten and extended, or cured between two plates, forming a membrane preferably with a thickness less than 1 mm.

[0080] As used herein, the term “support material” encompasses any material to which the polymeric gel may be applied, and which absorbs / adsorbs the polymeric gel. In one embodiment, the polymeric coating according to the invention is covalently attached to the support material. Absorption / adsorption and / or covalent attachment result in immobilization of the polymeric mesh on the support.

[0081] In one embodiment, the gel as such can be used as adsorbent. Alternatively, also a mixture comprising the dried, finally cross-linked gel and a rigid adsorbent is suitable. In one embodiment, a combination of activated carbon and the dry gel is applied. This gel, after temperature treatment and drying can also be mixed with the adsorbents, described as potential support materials below.

[0082] In one embodiment, the polymeric mesh may be synthesized in the presence of a support material.

[0083] The support material preferably comprises any kind of tissue or fabric, either woven or non-woven, or a monolithic backbone, or a membrane, or porous or non-porous particles, or any combination of at least two different of these material categories.

[0084] Support materials may be either porous or non-porous or may be a combination of both.

[0085] The form of the porous support material is not particularly limited. Any support material can be used for the preparation of the composite materials of the present application, provided that at least a polymer immobilized to the support surface remains stable under the conditions of preparation, rinsing, cleaning and, most importantly, application conditions.

[0086] The following support materials are examples of suitable starting or raw materials for the synthesis of polymeric mesh of the present application. This selection comprises examples and is not considered to be complete. Other materials as known to a skilledperson may also be applicable as a support. Preferred embodiments are combinations with the amino group-containing polymers as listed in the section “polyvalent amines”.

[0087] Fabrics made of synthetic fibers are selected from preferably poly(ester), poly(olefine), poly(amide), poly(acrylonitrile), poly(phenylene sulfide), poly(imide), aramide, poly(vinylamine), poly(vinylidene fluoride); melamine resins, acetyl cellulose, methylcellulose; natural fibers such as wool, cotton, cellulose, amylose, or chitosan; mineral fibers like glass, micro-glass, ceramic. The fabric media e.g. in the form of a filter as described above can be carried out as nonwovens, e.g. staple fibers, needle felts with or without scrim, wet-laid nonwoven, spun-bond nonwoven, melt blown nonwoven; woven fabrics or knitted fabrics, or combinations out of both aforesaid variants. The fabric filter support material can also consist of a combination comprising at least two of the aforesaid variants.

[0088] Granulate, powder or pellets (particulate materials), either porous or non-porous, e.g. comprising activated carbon, silica gel, zeolite, diatomaceous earth, other ceramic compound like alumina oxide, or comprising organic e.g. ion exchanger resin, and any mixture or combination of foresaid compounds may be used.

[0089] In a preferred embodiment, a cation exchanger is used for immobilization of the amino group-containing polymer. This cation exchanger may be based on polystyrene bearing sulfonate residues. In another embodiment, the cation exchanger is a polyacrylate or poly(methacrylate).

[0090] Preferably, the ion exchanger particles are spherical. The particle size preferably is between 5 pm and 2 cm, preferably between 20 pm and 5 mm, and most preferred between 100 pm and 1 mm.

[0091] In a further preferred embodiment, the support material for poly(vinylamine) or poly(vinylformamide-co-vinylamine) is a cation exchanger, a fabric, or glass fibers, also in combination with polymer fibers.

[0092] In preferred embodiments, such particulate materials can be combined with fabric filter media, e.g. by sticking on or by embedding in between two or more fabric layers or even by mixing it into single fabric layers between the single fibers.

[0093] Other support materials like synthetic membranes or foils, ceramic honeycombs, porous sponges on a synthetic, ceramic or natural (biologic) base, porous plate, cylinders or other geometric shapes made of sintered granulates which can be passed through by air or water may be used. Further, it is possible to combine at least two of the above and below materials and media, generating a kind of multi-layered sandwich structure, which can be varied.

[0094] Monolithic support materials are also applicable. Monolithic means a homogeneously porous piece of support material exhibiting a thickness of at least 0.5 mm, preferably made from silica, alumina, zirconia, steel (e.g. a porous frit), poly(acrylate), or activated carbon.

[0095] In a further preferred embodiment, the monolithic support material is a disk, a torus, a cylinder or a hollow cylinder, with at least 0.5 mm height and with an arbitrary diameter. Pellicular materials are also within the scope of the present invention. They exhibit a solid core and a porous surface or external layer. Some pellicular materials are commercially available comprising threads or solid particles coated with a porous layer.

[0096] In a preferred embodiment, the support particles comprise activated carbon.

[0097] As used herein and as commonly known, the term “activated carbon” (synonymously used with the term “activated charcoal”) is a form of carbon commonly used to filter contaminants from water and air, among many other uses. It is processed (activated) to have small, low-volume pores that increase the surface area available for adsorption or chemical reactions. The activation process is carried out at high temperature. It is distinguished between steam activation and chemical activation. Due to its high degree of microporosity, one gram of activated carbon has a high surface area such as at least 500 m2as determined by gas adsorption. Charcoal, before activation, has a specific surface area in the range of 2.0-5.0 m2 / g. An activation level sufficient for useful application may be obtained solely from high surface area. Further chemical treatment often enhances adsorption properties. Activated carbon is usually derived from waste products such as coconut husks. These bulk sources are converted into charcoal before being 'activated'. When derived from coal it is referred to as activated coal. Activated coke is derived from coke. Preferred is the use of activated carbon stemming from coconutshells, because of some unique properties. It is derived from a sustainable raw material source and known for its superior mechanical hardness. But also activated carbon materials from hard coal, lignite or wood are convenient for these purposes.

[0098] Especially in private households, devices comprising cartridges made from activated carbon are very popular for every-day cleaning of drinking water or breathing air.

[0099] For this purpose, the activated carbon particles are glued together, thus forming monolithic pieces, preferably 20 to 100 cm in length and 2 to 50 cm in diameter and preferably applied in cartridges with an inlet and outlet pipe. After the end of usage, these cartridges are easy to be exchanged. The particle size of activated carbon in monoliths is between 10 pm and 3 mm, preferably between 100 pm and 1 mm.

[0100] Like with the loose support material, the properties of activated carbon supports are significantly enhanced by coating with the cross-linked polymer. In addition to adsorptive capabilities, the polymer itself may function as the inter-connecting glue between carbon particles, just by cross-linking polymer chains already fixed to adjacent particles.

[0101] Also, other substances may be applied for gluing as are known in the prior art.

[0102] For this purpose, the polymer concentrations range preferably between 5% and 70%, more preferably between 10% and 60%, most preferably between 30% and 50%, of the carbon dry mass.

[0103] The coating and gluing process is preferably achieved using a glass or steel cylinder of appropriate size for starting the process. When the strand / brick is sufficiently firm, it will be further extruded within a continuous process, subsequently cut to desired size. The diameter of these adapted pieces preferably ranges from 2 to 50 cm.

[0104] Immobilization

[0105] Among the available methods of polymer immobilization cross-linking is preferred. The polymer immobilization may be also achieved by covalent binding to the support material, or by precipitation or adsorption, or by any other form of deposition from a solution, suspension or emulsion. In preferred embodiments, the total amount of polymerimmobilized to a support material is between 0.1 % and 200% of the support weight, more preferred between 1 % and 100%, most preferred between 5% and 50%. The degree of cross-linking for a polymeric mesh synthesized for the purpose of the present application should preferably not exceed 50%. Preferred are 2% to 40%, more preferred 5% to 30%, most preferred are 10% to 20%. The degree of cross-linking is calculated from the equivalent weight of the cross-linker applied, relating to the equivalents of the functional groups available in the related batch. E.g. using a bivalent cross-linker the molar amount is divided by two, to obtain the degree of cross-linking (20 mole equivalents are thus generating a 10% nominal degree of cross-linking).

[0106] The cross-linker may either be introduced together with the polymer to allow for a simultaneous reaction of both, or the cross-linking reaction may be carried out separately, in a subsequent step. Alternatively, the cross-linker may be attached via one functionality only to the amino group or to the carboxylic group containing polymer.

[0107] Whenever a polymer or an amino group-containing polymer is mentioned together with a cross-linker throughout this description, the above three embodiments are concerned.

[0108] Second aspect: Composite material comprising the cross-linked polymer and a support

[0109] According to the second aspect, the invention relates to a composite material comprising a cross-linked polymer comprising an amino group-containing polymer and a support. Support materials are defined above with respect to the first aspect.

[0110] In one embodiment, the support material is in particle form, preferably activated carbon or ion-exchanger particles.

[0111] In another embodiment, the support material is in the form of fibers, preferably glass fibers.

[0112] In still another embodiment, the support material is a tissue or a fabric, woven as well as non-woven.

[0113] Third aspect: Process for the synthesis of a composite material and composite material obtained by the process

[0114] According to the third aspect, the invention relates to a process for making a composite material comprising a cross-linked amino group-containing polymer, a support material and a cross-linker, and to a composite material obtained by the process as defined hereinunder.

[0115] The term “amino group-containing polymer” encompasses any polymer containing amino groups.

[0116] In one embodiment, the amino group-containing polymer is selected from poly(vinylformamide-co-vinylamine), a linear or branched poly(vinylamine), a poly(allylamine), a poly(ethyleneimine), a poly-lysine, a poly(vinylimidazol), a polypyrrol, a polyaniline, and copolymers containing such amino polymers. Accordingly, the respective cross-linked amino group-containing polymer is a cross-linked poly(vinylformamide-co- vinylamine), a cross-linked linear or branched poly(vinylamine), a cross-linked poly(allylamine), a cross-linked poly(ethyleneimine), a cross-linked poly-lysine, a crosslinked poly(vinylimidazol), a cross-linked polypyrrol, a cross-linked polyaniline, or crosslinked copolymers thereof.

[0117] In a preferred embodiment, the amino group-containing polymer is a polymer comprising residues of a polyvalent carboxylic acid and a polyvalent amine. Accordingly, the formed cross-linked polymer is the polymer as defined in the first aspect, namely a crosslinked polymer comprising residues of a polyvalent carboxylic acid, a polyvalent amine and a cross-linker.

[0118] In one embodiment, the process comprises the following steps (i) to (iv):(i) providing a support material,(ii) wetting the support material with a cross-linker and an amino group-containing polymer in a solvent;(iii) heating the wetted support material at a temperature in the range of from 80 to 195 °C or 80°C to 180°C, preferably 80 to 150°C, more preferred 80 to 110°,supplying thermal, oscillation, vibrational, or radiation energy, thus allowing the cross-linking, and(iv) optionally evaporating excess solvent.

[0119] In one embodiment, in step (iii), the time for supplying energy ranges from 20 minutes to four hours, preferably 20 minutes to two hours.

[0120] Accordingly, in step (ii), the cross-linker and the amino group-containing polymer are in the form of a mixture in the solvent, i.e. , in the form of individual molecules.

[0121] In one embodiment, the amino group-containing polymer is poly(vinylamine), also in combination with poly(vinylformamide), or is poly(vinylformamide-co-vinylamine), preferably immobilized to activated carbon.

[0122] In one further embodiment the support material for poly(vinylamine) is a cationexchanger, a fabric, or are glass fibers, also in combination with polymer fibers.

[0123] In another embodiment, the process comprises the following steps (i) to (iv):(i) providing a support material,(ii) wetting the support material with an amino group-containing polymer, wherein a cross-linker is attached via one functionality only to the amino group-containing polymer, in a solvent;(iii) heating the wetted support material at a temperature in the range of from 80 to 195 °C or 80°C to 180°C, preferably 80 to 150°C, more preferred 80 to 110°, supplying thermal, oscillation, vibrational, or radiation energy, thus allowing the cross-linking, and(iv) optionally evaporating excess solvent.

[0124] In one embodiment, in step (iii), the time for supplying energy ranges from 20 minutes to four hours, preferably 20 minutes to two hours,

[0125] In this embodiment, in step (ii), an amino group-containing polymer is used, wherein a cross-linker is attached via only one functionality to the amino group-containingpolymer prior to the wetting in step (ii). However, the attached cross-linker does not crosslink the polymer in step (ii).

[0126] In a preferred embodiment, epichlorohydrin is covalently bound to the amino group- containing polymer via one functional group only.

[0127] Such a product may be produced according to known methods.

[0128] A product based on adipic acid, diethylenetriamine and epichlorohydrin is suitable for use in step (ii).

[0129] Another example of a suitable polymer is made from adipic acid, aminoethylpiperazine, diethylenetriamine and epichlorohydrin.

[0130] Such polymers may have benefits in handling. E.g., in one embodiment, it is possible to provide such polymer as an aqueous solution, preferably an acidic solution. The pH value of this acidic solution is preferably in the range of from 3 to 5 such as 3.5 to 4.5.

[0131] Preferably, an aqueous solution contains the polymer in a concentration between 10 and 30 % (w / w).

[0132] In a preferred embodiment, the amino group-containing polymer used in step (ii) of the above two embodiments is a polymer comprising or consisting of residues of a polyvalent carboxylic acid and a polyvalent amine.

[0133] In a preferred embodiment, the polyvalent carboxylic acid and the polyvalent amine are selected from a di- or tricarboxylic acid and a di- or triamine.

[0134] In one embodiment, the polyvalent carboxylic acid is selected from a dicarboxylic acid and the polyvalent amine is selected from a triamine. In this embodiment, the polymer is basic.

[0135] In another embodiment, the polyvalent carboxylic acid is selected from a tricarboxylic acid and the polyvalent amine is selected from a diamine. In this embodiment, the polymer is acidic.

[0136] In a preferred embodiment, the concentration of the dissolved polymer in the solvent in step (ii) is in the range of from 2 to 300 % (w / w), preferably from 5 to 250 %, further preferred from 10 to 200 % or from 15 to 150 % or from 20 to 100 % or from 25 to 50 %, respectively relating to the weight of the support.

[0137] When this solution is evaporated without a support at ambient temperature, typically a solid gel can be isolated, entirely insoluble in common solvents, particularly so in water. Nevertheless, this kind of gel is swellable in water, with the swelling process being reversible upon drying (see examples).

[0138] In a preferred embodiment, the dicarboxylic acid is adipic acid, the triamine is diethylenetriamine and the cross-linker is epichlorohydrin.

[0139] In another preferred embodiment, the tricarboxylic acid is citric acid, the diamine is hexamethylenediamine and the cross-linker is epichlorohydrin.

[0140] In another preferred embodiment, the support material comprises activated carbon.

[0141] In another preferred embodiment, the support material comprises glass fibers combined with polyester fibers.

[0142] In still another preferred embodiment, the support material is a tissue or fabric.

[0143] In one embodiment, prior to step (ii) or in step (ii), the support material is contacted with a detergent solution.

[0144] Detergents will generally improve the homogeneous coating of the support surface, preferably when using activated carbon. Any detergents are suitable, both ionic and nonionic ones.

[0145] Also preferred are anionic detergents like sodium dodecyl sulphate (SDS) or cholate derivatives, when the polymer is bearing basic groups such as amino groups. Cationic detergents like cetyl trimethylammonium bromide are preferred when the polymer comprises acidic groups.

[0146] In one embodiment, the detergent is an anionic tenside or surfactant based on sodium dodecyl sulphate. Such products are commercially available as SDS.

[0147] In another embodiment, the detergent is a non-ionic tenside or surfactant based on polyoxymethylene. Such products are commercially available as Brij 35.

[0148] In another embodiment, the detergent is a non-ionic tenside or surfactant based on polysorbate 20. Such products are commercially available as Tween 20.

[0149] The nominal chain length with Brij is preferably between 30 and 98, most preferred is Brij 35. The nominal chain length with Tween is preferably 40 to 80, most preferred is 40.

[0150] However, further detergents as known from the prior art may be used for this purpose.

[0151] In one embodiment, when the support material used in step (i) is in particle form and consists of or comprises activated carbon, and when the cross-linker is an oxirane or the polymer comprises an oxirane, said carbon particles are glued together by the oxirane, thus forming a solid piece / monolith. The cross-linked polymer itself serves as the preferred glue. However, other substances may be applied for this purpose.

[0152] Solvents

[0153] The solvent may be any solvent suitable to dissolve (or to at least partially dissolve and / or suspend) the materials used in step (ii). Dispersions are also suitable.

[0154] Examples of polar solvents are selected from water and sulfoxide-based solvents such as dimethyl sulfoxide or diethyl sulfoxide, formamide-based solvents such as N,N- dimethyl formamide and N,N-diethyl formamide, acetamide-based solvents such as N,N- dimethylacetamide und N,N-diethylacetamide, pyrrolidone-based solvents such as N- methyl-2-pyrrolidone und N-vinyl-2-pyrrolidone, ether-based solvents such as tetrahydrofuran, dioxane, und dioxolane, alcohol-based solvents such as methanol, ethanol und butanol, cellosolve-solvents such as butyl cellosolve, hexamethylphosphoramide, y- butyrolactone, or a mixture of two or more thereof.

[0155] In a preferred embodiment of the process, the solvent is water.

[0156] The invention also relates to a composite material as defined in the second aspect, wherein the composite material is obtainable by a process as defined in the third aspect.

[0157] Wet-laid process

[0158] In a further preferred embodiment, the processes defined above are based on a wet-laid process. Wet-laid processes are basically known in the art.

[0159] Wet-laid processes as known e.g. to produce paper or filter media as disclosed in WO 2020 / 079233. For a detailed description of these processes see this document. Such processes start from small fibers and a binder or adhesive, wherein the fibers are glued together, preferably at enhanced temperatures, thus forming porous paper sheets or paper webs. These prior art filter media are effective for the removal of fine particles. The related filter classes range from M5 - M6, F 7 - F9 acc. EN 779 and H10 - H13 acc. EN 1822.

[0160] For the application in such wet-laid processes, in one embodiment, polymeric adhesives may be used, forming a nano-porous mesh, thus capable of adsorbing undesired compounds from gasses and liquids, mainly hazardous substances.

[0161] In one preferred embodiment, a functional polymer is used as an adhesive (binding agent, binder) for particles, preferably for the support materials defined herein, more preferably for fibers, thus generating a composite material, comprising a polymeric coating according to the invention present inside and between the immobilized polymer coils and globules, and, in addition, a second web or sieve, due to the space left between the support material fibers or particles.

[0162] The present invention, thus, in one embodiment, relates to a composite comprising fibers, particles, or fibers together with particles, and a functional polymer as an adhesive.

[0163] Within a more preferred embodiment, the functional polymer adhesive is combined with a cross-linking agent allowing to glue the fibers and / or particles together, thus forming a mechanically and thermally stable composite, exhibiting a web with a pore size between 50 nm and 1 mm, preferably between 200 nm and 100 pm, more preferred between 1 pm and 50 pm, wherein the support fibers and / or particles are coated with the cross-linked,preferably nano-porous layer of the polymer. The pore size is determined according to ASTM F316-03.

[0164] Moreover, the porous polymeric mesh of said composite material comprises pores in a nanometer range, due to the space available inside and between the immobilized coils and globules of the functional polymer. These nanopores of said polymeric mesh are exhibiting an upper, but variable pore size radius Rhi, thus capable of retaining a significant amount of compounds with a hydrodynamic radius below this exclusion limit Rhi (nm) inside the pore volume. Rhi ranges preferably below 20 nm, more preferred below 10 nm, most preferred below 6 nm. This hydrodynamic pore radius is determined according to methods disclosed in WO 2020 / 079233.

[0165] Accordingly, said adhesive comprising a polymer and preferably a cross-linker, works also as binding compounds as listed hereinunder.

[0166] Moreover, in one embodiment, the present application relates to a composite material, wherein short fibers or small particles are connected with / by a (cross-linked) mixture of a functional polymer and a cross-linking agent.

[0167] Within preferred embodiments, the binding agent is a basic polymer, preferably an amino group-containing polymer, more preferred poly(allylamine) or poly(ethyleneimine), most preferred poly(vinylamine) or co-polymers thereof with vinyl formamide such as poly(vinylformamide-co-vinylamine), preferably applied in combination with a cross-linker. Alternatively, the polymer comprises a multivalent carboxylic acid.

[0168] Fibers of the present invention are solid, thin materials, preferably made from glass or from polymers.

[0169] Within preferred embodiments, the preferred diameter of the fibers is between 0,1 pm and 100 pm, with respect to filter media made with a wet-laid process. The more preferred diameter of glass fibers is between 0.1 pm and 20 pm. The more preferred diameter of synthetic polymer fibers is between 2 pm and 30 pm.

[0170] Within preferred embodiments, the fiber length is between 20 pm and 60 mm. The length of glass fibers is preferably between 50 pm and 10 mm, the length of polymeric fibers is preferably ranging between 3 mm and 30 mm.

[0171] Accordingly, the present application also discloses a composite material, wherein short fibers are connected with / by a (cross-linked) mixture of a functional polymer and a cross-linking agent.

[0172] Within preferred embodiments, mixtures of fibers are used to serve as a support material with enhanced stability and / or elasticity. When most of the fibers comprise glass materials, it is advantageous to add amounts between 0.5% and 3% of polymeric fibers in order to improve the stability and the elasticity of the resultant web.

[0173] Support materials are used as listed above also in combination with glass fibers. Particles are preferably made from silica or activated carbon, fibers preferably from glass or polyester.

[0174] Within preferred embodiments, the particle size of the particles incorporated in a composite material is preferably below 20 mm, more preferred below 5 mm, and most preferred below 500 pm.

[0175] Within an additional preferred embodiment, also nanoparticles with diameters preferably between 0.5 nm and 500 nm are connected with functional polymers. Examples are fullerenes or noble metals like nano sized gold.

[0176] Particle materials are preferably porous, exhibiting preferably a specific surface area above 100 m2per gram, and a pore volume above 0.5 ml per gram. Any organic or inorganic material is applicable, preferred are particles made from materials of the above list, more preferred made from poly(acrylic acid), poly(methacrylic acid), poly(acrylamide), poly(methacrylamide), polystyrene and polystyrene sulfonic acid, alumina, silica, and activated carbon.

[0177] Within additional preferred embodiments, a support material, preferably comprising fibers and / or particles, is suspended in a liquid medium, then precipitated, and aspirated on a sieve or a frit. The solid, preferably moist residue is contacted with a reagent solution orsuspension, comprising a functional polymer and a cross-linker, then excess liquid is aspirated, the solid layer is dried, and heated at a temperature between 60°C and 240°C, preferably between 80°C and 190°C.

[0178] Due to the interactions between the functional polymer, the complementary crosslinker, and the support material, a web is generated, comprising the empty space left between the support fibers and particles. Simultaneously a polymeric mesh is formed on the surface of the support material fibers and particles, or combinations of fibers and particles. Said composite material thus exhibits two different porosities, comprising the nano sized mesh of the cross-linked functional polymer and the web with larger space between to the interconnected particles or fibers. The relevant pore diameter ranges of both morphologies are cited above.

[0179] The preferred products of the above process are filter media, preferably starting materials for filter elements, capable of adsorbing various compound from liquids and gasses. The chemical structure of the polymer used, in particular its functional groups, is selected in advance according to the rules of complementary interaction, thus enabling a selective strong binding of target compounds.

[0180] Within alternative preferred embodiments, the functional polymer is added and adsorbed by the fibers or particles.

[0181] Finally, within further preferred embodiments, the cross-linker and the functional polymer are added and adsorbed by the fibers and / or particles already during step (ii), this precursor of the composite material is then precipitated and aspirated on a sieve or a frit, and the resulting dried solid layer is heated, until the functional polymer becomes immobilized on the surface of the support material.

[0182] Preferred are the support materials, functional polymers and cross-linkers as listed above and below.

[0183] Most preferably is the process for the production of wet-laid materials relating to fibers made from glass, polyester or poly(vinyl alcohol) and to particles made from glass, silica, alumina, or activated carbon.

[0184] Within preferred embodiments, the fibers are mixed with porous or non-porous particles, allowing the synthesis of composite materials exhibiting high surface values and thus an enhanced binding capacity. Any combination of the fibers and particle materials from the above and below lists are applicable. Preferred examples of such mixtures, without any limitation of the broad selection range, are: glass fibers together with silica gel or with activated carbon or derivatives thereof; polyester fibers together with derivatives made from activated carbon; or combinations thereof.

[0185] In one embodiment, the present application is therefore related to a composite material comprising the following components: at least one functional polymer or a derivative of a functional polymer, at least one cross-linker and at least one kind of fibers, particles, alternatively a mixture of fibers together with particles.

[0186] Moreover, the present application relates to a process for the preparation of the above composite material, wherein fibers, particles, or fibers together with particles are connected by adhesives / binders comprising at least one functional polymer and at least one cross-linker.

[0187] The present application also relates to the above composite material, wherein the fibers, particles, or fibers together with particles are connected by adhesives / binder comprising at least one functional polymer and at least one cross-linker, leaving open space between the connected support components, thus generating a web exhibiting the pore size range of the composite materials as defined above.

[0188] Within additional preferred embodiments, a combination of functional polymers is applied, preferably comprising at least one neutral and one cationic or anionic compound, more preferred at least one basic and at least one acidic component. Preferred examples of neutral polymer compounds are poly(vinyl acetate), poly(vinyl alcohol), poly(acrylates), and poly(methacrylates).

[0189] Each functional polymers and cross-linker is either applied as a solution, as a liquid or as a solid material.

[0190] Within preferred embodiments, the functional polymer of the above manufacturing process is comprising at least one basic residue, more preferred at least one primary or secondary amino group.

[0191] Alternatively, the functional polymer preferably comprises at least one acidic residue, more preferred at least one carboxylic group.

[0192] Within preferred embodiments, the cross-linker of the above manufacturing process comprises either at least two acidic residues or at least two basic residues, complementary with the basic respectively acidic residues of the functional polymer. The basic residues are preferably primary or secondary amino groups. The acidic residues are preferably carboxylic groups.

[0193] Within a further preferred embodiment, the cross-linker is already attached with one functional group to the polymer, as disclosed in the first aspect, before it is mixed with the support material.

[0194] The functional polymers and the cross-linkers are preferably not activated and not comprising active groups, more preferably the acids or bases are applied as a salt.

[0195] In addition, the formation of wet-laid materials is important, using glass fibers when the fibers are made from glass, optionally combined with polymeric fibers, as a support material. Concerning wet-laid materials, in one embodiment, at least one additional binder may be added to keep the micro-fibers connected, preferably an acrylic compound.

[0196] Derivatisation

[0197] The polymer of the present application may also be derivatized. The degree of derivatisation may be between 0.5% and 100%, preferably between 10% and 90%. Crosslinking is considered a special embodiment of derivatisation.

[0198] Any synthesis steps within the present patent application may be carried out according to the various methods and protocols as known from the prior art. Any chemistry known to a skilled person in the art may be used to realize these strategies. Activation and derivatisation reactions are closely related to the concepts as used in peptide synthesis.

[0199] The methods, substances, and reactions as e.g. published in Houben-Weyl, Vol. E 22a, 4th Edition Supplement are applicable in many respects. Mainly carbodiimides, active esters, carbonyl diimidazole (CDI), and mixed anhydrides are useful.

[0200] Without any limitation of other suitable and accessible sources, the following citations contain useful protocols for polymer immobilization and derivatization, also comprising the chemistry of functional group activation: WO 90 / 14886, WO 98 / 32790, WO 96 / 09116, EP 1 224 975, and Journal of Chromatography, 587 (1991) 271-275.

[0201] In a preferred embodiment, the derivatisation reagent is an anhydride or a lactone.

[0202] Fourth aspect: Applications such as a method of removing harmful substances from an environment

[0203] According to a fourth aspect, the invention relates to a method for removing harmful compounds from an environment selected from a gas, preferably air, or water and other liquids, preferably an aqueous environment, more preferably an aqueous solution, wherein the polymeric mesh as defined in the first aspect, the composite as defined in the second aspect and / or third aspect or a mixture of the polymeric mesh or the composite with an adsorbent is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.

[0204] In a preferred embodiment, the harmful compound is a basic, neutral or acidic compound, such as a drug or pesticide, and their metabolites, a fluorinated carboxylic and sulphonic acid, as well as a combination of two or more thereof.

[0205] In one embodiment, the support materials are particles smaller than 5 mm, preferably smaller than 1 mm, most preferred smaller than 500 pm, wherein undesired substances are first adsorbed by the composite material, and the aqueous solution is finally separated after the depletion of the target compounds, using a membrane.

[0206] In one embodiment, a combination of at least two composite materials is used, at least one of them comprising an excess of basic groups, respectively acidic groups.

[0207] The polymeric mesh of the present invention may be used for numerous purposes. Among these, the decontamination of water from microorganisms is highly significant. A respective depletion for contaminating bacteria and viruses in the range of about five orders of magnitude has already been achieved (see examples).

[0208] Therefore, the present invention provides a method for the binding of microorganisms, preferably of bacteria and viruses, from wastewater, river water, well water, ground water and drinking water, characterized in that said water is contacted with a composite material as defined above.

[0209] The present invention also provides a method for the binding of microorganisms, preferably of bacteria and viruses from piped drinking water before point of use and after point of entry, characterized in that the water is contacted with a composite material, comprising an amino group containing polymer, preferably a cross-linked polymer for a sufficient time.

[0210] Afterwards the water is always filtered off from the composite, preferably using a membrane.

[0211] Bacteria and viruses are strongly and irreversibly adsorbed on the composite surface solely by physical interactions. The cross-linked polymer does not act as a biocide at all and, at the same time, does not release harmful substances (leachables). Using activated carbon as the support, the TOC (total organic content) is well below 10 ppm and does not contain fragments stemming from the polymer.

[0212] In addition, a major part of bacterial and viral fragments or degradation products remains also tightly bound to the surface polymer, mainly including peptides, proteins, oligonucleotides, as well as nucleic acids (DNA, RNA, fragments thereof) and membrane fragments.

[0213] Also, most of allergenic peptides and proteins remain adsorbed from various composite materials containing the cross-linked polymer.

[0214] The depletion of birch pollen allergenic components was thus achieved up to 99% (see examples).

[0215] Thus, there is a major difference between the new materials and common air filters for pollen and pollensomes, because after binding to the cross-linked polymer the very small, effective allergenic moieties will not be released to the environment anymore. This is very important for any room ventilation processes. Only the pollen is bound by the filters in common use, subsequently releasing the smaller pollensomes and the allergenic proteins. The active allergenic proteins exhibit an average size below 20 nm, pollensomes below 200 nm are only retained by HEPA filters, whereas a pollen with up to a few micrometres will not already pass a filter of class M5. These pollens are thus retained, representing a deposit for their dangerous smaller sized components.

[0216] The desorption of these allergenic nanoparticles, preferably of allergenic proteins, then occurs continuously in small portions, critical mainly in applications with recirculating air, e.g., in indoor applications of commercial house filter devices.

[0217] The cross-linked polymer according to the invention coated onto filter materials overcome these known drawbacks of current state of the art-filter materials. These filter materials typically comprise support materials as listed above in the section “Support material”.

[0218] Accordingly, the present invention also provides a method, wherein the basic polymers-containing composite is used to bind bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids.

[0219] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material as defined in the second or third aspect comprising activated carbon or an ion exchanger, preferably used as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides.

[0220] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material as defined in the second or third aspect comprising glass fibers, polyester fibers, or any woven or non-woven support material, is contacted with said harmful compounds,preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides.

[0221] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from a gas, preferably air, or water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in the second or third aspect comprising activated carbon or an ion exchanger, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.

[0222] In one embodiment of the above embodiment, the bacteria are legionella, pseudomonas aeruginosa, staphylococcus aureus, or klebsiella pneumoniae.

[0223] Another field of application for the materials according to the present invention, concerns wound treatment. A sepsis is driven by the degradation products of Gram-positive and Gram-negative bacteria, known as endotoxins or lipopolysaccharides and lipoteichoic acids, altogether responsible for severe complications during the wound healing process. The use of materials of the present invention provides a strong potential to avoid many cases of sepsis. Also, diphtheria and cholera toxins will efficiently be captured, directly from wound exudate. Together with the binding of exotoxins is an important potential for the manufacturing of novel, highly effective wound dressing materials.

[0224] The present invention therefore relates to the binding of endotoxins, lipoteichoic acids, other endo- or exotoxins, using a composite material coated with a cross-linked polymer as defined herein.

[0225] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, most preferred a body fluid, wherein a composite material as defined in the second or third aspect comprising a fabric, or a wound dressing material, also combined with activated carbon, is contacted with saidharmful compounds, preferably wherein said harmful compounds are selected from endotoxins or lipoteichoic acid and other endogenic or exogenic pyrogenic substances.

[0226] Activated carbon is also capable of binding molecules with a molecular mass below 500 Da, independent from their structure, by non-specific and vastly unknown mechanisms. The carbon molecular structure comprises a multitude of functional groups on its surface, e.g., phenolic, and heterocyclic ones, all originating from their natural plant components. In addition, also the inorganic content of around 2% (w / w) may play a role.

[0227] Consequently, severe differences in selectivity and binding capacity are resulting between activated carbons of different sources.

[0228] But even with low metabolite concentrations of drugs or agricultural pesticides no complete depletion was achieved to date. In average less than 90% were reported. Candesartan, Benzotriazole, and Diclofenac have been adsorbed to 40% until 80% from initial concentrations between 1 ppm and 50 ppm in aqueous solution. These results are dependent on the brand of the activated carbon applied.

[0229] It is also known that the depletion of pesticides and their metabolites is not satisfactory at all. One example comprised the so far unresolved adsorption problems with Chlorothalonil metabolites, stemming from a formerly worldwide used fungicide.

[0230] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in the second or third aspect comprising activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pesticides, drugs or their metabolites, more preferred from chlorothalonil metabolite R471811. Further examples of pesticides and pharmaceutical ingredients are Atrazin, Bentazon, Metazachlor, Simazin, Tritosulfuron, Diuron, Metolachlor, Irbetasan, Benzotriazol, Methylbenzotriazol, Naproxen, Dichlofenac, Tramadol, Metoprolol, Pentobarbital, Indometacin. Examples of metabolites are 2-Hydroxyatrazin, Methyl-desphenyl chloridazon or chlorothalonil derivatives R417888, R419492, R182281 , R611965,R611968, R611168, SYN507900, SYN 548580, and SYN548581.

[0231] Nevertheless, activated carbon plays an important role for the purification not only of ground or drinking water, but also of wastewater, due to its commercial availability in multi thousands ton scale at low price, combined with the broad applicability.

[0232] As there is a consent about concentrations in a ppm range being hazardous for human health and dangerous for animals, many ground water and drinking water sources already require comprehensive purification efforts to meet official regulatory requirements. Those requirements are often not met by activated carbon.

[0233] The drinking water quality in developing countries is very poor at the average. Even in industrial countries increasing contamination with drugs and their metabolites, but also with residuals from extensive use of agricultural chemicals (fungicides, pesticides, and herbicides) actually represents a growing major environmental problem.

[0234] A severe problem are also several industrial chemicals, mainly fluorinated ones. In industrial countries no effective solution was so far available to remove polyfluorinated compounds (PFAS), preferably polyfluorinated acids (e.g. PFOA) and sulphonic acids (e.g. PFOS) from ground and drinking water down to the legal limit.

[0235] Due to the present invention, these unsatisfactory situations have now been overcome. The amino groups and the methylene chains of the relating polymers, preferably cross-linked polymers as defined herein, retaining such substances due to ionic interactions, combined with lipophilic binding.

[0236] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in the second or third aspect comprising activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from polyfluorinated compounds, preferably carboxylic and sulphonic acids (PFAS), more preferred from short chain moieties like perfluoro octanoic acid (PFOA) or products from GenX processes.Further examples of such substances are trifluoroacetic acid TFA, perfluorobutanoic acid PFBA, perfluoropentanoic acid PFPeA, perfluorohexanoic acid PFHxA, perfluoroheptanoic acid PFHpA, perfluorononanoic acid PFNA, perfluorodecanoic acid PFDA, perfluoroundecanoic acid PFUnA, perfluorododecanoic acid PFDoA, perfluorotridecanoic acid PFTrDA, perfluorotetradecanoic acid PFTeDA, perfluorobutanesulfonic acid PFBS, perfluoropentanesulfonic acid PFPeS, perfluorohexanesulfonic acid PFHxS, perfluoroheptanesulfonic acid PFHpS, perfluorooctanesulfonic acid PFOS, N-ethyl perfluorooctanesulfonamidoacetic acid NEtFOSAA, methylperfluorooctanesulfonamidoacetic acid NMeFOSAA, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluorodecanesulfonic acid, Pperfluoro-3-methoxypropanoic acid PFMPA, perfluoro-4-methoxybutanoic acid PFMBA, perfluoro(2-ethoxyethanesulfonic acid PFEESA, nonafluoro-3,6-dioxaheptanoic acid NFDHA, hexafluoropropylene oxide dimer acid HFPO-DA, 4,8-dioxa-3H- perfluorononanoic acid ADONA, 9-chlorohexadecafluoro-3-oxanonane-1 -sulfonic acid 9CI-PF3ONS, 11 -chloroeicosafluoro-3-oxanonane-1 -sulfonic acid 11 CI-PF3OUdS.

[0237] Therefore, the present application relates to the binding of fluorinated compounds, preferably fluorinated carboxylic acids, and sulphonic acids, comprising contacting solutions comprising said substances, preferably ground water and drinking water, with a composite material, comprising the cross-linked polymer defined herein for a sufficient time, and subsequently removing the composite, preferably using a membrane.

[0238] A preferred support for said composite is activated carbon. Also preferred are silica gel, aluminium oxide and other support materials such as ion exchangers, preferably cation exchangers, as listed above.

[0239] Accordingly, the present invention provides methods, wherein the amino group- containing polymer is used for adsorbing acidic to neutral compounds, mainly drugs, pesticides and their metabolites, and fluorinated compounds, preferably fluorinated carboxylic and sulphonic acids.

[0240] Within a batch application process, it was found, that the loadability of the activated carbon is increasing and the time for adsorption is decreasing with decreasing particle size.However, these small particles subsequently must be separated again from the purified drinking water. This can be achieved by a membrane of appropriate size and porosity. According to the present invention, one important embodiment comprises appropriately small-sized activated carbon particles, coated with a cross-linked polymer, combined with a membrane filter, capable of retaining this carbon particles after the adsorption step. The particle size is preferably between 0.2 pm and 2 mm, more preferred between 5 pm and 500 pm for this purpose.

[0241] In a preferred embodiment, the activated carbon coated with the cross-linked polymer is mixed with the contaminated water and optionally stirred for a certain time. Then the suspension is separated using the membrane filter. The contact time is preferably below two hours, more preferably below one hour, and still more preferably below 30 minutes. The ratio of activated carbon to the amount of water is depending on the nature and the concentration of the undesired substance, preferably one part of activated carbon and 100 to 105parts of water (w / w).

[0242] Accordingly, the present invention relates to a purification process, wherein an amino polymer containing composite material as defined herein is contacted with the contaminated liquid sample for a sufficient time, and the subsequent separation from the solid material is achieved using a membrane, thus completely retaining the solids.

[0243] The present invention thus also relates to a method for the purification of a suspension, preferably wherein the support materials are particles smaller than 500 pm, and wherein the undesired substances are first adsorbed to the composite, and the aqueous solution is finally separated from said suspension after the depletion of the target compounds, using a membrane.

[0244] Also, wastewater requires additional purification. The major problems are here multi-resistant germs and their DNA residuals, including potentially antibiotic resistance or other pathogenic factors mediating plasmids. Both are interacting with non-pathogenic bacteria, generally occurring in rivers or any reservoirs for treated water, transfecting (converting) some of them to acquire potentially pathogenic resistances. Multi-resistance mediating DNA fragments may also take part in the conversion of ubiquitously occurring bacteria into pathogenic stems, e.g., by horizontal gene transfer. All said conversions aretaking place, e.g., within wastewater treating units. As bare activated carbon does not bind and / or deactivate bacteria and viruses, a more potent solution was required to overcome these serious hazards to human and animal health.

[0245] This has been achieved by the present application: The coating of the support materials as listed above with a basic, in particular amino group-containing polymer solved this issue.

[0246] Accordingly, a composite material with at least one amino group-containing polymer, preferably a cross-linked polymer as defined herein, comprising at least one amino group together with activated carbon, preferably from coconut shell, retains bacteria and any kind of nucleotides and oligonucleotides, as well as all kinds of nucleic acids and fragments thereof, including the different molecular forms of plasmid DNA. Also, the abovedescribed combination with a membrane is particularly advantageous for the purification of wastewater.

[0247] In one embodiment, the invention provides a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in the second or third aspect comprising activated carbon or an ion exchanger, is contacted with said harmful compounds, preferably selected from multi-resistant germs, preferably from bacteria and viruses and their DNA, or from oligonucleotides, containing the gene sequences responsible for the multi-resistance.

[0248] The unspecific adsorptive power of the activated carbon together with the selective interaction using the cross-linked polymer as defined herein significantly enhances the depletion capabilities.

[0249] Moreover, while basic polymers provide anion exchange functionality, acidic polymers contribute cation exchanger capability.

[0250] In addition, e.g. in the case of polymer obtained from adipic acid and a triamine, without being bound by theory, the lipophilic oligo methylene chains, in combination with the simultaneously present amide groups, making hydrogen bridge interaction available, allow for binding of predominantly uncharged targets or even rather lipophilic molecules.

[0251] But also, other support materials, particles and threads, like silica gel, glass fibers, or different fabrics and tissues, combined with a cross-linked polyamine polymer, are useful for the depletion of nucleic acids and microbes from water as well as from the gas phase, most significantly from air.

[0252] The production process for said composite materials comprising cross-linked polymers as defined herein is preferably carried out in the following way:

[0253] In one embodiment, the support material was mixed with an appropriate amount of an aqueous solution, comprising 2% to 30% of the polymer and the cross-linker or the polymer comprising the cross-linker attached via one function only to the polymer, and heated between 60 °C and 210 °C, preferably between 80 °C and 140 °C, more preferred between 90° C and 120°C for a time between 20 and 120 minutes. Residual water is evaporated preferably under reduced pressure.

[0254] To form a monolithic piece of activated carbon the polymer content may be increased up to 70 %.

[0255] The polymer as defined herein may be added by any known method of coating, preferably dipping or spray coating.

[0256] By contrast, acidic polymers, e.g., comprising poly(acrylic) acids and derivatives thereof are appropriate for capturing basic compounds, preferably basal fungi as well as fungal spores. Preferred is the combination of polyvalent carboxylic acids with a diamine and a cross-linker. More preferred are tricarboxylic acids in combination with a diamine and an oxirane cross-linker.

[0257] Accordingly, the present invention also provides methods of using a composite material comprising an acidic polymer, binding basic to neutral compounds mainly pesticides and drugs, and their metabolites, fungi, and their spores.

[0258] Therefore, the present invention also relates to a process, wherein the tricarboxylic acid is citric acid, the diamine is hexamethylenediamine and the cross-linker is epichlorohydrin.

[0259] A combination of basic and acidic composite materials will almost entirely deplete most of the contaminants from liquid or gaseous media, applied either as a mixed bed or in two subsequent steps.

[0260] Thus, the present invention also relates to the use of a combination of basic and acidic composite materials.

[0261] Fifth aspect: Method of using an acidic polymer

[0262] According to a fifth aspect, and as defined above, the invention relates to a method of using an acidic polymer for the binding of basic to neutral compounds, preferably pesticides, drugs, and their metabolites, fungi, and their spores; wherein the polymer preferably comprises residues of a polyvalent carboxylic acid selected from citric acid, residues of a polyvalent amine selected from hexamethylenediamine, and a cross-linker selected from epichlorohydrin.

[0263] Sixth aspect: Method of using a cross-linked polymer comprising an amino qroup- containinq polymer

[0264] In another aspect, the invention relates to the use of a cross-linked polymer comprising an amino group-containing polymer.

[0265] Cross-linked polymers comprising an amino group-containing polymer are known from WO 2020 / 079233 A2. Specific amino group-containing polymers are selected from the group consisting of poly(vinylformamide-co-vinylamine), a linear or branched poly(vinylamine), a poly(allylamine), a poly(ethyleneimine), a poly-lysine, a poly(vinylimidazol), a polypyrrol, a polyaniline, and copolymers containing such amino polymers.

[0266] Such amino group-containing polymers are used in the methods defined below.

[0267] The cross-linkers as defined in the first aspect are used for cross-linking as well as the method for cross-linking as defined in the third aspect.

[0268] The support materials as defined in the first aspect are used for immobilization as well as the method for immobilization as defined in the third aspect.

[0269] Composite material comprising a cross-linked polymer comprising an amino group- containing polymer selected from poly(vinylformamide-co-vinylamine), a linear or branched poly(vinylamine), a poly(allylamine), a poly(ethyleneimine), a poly-lysine, a poly(vinylimidazol), a polypyrrol, a polyaniline, and copolymers containing such amino polymers, allow for advantageous application as set out below.

[0270] In one embodiment, the invention relates to a method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material comprising a cross-linked polymer comprising an amino group-containing polymer and activated carbon or an ion exchanger, preferably used as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides.

[0271] In another embodiment, the invention relates to a method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material comprising a cross-linked polymer comprising an amino group-containing polymer and glass fibers, polyester fibers, or any woven or non-woven support material, as listed above, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides.

[0272] In another embodiment, the invention relates to a method for removing harmful compounds from an environment selected from a gas, preferably air, or water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material comprising a cross-linked polymer comprising an amino group- containing polymer and activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.

[0273] In one embodiment, the invention further relates to a method according to the above embodiment, wherein the bacteria are legionella, pseudomonas aeruginosa, staphylococcus aureus, or klebsiella pneumoniae.

[0274] In another embodiment, the invention relates to a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material comprising a cross-linked polymer comprising an amino group-containing polymer and activated carbon or an ion exchanger, is contacted with said harmful compounds, preferably selected from multi-resistant germs, preferably from bacteria and viruses and their DNA, or from oligonucleotides, containing the gene sequences responsible for the multi-resistance.

[0275] In another embodiment, the invention relates to a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material comprising a cross-linked polymer comprising an amino group-containing polymer and activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pesticides, drugs or their metabolites as listed above, more preferred from chlorothalonil metabolite R471811.

[0276] In another embodiment, the invention relates to a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material comprising a cross-linked polymer comprising an amino group-containing polymer and activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from polyfluorinated compounds, preferably carboxylic and sulphonic acids (PFAS), more preferred from short chain moieties like perfluoro octanoic acid (PFOA) or products from GenX processes.

[0277] In another embodiment, the invention provides a method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, most preferred a body fluid, wherein a composite material comprising a cross-linked polymer comprising an amino group-containing polymer comprising a fabric, or a wound dressing material, also combined with activated carbon, is contacted with said harmful compounds, preferably wherein saidharmful compounds are selected from endotoxins or lipoteichoic acid and other endogenic or exogenic pyrogenic substances.Examples

[0278] Example 1

[0279] Preparation of solid cross-linked polymer

[0280] 12 ml FennoStrength (Kemira, Unterschweinstiege 2-14, 60549 Frankfurt am Main, Germany) were adjusted to pH 10 by the addition of 7 ml sodium hydroxide solution (85 mM), followed by drying in vacuo at 100 °C for 100 min. The resulting solid film was found immediately swelling in water, but remaining insoluble.

[0281] A product sample was contacted with a solution of Reactive Red in water (20 mg / ml), heated to and kept at 90 °C for 15 minutes and subsequently washed with water thrice, each time with 25 ml. The third wash water fraction appeared entirely clear, whereas the solid material remained in red. Thereby the color depth was distributed inhomogeneously.

[0282] Determination of antibacterial activity according to ISO 20743:2013: Klebsiella pneumoniae DSM 789 bacteria depletion by 4.25 orders of magnitude (TITK - Thuringisches Institut fur Textil- und Kunststoff-Forschung e.V., BreitscheidstraR>e 97, 07407 Rudolstadt, Germany).

[0283] Example2

[0284] Reaction of the polymer with Diaminopropane as the cross-linker

[0285] The degree of additional cross-linking achieved was about 10%.

[0286] 10 ml FennoStrength (Kemira) were adjusted to pH 10 by the addition of 5.5 ml sodium hydroxide (85 mM) before 0.3 mmol diamino propane were added (22 mg; 25 pl, d= 0.88 g / l; 10 ml polymer is equivalent to about 6 mmol amino monomer units). After drying in vacuo at 100°C for 100 min a denser film was resulting, as compared to Example 1. Afterthe addition of water swelling started within 5 minutes. Upon heating to 50°C the swelling continued further.

[0287] A product sample was contacted with a solution of Reactive Red in water (20 mg / ml), heated to and kept at 90 °C for 15 minutes and thereafter washed with water thrice. The third wash water was clear, whereas the solid remained red. The color on the stained material was distributed very homogeneously.

[0288] Example 3

[0289] Preparation of polymer-coated activated carbon for the purpose of bacteria binding.

[0290] The polymer was preferably immobilized on the outer particle surface, to reach a total polymer content of about 5% (w / w).

[0291] 30 g Jacobi Activated Carbon (coconut shell, 8x30 mesh, Jacobi Carbons Service (Europe) GmbH, Vistrastrafce 12, 14727 Premnitz, Germany) were heated to 160 °C. To the surface of the hot carbon in total 20 ml FennoStrength (Kemira, pH 9.5) solution were sprayed in four equal portions. For this purpose, the pH value of 10 ml of the original supplier solution was adjusted to 9-10 using 1 N sodium hydroxide solution. The resulting solution was finally adjusted to a final volume of 20 ml with water. After each portion the carbon was heated again to 160 °C and the carbon particles were mixed with stirring. The average temperature did not drop below 100 °C, not even immediately after the spraying. The solvent water became rapidly evaporated. The product was further dried for 20 minutes at 107°C and analyzed by reaction with Reactive Red and with fluorenyl isothiocyanate. The reaction product was investigated at 100-fold magnification, both under the light microscope, as well as the fluorescence microscope. About 60% of the outer particle surface had turned into a bright red color. At the emission wavelength of 520 nm the external surface of the individual particles appeared rather homogeneously stained.

[0292] Safety Instruction: Handle with care. Always avoid inhalation of dust or vapors! The reactive polymer must always be handled under a fume hood or similar device, particularly while adding the polymer solution to the heated carbon support material.

[0293] Example 4

[0294] Preparation of coated activated carbon made from wood

[0295] Determination of the pore volume by water uptake: 2 g of activated carbon were filled with 5.5 ml of water. The pore volume turned out significantly bigger than with other coal types.

[0296] Preparation of 200 g of said material, with a polymer content of 33%: the pores of 180 g of Jacobi Activated Carbon (charcoal) were filled with 566 ml of a solution of FennoStrength (Kemira, pH 9.5), containing 60 g of dissolved polymer. The suspension was thoroughly mixed and heated in vacuo to 107 °C for 150 min. The product was further dried overnight, washed with water and dried again.

[0297] Example 5

[0298] Preparation of monolithic activated carbon

[0299] Five equal portions taken from 150 ml FennoStrength (Kemira) were poured on to 75 g of Jacobi Activated Carbon (coconut shell, 8 to 30 mesh). After every liquid portion a significant amount of air was released from the carbon, leading to the formation of a dense foam. Each time the next portion was added, as soon as the foam subsided. The suspension was kept for one hour at 80 °C in a drying cabinet. As soon as the water was entirely evaporated a dense, firm but brittle solid material remained.

[0300] Example 6

[0301] Preparation of coated monolithic activated carbon using 50 to 200 mesh material and a cross-linker

[0302] 1 ml FennoStrength (Kemira) containing 145 mg polymer (58 mmol of monomer units) and 125 pl (1 .4 mmol) diamino propane were mixed with 400 mg of Jacobi Activated Carbon (coconut shell, fine quality 50 to 200 mesh) and heated to 100 °C under vacuum. After evaporation of water, it was not possible to divide the coated carbon into individual particles or initially existing assemblies of particles by simple mechanical means.

[0303] Example 7

[0304] Preparation of coated activated carbon in the presence of Tween 20 detergent

[0305] The pores of 5 g of Jacobi Activated Carbon (coconut shell, fine quality 50 to 200 mesh) were filled with 5 ml of a 1 % Tween 20 (Carl Roth GmbH + Co. KG, Schoemperlenstr. 3-5, 76185 Karlsruhe, Germany) solution (0.01 v / v). Subsequently, 2.3 ml FennoStrength (Kemira), adjusted to pH 9.5 were added (c=150 mg / ml polymer), thoroughly mixed, and heated to 120°C for 100 min under vacuum. The resultant solid material appeared dry, displaying a densely connected layer on top. The rest of the particles had not been connected.

[0306] A product sample was contacted with a solution of Reactive Red in water (20 mg / ml), heated to and kept at 90°C for 15 minutes and washed with water. It was observed under the light microscope that the particles were coated with a thus colored layer of polymer.

[0307] Example 8

[0308] Preparation of coated activated carbon in the presence of Brij 35 detergent

[0309] The pores of 5 g of Jacobi Activated Carbon (coconut shell), coarse quality 8 to 30 mesh, were filled with 5 ml of a Brij 35 (Carl Roth GmbH + Co. KG, Schoemperlenstr. 3-5, 76185 Karlsruhe, Germany) solution (0.2 mg / ml). Subsequently 0.5 ml FennoStrength (Kemira) were added (c=75 mg / ml polymer), thoroughly mixed to obtain a homogeneous suspension, and heated to 100°C for 45 min under vacuum. The resultant solid material was almost dry, the particles appeared not be fused together. After mixing with another 3 ml of the same polymer (225 mg) no further gas release was observed. Upon drying at 110°C for one hour a solid mass was formed. Under mechanical stress the solid disaggregated. After the addition of 10 ml of water, the solid dissociated into individual particles. The material contained 4.5% (w / w) of polymer in total.

[0310] A product sample was contacted with a solution of Reactive Red in water (20 mg / ml), heated to and kept at 90°C for 15 minutes, before washing with water as before. Itwas observed under the light microscope that the majority of single particles was coated with a colored layer of polymer.

[0311] Example 9

[0312] Preparation of a coated cellulose fabric

[0313] 15 g of a cotton (make TOLKO aus OkoTex Baumwolle: Amazon.de: Garten) issue were dipped in a solution of FennoStrength (Kemira, pH 9.5), prepared from 5.5 ml original solution from the supplier by adjusting the pH with 0.5 M sodium hydroxide solution and the volume with water to reach 30 ml. The fabric was heated to and kept at 110°C for 10 min, followed by drying at reduced pressure (50 mbar) for a further 90 minutes. The product was stained with Reactive Red and fluorenyl isothiocyanate. The resulting colored product was compared to the untreated cotton. The coated cellulose was found homogeneously stained by the dye, exhibiting a deep red color, whereas the starting material appeared in pink. The color could not be washed out from the coated fabric by a 1 N hydrochloric acid solution. By contrast, the dye was readily dissolved into the HCI solution from the starting material.

[0314] Cotton coated with poly(vinylamine): Within one hour, 1 g of the dressing material completely adsorbed 10 EU* of endotoxins at least (Mikrobiologisches Labor Dr. Michael Lohmeyer GmbH, MendelstraR>e 11 D-48149 Munster, Germany). As a rule of thumb, 10 EU are equivalent to 1 ng of endotoxin.

[0315] Recombinant factor-C-Test (Ph. Eur. 10.3, 2.6.32)

[0316] Endotoxin-test used: Haemotox rFC. Supplier: Haemochrom Diagnostica GmbH, Essen, Germany.

[0317] X Reference Standard Endotoxin: RSE Ph. Eur. Reference Standard Endotoxin BRP batch 5.1 (2012) von E. coli 0113:H10: K-endotoxin. The same batch of material was adopted in October 2012 as the WHO 3rd IS for Endotoxin with assigned content of 10 000 lU / vial (1 IU = 1 EU)

[0318] Example 10

[0319] Preparation of a filter medium in a wet-laid process using a sheet former

[0320] 2 g of a solid glass fiber mixture (60 % B 39, 10 % B 06, and 30 % EC 06) were suspended by stirring in 250 ml of 1.2 mM aqueous hydrochloric acid. This suspension was filled into the vessel of a sheet former and was immediately aspirated through the frit on the bottom of the sheet former vessel. A thin, dense, and homogeneous fiber layer was formed on the top of the frit.

[0321] 2.7 ml polyethylene glycol) diglycidyl ether, average molecular mass (Mn) 500, were dissolved in 240 ml water. 10.25 ml of Lupamin 45-70, poly(vinylformamide-co- polyvinylamine) solution in water (c = 130 g / l), were added, containing 1.33 g of said polymer. This solution was poured into the vessel on the top of the above fiber layer and aspirated after 10 min.

[0322] The fragile moist intermediate was removed from the frit. After coasting with a roller tool the remaining weight was 20.8 g.

[0323] The reaction of the polymer and the cross-linker was performed by heating to 140°C for 20 min. An 0.5 mm thin, mechanically stabile porous sheet was isolated. The dry weight was 2.3 g.

[0324] After incineration at 600°C the weight of the remaining solid decreased to 1.84 g, representing the glass fiber matrix. Accordingly, the mass of the cross-linked amino polymer was 456 mg (19.8%).

[0325] Sheet former from Estanit GmbH, Mulheim / Ruhr, Germany

[0326] Allergen Elimination of filter media sample

[0327] The sample was tested for allergen elimination potential with birch pollen allergen Bet v 1. Positive control (allergen without sample) 815 ng / ml Allergen concentration after contact 11 ng / mlElimination potential 99 %.

[0328] Determination of antibacterial activity according to ISO 20743:2013

[0329] Klebsiella pneumoniae DSM 789, bacteria depletion by 6.3 orders of magnitude.

[0330] Staphylococcus aureus DSM 799, bacteria depletion by 5.9 orders of magnitude.

[0331] Determination of antiviral activity based on ISO 18184:2019

[0332] Antiviral efficacy value after 2h incubation, virus depletion by 4.9 orders of magnitude.

[0333] All data from OFI - Osterreichisches Forschungs- und Prufinstitut, Franz-Grill- StraR>e 5, 1030 Wien, Austria.

[0334] Example 11

[0335] Preparation of coated filter mats made from polyester

[0336] 1 I of the dissolved detergent were poured to 5 I of the polymer solution and thoroughly mixed. Subsequently five equal portions, each 400 ml of the cross-linker were added and the resulting solution is filled up to 10 I with water.

[0337] A filter mat F5 made from polyester staple fiber (130 g, length 620mm, 620 width mm, thickness 20 mm) is placed on a perforated stainless steel sheet, equally and crosswise sprayed with 100 ml of the polymer solution, and allowing to take effect for 10 min., before heating to 185°C for another 15 min.

[0338] Lupamin® 4570 Polymer based on: Vinylamin, N-Vinylformamid Solenis Fascinatio Boulevard 522 2909 VA CAPELLE A / D IJSSEL Netherlands

[0339] Detergent: Polyethylene glycol 6000, ROTIPURAN® Ph.Eur Carl Roth GmbH + Co KG Schoemperlenstr. 3-5 D-76185 Karlsruhe Deutschland

[0340] Cross-linker: Succinic acid, Carl Roth GmbH + Co KG Schoemperlenstr. 3-5 D- 76185 Karlsruhe Deutschland, >99 %, p.a., ACS, molecular formula C4H6O4, molecular mass (M) 118,09 g / mol.

[0341] Determination of antibacterial activity according to ISO 20743:2013 (TITK - Thuringisches Institut fur Textil- und Kunststoff-Forschung e.V., BreitscheidstraR>e 97, 07407 Rudolstadt, Germany)

[0342] Klebsiella pneumoniae DSM 789 bacteria depletion by 5.4 orders of magnitude

[0343] Staphylococcus aureus DSM 799 bacteria depletion by 5.4 orders of magnitude.

Claims

CLAIMS1 . A polymeric mesh comprising a cross-linked polymer, wherein the cross-linked polymer comprises residues of a polyvalent carboxylic acid, a polyvalent amine, and a crosslinker.

2. The polymeric mesh according to claim 1 , wherein the cross-linked polymer is a gel.

3. The polymeric mesh according to claim 1 , wherein the cross-linked polymer is immobilized on a support material, thus forming a composite material4. The polymeric mesh according to any of claims 1 to 3, wherein the cross-linker is an oxirane compound or an organic dihalide; or wherein the polyvalent carboxylic acid is a dicarboxylic acid and the polyvalent amine is a triamine, preferably wherein the dicarboxylic acid is adipic acid, the polyvalent amine is diethylenetriamine, and the cross-linker is epichlorohydrin, preferably wherein epichlorohydrin is attached via one functionality only to the polyvalent amine; or wherein the polyvalent carboxylic acid is a tricarboxylic acid, and the polyvalent amine is a diamine, preferably wherein the tricarboxylic acid is citric acid, the polyvalent amine is hexamethylenediamine, and the cross-linker is epichlorohydrin.

5. A composite material comprising a cross-linked polymer, the cross-linked polymer being defined in claim 4, wherein the cross-linked polymer is immobilized on a support material.

6. The composite material according to claim 5, wherein the support material comprises particles, preferably wherein the particles comprise activated carbon or an ionexchanger; or wherein the support material is a tissue or a fabric; or wherein the support material comprises glass fibers, preferably combined with polyester fibers.

7. A process for the synthesis of a composite material as defined in claim 5 or 6, comprising steps (i) to (iv):(i) providing a support material,(ii) wetting the support material with a cross-linker and an amino group-containing polymer in a solvent, wherein the polymer comprises the residues of a polyvalent carboxylic acid and residues of a polyvalent amine;(iii) heating the wetted support material at a temperature in the range of from 80°C to 195°C or 80°C to 180°C, preferably 80°C to 150°C, more preferred 80°C to 110°, supplying thermal, oscillation, vibrational, or radiation energy, thus allowing the cross-linking, and(iv) optionally evaporating excess solvent.

8. A process for the synthesis of a composite material as defined in claim 5 or 6, comprising steps (i) to (iv):(i) providing a support material,(ii) wetting the support material with an amino group-containing polymer, wherein the amino group-containing polymer comprises the residues of a polyvalent carboxylic acid and residues of a polyvalent amine, and wherein a cross-linker is attached via one functionality only to the amino group-containing polymer, in a solvent;(iii) heating the wetted support material at a temperature in the range of from 80°C to 195°C or 80°C to 180°C, preferably 80°C to 150°C, more preferred 80°C to 110°C, supplying thermal, oscillation, vibrational, or radiation energy, thus allowing the cross-linking, and(v) optionally evaporating excess solvent.

9. The process according to claim 7 or 8, wherein the polyvalent carboxylic acid is adipic acid, the polyvalent amine is diethylenetriamine, and the cross-linker is epichlorohydrin; or wherein the polyvalent carboxylic acid is citric acid, the polyvalent amine is hexamethylenediamine, and the cross-linker is epichlorohydrin.

10. The process according to anyone of claims 7 to 9, wherein the solvent in step (ii) is water; or wherein the support material comprises activated carbon particles, preferably having a median pore diameter between 15 and 200 nm; preferably wherein the carbon particles are glued together by the epoxy-containing polymer, thus forming a solid piece / monolith; or wherein the support material comprises glass fibers combined with polyester fibers; or wherein the support material is a tissue or fabric.

11. The process according to anyone of claims 7 to 10, wherein prior to step (ii) or in step (ii) the support material is contacted with a detergent solution, preferably wherein the detergent is based on sodium dodecyl sulphate or a polyoxymethylene or a polysorbate.

12. The process according to anyone of claims 7 to 11 , wherein the polymer is derivatized by means of a derivatizing reagent, preferably wherein a reagent used for derivatisation is an anhydride or a lactone.

13. A composite material as defined in claim 5 or 6, obtainable by a process as defined in anyone of claims 7 to 12.

14. A method for removing harmful compounds from an environment selected from a gas, preferably air, or water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein the polymeric mesh as defined in anyone of claims 1 to 4, or a mixture of the polymeric mesh with an adsorbent, or a composite material as defined in claim 5 or 6 or 13 is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.

15. The method according to claim 14, wherein the harmful compound is an acidic or a neutral compound, such as a drug or a pesticide, and metabolites thereof, a fluorinated carboxylic and sulphonic acid, as well as a combination of two or more thereof; orwherein the support material comprises particles smaller than 500 pm, wherein undesired substances are first adsorbed by the composite material, and the aqueous solution or suspension is finally separated after the depletion of the target compounds, using a membrane; or wherein a combination of at least two composite materials is used, at least one of them comprising a basic polymer and at least one of them comprising an acidic polymer.

16. A method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material as defined in claim 5 or 6 or 13 comprising activated carbon or an ion exchanger, preferably used as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides.

17. A method for removing harmful compounds from an environment selected from a gas, preferably air, wherein a composite material as defined in claim 5 or 6 or 13 comprising glass fibers, polyester fibers, or any woven or non-woven support material, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pollensomes or allergenic proteins or peptides.

18. A method for removing harmful compounds from an environment selected from a gas, preferably air, or water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in claim 5 or 6 or 13 comprising activated carbon or an ion exchanger, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from bacteria, viruses, pollen, pollensomes, and their degradation products, mainly DNA, oligonucleotides, proteins, peptides, lipids, and a combination of two or more thereof.

19. The method of claim 18, wherein the bacteria are legionella, pseudomonas aeruginosa, staphylococcus aureus, or klebsiella pneumoniae.

20. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in claim 5 or 6 or 13 comprising activated carbon or an ion exchanger, is contacted with said harmful compounds,preferably selected from multi-resistant germs, preferably from bacteria and viruses and their DNA, or from oligonucleotides, containing the gene sequences responsible for the multi-resistance.21 . A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in claim 5 or 6 or 13 comprising activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from pesticides, drugs or their metabolites, more preferred from chlorothalonil metabolite R471811.

22. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, wherein a composite material as defined in claim 5 or 6 or 13 comprising activated carbon or an ion exchanger, preferably used in a tank or as a monolithic compound, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from polyfluorinated compounds, preferably carboxylic and sulphonic acids (PFAS), more preferred from short chain moieties like perfluoro octanoic acid (PFOA) or products from GenX processes.

23. A method for removing harmful compounds from an environment selected from water or any other liquid, preferably an aqueous environment, more preferably an aqueous solution, most preferred a body fluid, wherein a composite material as defined in claim 5 or 6 or 13 comprising a fabric, or a wound dressing material, also combined with activated carbon, is contacted with said harmful compounds, preferably wherein said harmful compounds are selected from endotoxins or lipoteichoic acid and other endogenic or exogenic pyrogenic substances.

24. A method of using an acidic polymer for the binding of basic to neutral compounds, preferably drugs, pesticides, and their metabolites, fungi, and their spores; wherein the polymer is a cross-linked polymer comprising preferably residues of a polyvalent carboxylic acid selected from citric acid, residues of a polyvalent amine selected from hexamethylenediamine, and a cross-linker selected from epichlorohydrin.