EP1159060A2 - Multilayer membranes and method for the production thereof - Google Patents

Abstract

The invention applies to the fields of chemistry and relates to multilayer membranes, such as those used, for example, to separate aqueous alcohol mixtures by means of pervaporation. The aim of the invention is to provide a multilayer membrane having a defect-free, separation-active layer and exhibiting a high separation capacity. To this end, the invention provides multilayer membranes consisting of a dense or microporous supporting material and of at least one single layer which is applied thereto and which is attached to the supporting material by polyelectrolyte complexes, whereby few single layers are applied and the first single layer predominantly covers the surface of the supporting material. The aim of the invention is also accomplished by using a method for producing multilayer membranes in which at least one single layer consisting of at least one anionic polyelectrolyte material or, alternatively, of at least one cationic polyelectrolyte material or of at least one non-stoichiometric polyelectrolyte complex is applied to a dense or microporous supporting material which is functionalized with ionic and/or ionizable groups.

Description

Multi-layer membranes and process for their manufacture

Technical field

The invention relates to the fields of chemistry, the converting industry, biotechnology and the food industry and relates to multilayer membranes, such as those used for the separation of aqueous alcohol mixtures by means of pervaporation, and methods for their production.

State of the art

Numerous dense polymer membranes have been described for dewatering organic solvents by means of pervaporation, with the aid of which water is preferably transported (J. Neel in RYM Huang: Pervaporation Membrane Separation Processes, Elsevier 1991, Chapter 1; and J. Neel in RD Noble and SA Stern: Membrane Separations Technology; Elsevier 1995, Chapter 5).

Since the transport through such membranes takes place by means of diffusion, the general aim is to produce membranes with the thinnest possible active layers. The phase inversion method is used for the production of such membranes (S. Loeb, S. Sourirajan, Adv. Chem. Ser. 38, 117 (1962)), which provides asymmetrical membranes with an integrated, separation-active layer. However, the desired membranes can also be created using a composite structure, e.g. by the deposition of polyelectrolyte complex layers on a carrier material.

The construction of thin layers on solid substrates by means of consecutive alternating polyelectrolyte adsorption was first described in the early 1990s (G. Decher, J.-D. Hong, J. Schmitt, Thin Solid Films, 210/211, 831-835 (1992)). So far, little has been reported about the use of this technique for the production of thin layers for the construction of composite membranes. From DE 42 29 530 a polyelectrolyte composite membrane (Symplex) is known which is used for dewatering organic solvents. Cellulose sulfate (polyanion) and polydimethyldiallylammonium chloride (polycation) are used as polyelectrolytes. This symplex is applied to a non-ionic microporous support layer to ensure mechanical stability. In this process, only one complex layer is built up. However, since the porous carrier material has to be sealed, high mass inserts (2-5% by mass) of the symplex-forming components are necessary with this method, which lead to relatively high layer thicknesses (a few 100 nm) due to the manufacturing technique.

A pervaporation and gas separation membrane composed of a polyelectrolyte complex multilayer system has been described (L. Krasemann, B. Tieke J. Membr. Sei., 150, 23-30 (1998)). The porous carrier material used was subjected to a technically complex plasma treatment before the polyelectrolyte multilayer complex was built up. As a result, ionic groups are generated on the surface, which ensure improved adhesion of the adsorbed polyelectrolyte multilayer complex to the support material through electrostatic interaction. Due to the porosity of the carrier material, a high number of polyelectrolyte complex layers (> 30 double layers corresponding to> 60 single layers) is necessary in order to obtain a defect-free, separation-active layer and thus an effective membrane. A further disadvantage of this membrane, in addition to the necessary plasma pretreatment of the carrier material and the high number of polyelectrolyte complex layers, is the insufficient stability of the polyelectrolyte multilayer system with water contents of> 24% by mass in the feed.

Also known (J.-M. Leväsalmi, TJ McCarthy, Macromolecules, 30, 1752-1757 (1997)) is a gas separation membrane based on a polyolefin carrier material and a polyelectrolyte complex multilayer system. However, it is necessary to hydrophilize the hydrophobic polyolefin support before the polyelectrolyte complex multilayer system is built up by wet-chemical modification with chromosulfuric acid and nitric acid in order to generate ionogenic groups which inhibit the adsorption of the first polyelectrolyte layer by electrostatic Making interactions possible. However, an effective membrane is only obtained by applying a high number of polyelectrolytes.

According to R.M. France, R.D. Short, J. Chem. Soc, Faraday Trans., 93 (17), 3173-3188 (1997) also knows that the oxygen functionalities introduced by plasma treatment on polymer surfaces are only stable to a limited extent and can be washed off with a solvent that is inert to the polymer substrate . Furthermore, it was shown in this study that at least 40% of the oxygen functionalities can be assigned to hydroxyl groups, which can be regarded as inactive with regard to the formation of the polyelectrolyte complex.

Presentation of the invention

The object of the present invention is to provide a multi-layer membrane with a defect-free separation-active layer and a high separation performance and to produce this by a more easily manageable and inexpensive method.

The object is achieved by the invention specified in claims 1 and 19. Further training is the subject of the subclaims.

The multilayer membranes according to the invention consist of a dense or microporous support material and a separating layer applied thereon, this separating layer being composed of at least one individual layer. The carrier material is at least chemically constructed in the same way. Advantageously, it is chemically uniform and structurally asymmetrical. However, it is also possible according to the invention that the carrier material is constructed chemically and structurally in the same way throughout. In any case, the carrier material itself can also be active with regard to the separation problems to be processed.

The separation-active layer is in the form of a polyelectrolyte complex multilayer system in which the carrier material is connected to a single layer by a polyelectrolyte complex or, in the case of several individual layers on the carrier material, these individual layers are also connected to one another by a polyelectrolyte complex. In the case of a plurality of individual layers, the individual layers applied one above the other alternately consist of at least one anionic and at least one cationic polyelectrolyte material which, after application, forms a complex bond with the previously applied individual layer. According to the prior art, two such individual layers originally charged differently are referred to as double layers.

The anionic polyelectrolyte materials are sulfonic acid groups and / or their salts and / or phosphonic acid groups and / or their salts and / or phosphoric acid groups and / or their salts and / or carboxyl groups and / or their salts and / or sulfate groups Homopolymers and / or copolymers of olefinically unsaturated monomers and / or polysaccharides containing carboxyl groups and / or their salts and / or polypeptides containing carboxyl groups and / or their salts.

The cationic polyelectrolyte materials are polymeric amine and / or ammonium or phosphine and / or phosphonium compounds.

According to the invention, the number of individual layers applied is considerably less than according to the prior art.

After that, 20 to 60 double layers, i.e. 40 to 120, are usually used

Single layers applied.

According to the solution according to the invention, advantageously only between 1 and 30 individual layers need to be applied in order to achieve the same or even a better one

To obtain separation effect than according to the prior art. Even more advantageously, between 2 and 20 individual layers corresponding to the invention are sufficient

Solution for achieving a better separation effect.

Furthermore, the layer thicknesses of the individual individual layers of the separation-active layer are also located in the area of the thinner layer thicknesses from the area of the known layer thicknesses.

On the one hand, relatively thin layer thicknesses for single and also double layers are known from the prior art. These are around 1 nm per double layer. Around with such a layer thickness of the double layers to achieve a sufficient separation effect, a number of layers of 20 to 60 double layers is necessary.

It is also known from the prior art to apply a smaller number of layers. However, these are then much thicker and are around 500 nm each

Double layer.

According to the solution according to the invention, thin layers in small numbers are sufficient to achieve an equally good or substantially improved separating effect compared to that of the prior art.

Likewise, in the solution according to the invention, in particular for the first

Single layer on the carrier material requires a smaller amount of polyelectrolyte material than is known from the prior art. With this lesser amount of

However, polyelectrolyte material is still predominantly covering the surface of the carrier material. The amount applied is advantageously 5 to 500 μg / cm ² carrier surface, more preferably 50 to 300 μg / cm ²

Carrier surface.

After and / or during the application, a complex formation takes place between the carrier material and the applied first individual layer. This

However, complex formation does not only take place in a near-surface area of the

Carrier material instead, but at least partially extends deeper.

This is possible because the carrier material is constructed in a uniform manner at least chemically and advantageously also structurally throughout.

This creates a certain interlocking between the first individual layer and the

Carrier material reached, resulting in a much better adhesion of this first

Single layer leads on the carrier material.

More than 50%, advantageously more than 80%, of the surface of the carrier material is covered with the first single layer applied. The material of the first individual layer advantageously covers the carrier surface when applied in larger islands or in larger areas or in interconnected islands or in interconnected areas. The membrane according to the invention is used for dewatering organic substances, for example solvents, or mixtures of substances (aldehydes, ketones, ethers, alcohols, amines, acids) or for separating organics / organics * by means of pervaporation or for removing water vapor and / or hydrogen sulfide from substances or Mixtures of substances, such as water vapor and / or hydrogen sulfide from methane, by means of gas separation. The membrane according to the invention should only be used for the separation of substances or mixtures of substances which are inert towards the membrane.

The anionic polyelectrolyte component is preferably homopolymers and / or copolymers and / or their salts, such as, for example, water-soluble sulfonic acid groups. Poly (styrene sulfonic acid), poly (styrene sulfonic acid-old maleic anhydride), poly (vinyl sulfonic acid) sodium salt, poly (styrene sulfonic acid) sodium salt, and / or homo- and / or copolymers and / or their salts such as e.g. Poly (vinylphosphonic acid) and / or phosphoric acid groups containing homopolymers and / or copolymers and / or their salts, e.g. Poly (vinylphosphoric acid) sodium salt and / or carboxyl groups and / or their salts and / or sulfate group-containing polymeric compounds or homo- and / or copolymers of olefinically unsaturated monomers and / or carboxyl-functionalized polysaccharides and / or their salts and / or carboxyl group-containing polypeptides and / or their salts.

Water-soluble nitrogen-containing polymer compounds and / or their salts such as e.g. Polyallylammonium chloride, polydimethyldiallylammonium chloride, polyvinylpyridinium salts, polyethyleneimine, tetraalkylammonium salt groups containing polymer compounds and / or polyvinyl compounds with quaternizable and / or quaternized nitrogen atoms, amino-functionalized poiysaccharides such as e.g. Chitosan and their salts and / or polypeptides containing amino groups (e.g. polylysine) and / or their salts are used.

The polyelectrolytes or polyelectrolyte components are preferably present in an aqueous solution and are applied to the carrier material. The aqueous solution may optionally contain additional ionic and / or nonionic additives, such as low molecular weight electrolytes such as NaCl. The carrier material can be a dense or microporous sheet or a membrane, in particular a sheet which is preferably non-porous. This carrier material consists of a water-insoluble polymer with carboxyl and / or amino and / or sulfonic acid groups and / or phosphonic acid groups and / or

Phosphoric acid groups and / or their salts and / or sulfate groups, preferably functionalized with carboxyl groups.

The carrier material advantageously consists of one or more carboxyl-functionalized polyamide (s) and / or one or more carboxyl-functionalized homo- and / or copolymer of olefinically unsaturated monomers and / or of one or more reaction product (s) made of carboxyl-functionalized polyolefin (s) and / or homo - and / or copolymer of olefinically unsaturated monomers and polyamide (s).

Such a polymer is either used directly as a carrier material for the production of the membranes according to the invention or is applied to a nonwoven as a carrier material consisting of polyamide, polypropylene, polyester, polyphenylene sulfide or a fine silk fabric, preferably from solution.

The inventive multilayer membrane is produced by applying at least one single layer made of at least one anionic or at least one cationic polyelectrolyte material or from at least one separately produced non-stoichiometric polyelectrolyte complex by consecutively alternating application of the oppositely charged polyelectrolyte materials on the carrier material. The order in which the individual polyelectrolyte components are applied to the carrier results from the charge of the carrier material used.

The individual layers are advantageously applied by immersing the carrier material, possibly with the individual layers already applied, into a solution which contains the respective anionic or cationic polyelectrolyte material (s) or the non- contains stoichiometric polyelectolyte complex (s) and possibly additional ionic and / or nonionic additives. The production of the multilayer membrane according to the invention can likewise advantageously also be carried out in the finished module by rinsing the module with the corresponding polyelectrolyte solutions. For this purpose, the carrier material is introduced into a module and connected accordingly. At least immediately before use of the multilayer membrane, depending on the charge of the support material, the module must be rinsed with at least one solution which contains oppositely charged polyelectrolyte components or a non-stoichiometric polyelectrolyte complex. To apply several individual layers, one must alternately rinse with a solution that contains differently charged polyelectrolyte components or complexes. Between the application of the individual layers, the module is rinsed and / or dried with a liquid for washing, advantageously with water.

The individual layers are preferably applied at elevated temperatures. The temperature is advantageously not chosen above the boiling point of the solvent used. It is particularly advantageous to apply the individual layers at temperatures in the range or above the glass transition temperature T _{g of} the support material.

The mass fraction of the polyelectrolyte components in the solutions is between 0.01 and 5% by mass, preferably between 0.03 and 3% by mass.

The carrier material is a dense or microporous material functionalized with ionic and / or ionizable groups.

After the application of each individual layer, complex formation takes place between this individual layer and the preceding oppositely charged individual layer, which leads to firm adhesion of the individual layers to one another.

After each coating step and / or after the application of all individual layers, the multilayer membrane according to the invention is preferably washed with water or with a mixture of water and an organic solvent, preferably alcohol and in particular in a mixing ratio of 4: 1. The multilayer membranes can be dried after the application of one and / or all of the individual layers and after washing. It has proved to be advantageous in that the multilayer membrane is dried after each coating step.

The polyelectrolyte complex layers applied to the support represent the actual release-active layer. However, the support material can also contribute to the release effect.

The multilayer membranes according to the invention can be immersed in an aqueous solution containing the polyelectrolyte components, or by other known ways of applying a thin layer, such as e.g. Spraying or spin coating can be obtained. However, it is also possible to apply the individual layers in a finished module by rinsing with the respective polyelectrolyte solutions.

The multilayer membranes according to the invention are distinguished in that the use of a carrier material functionalized with ionic and / or ionizable groups ensures particularly good adhesion between the polyelectrolyte complex multilayer system and the carrier material. Furthermore, the multilayer membranes according to the invention are distinguished by a high water (steam) permeability or permeability of hydrophilic components and by a good selectivity for water and water vapor and for hydrophilic components in relation to other components. They can also be used multiple times, have high mechanical stability and are easy to handle. Furthermore, the multi-layer membrane production process is characterized by a low use of polyelectrolytes and the formation of very thin, defined separating layers that enable a high permeate flow.

Ways of Carrying Out the Invention

The invention is explained in more detail using several exemplary embodiments.

The permeate flow J in kg / m ² h under the given test conditions (temperature, composition of the feed, permeate-side pressure) and the separation factor α of the multilayer membranes are used for the permeate-related characterization of the multilayer membranes. The α value is dimensionless Size that is defined as the concentration ratio of the binary mixtures in the permeate to that in the feed.

Permeate "Inlet _ ^ water ^' ^ organic component

"Permeate feed

^ Water ^' ^ organic component

Unless stated otherwise, the test conditions were as follows: permeate-side pressure: 2000 Pa temperature: 50 ° C

Example 1 :

To produce a multilayer membrane according to the invention, a polyelectrolyte complex multilayer system is applied to the polymeric carrier material, consisting of a carboxyl-functionalized polyamide-6 with a carboxyl group concentration of 207 μmol / g. The multi-layer system is made by consecutive alternating immersion of the carrier material in aqueous

Polyelectrolyte component solutions built. The polymer carrier is washed with water between each coating step. Polyacrylic acid or polyethyleneimine serve as the polyanion or polycation component. The concentration of the solutions is in each case 20 mmol / l, based on the monomer unit of the polyelectrolyte components. The polyanion and the polycation material alternately apply 6 individual layers, ie a total of 12 single layers or 6 double layers.

The amount of layer material applied to the carrier surface is approximately 60 μg / cm ² per individual layer. The layer thickness of the entire release-active layer on the carrier material is approximately 7 nm.

The following results are obtained when dewatering organic solvents:

Ethanol / water (80/20) T = 50 ° C; J = 0.21 kg / m ² h; α = 2344

Ethanol / water (90/10) T = 50 ° C; J = 0.02 kg / m ² h; α = 1400

2-propanol / water (70/30) T = 50 ° C; J = 0.67 kg / m ² h; α = 4700

2-propanol / water (80/20) T = 50 ° C; J = 0.30 kg / mh; α = 4044 Example 2:

In the production of the multilayer membrane according to the invention, as in

Example 1 procedure, the after the application of the last polyelectrolyte layer

Multi-layer membrane is dried at 70 ° C.

The following results are obtained when dewatering organic solvents:

Ethanol / water (80/20) T = 50 ° C; J = 0.18 kg / m ² h; α = 3000

Ethanol / water (90/10) T = 50 ° C; J = 0.01 kg / m ² h; α = 1685

2-propanol / water (70/30) T = 50 ° C; J = 0.50 kg / m ² h; α = 6500

2-propanol / water (80/20) T = 50 ° C; J = 0.25 kg / m ² h; α = 5980

Example 3:

In the production of the multilayer membrane according to the invention, as in

Example 1 procedure, the polycation being polydimethyldiallylammonium chloride

Place of polyethyleneimine is used. There will be a total of 10

Double layers applied.

The following results are obtained when dewatering organic solvents:

Ethanol / water (80/20) T = 50 ° C; J = 0.45 kg / m ² h; α = 467

Ethanol / water (90/10) T = 50 ° C; J = 0.21 kg / m ² h; α = 300

2-propanol / water (70/30) T = 50 ° C; J = 0.69 kg / m ² h; α = 605

2-propanol / water (80/20) T = 50 ° C; J = 0.38 kg / m ² h; α = 521

Example 4:

The multilayer membrane according to the invention is produced as in Example 1, the polyanion being poly (styrene sulfonic acid) sodium salt Place of polyacrylic acid is used and a total of 10 double layers are applied.

The following results are obtained when dewatering organic solvents:

Ethanol / water (80/20) T = 50 ° C; J = 0.62 kg / m ² h; α = 337

2-propanol / water (70/30) T = 50 ° C; J = 0.89 kg / m ² h; α = 589

Example 5:

In the production of the multilayer membrane according to the invention, as in

Example 1 procedure, poly (styrene sulfonic acid) sodium salt being used as the polyanion and polydimethyldiallylammonium chloride being used as the polycation. A total of 10 double layers are applied.

The following results are obtained when dewatering organic solvents:

Ethanol / water (80/20) T = 50 ° C; J = 0.99 kg / m ² h; α = 289

2-propanol / water (70/30) T = 50 ° C; J = 1.11 kg / m ² h; α = 385

Example 6

In the production of the multilayer membrane according to the invention, as in

Procedure 1, wherein the carrier material consists of a modified polyacrylonitrile. 3 double layers are applied.

The following results are obtained when dewatering organic solvents:

2-propanol / water (70/30) T = 50 ° C; J = 0.48 kg / m ² h; α = 820

2-propanol / water (80/20) T = 50 ° C; J = 0.50 kg / m ² h; = 2243 Example 7

In the production of the multilayer membrane according to the invention, as in

Example 1 process, the support material consisting of a modified polyacrylonitrile and the application of the polyelectrolyte layers at 80.degree. It will be one

Double layer applied.

The following results are obtained when dewatering organic solvents:

2-propanol / water (70/30) T = 50 ° C; J = 1.18 kg / m ² h; α = 2002

2-propanol / water (80/20) T = 50 ° C; J = 1.17 kg / m ² h; α = 1231

Claims

claims 1.Multi-layer membranes consisting of a dense or microporous carrier material, which is at least chemically consistently constructed in the same way, and of at least one single layer applied thereon, which is a separation-active layer, and are connected to the carrier material and, in the case of a plurality of individual layers, to one another by polyelectrolyte complexes, the known one being applied Number of individual layers, a significantly smaller number of individual layers is applied and the layer thickness of these individual layers is in the range of thinner layer thicknesses from the known range of layer thicknesses, and the first individual layer of the release-active layer is predominant in smaller amounts compared to the known amount applied Part of the surface of the carrier material is covered and with the carrier material complex formation has occurred, which at least partially does not only cover the area near the surface of the carrier material concerns. 2. Multi-layer membranes according to claim 1, in which the carrier material consists of a water-insoluble material, is a flat membrane or a hollow fiber and / or an asymmetrical membrane. 3. Multi-layer membranes according to claim 1, in which the carrier material is applied or deposited on a fine silk fabric or on a non-woven fabric, the non-woven fabric consisting of a polyamide, polyester, polypropylene or polyphenylene sulfide. 4. multilayer membranes according to claim 1, in which the carrier material used is a material functionalized with ionic and / or ionizable groups. 5. Multi-layer membranes according to claim 1, in which the layer material used is an anionic or cationic polyelectrolyte material. 6. Multi-layer membranes according to claim 1, in which between 1 and 30, advantageously 2 to 20, individual layers are applied to the carrier material. 7. Multi-layer membranes according to claim 1, in which the layer thicknesses of the individual layers of the separation-active layer are between 0.3 and 1.5 nm / single layer, advantageously between 0.5 and 0.9 nm / single layer. 8. Multi-layer membranes according to claim 1, in which the applied amount of the respective individual layers is in the range from 5 to 500 μg / cm ² carrier surface, advantageously between 50 and 300 μg / cm ² carrier surface. 9. multilayer membranes according to claim 1, in which the covering of the surface of the carrier material with the material of the first single layer of the separation-active layer has occurred in larger islands or in larger areas or in interconnected islands or in interconnected areas. 10. Multi-layer membranes according to claim 9, in which the surface of the carrier material is covered with the material of the first individual layer of the separation-active layer by more than 50%, advantageously by more than 80%. 11. Multi-layer membranes according to claim 1, in which the complex formation between the carrier material and the material of the first single layer of the separation-active layer in large parts of the covering not only in the region of the carrier material near the surface, advantageously for the most part not only in the region of the carrier material near the surface, is done. 12. A method for producing multilayer membranes according to any one of claims 1-11, in which at least one single layer of at least one anionic polyelectrolyte material or on a dense or microporous support material functionalized with ionic and / or ionizable groups at least one cationic polyelectrolyte material is applied alternately or from at least one non-stoichiometric polyelectrolyte complex and, depending on the charge of the material, the next individual layer of a material with the opposite charge is applied to the respective surface, with complex formation after the application of the next individual layer in each case between first between the carrier material and the material of the first individual layer and then between the respectively oppositely charged layer materials and the multilayer membranes are washed and / or dried after each coating and / or after the application of all individual layers. 13. The method according to claim 12, in which as the carrier material a water-insoluble material, the carboxyl groups and / or carboxylate groups and / or sulfonic acid groups and / or sulfonate groups and / or phosphonic acid groups and / or phosphonate groups and / or phosphoric acid groups and / or phosphate groups and / or sulfate groups and / or has amino groups and / or ammonium groups, the carrier material advantageously consisting of one or more carboxyl-functionalized polyamide (s) and / or one or more carboxyl-functionalized homo- and / or copolymer (s) of olefinically unsaturated monomers and / or of one or several reaction product (s) consists of carboxyl-functionalized polyolefin (s) and / or homo- and / or copolymer (s) of olefinically unsaturated monomers and polyamide (s). 14. The method according to claim 12, in which a carrier material is used which consists of one or more amino- and / or ammonium-functionalized polymer compound (s), preferably aliphatic polyamide (s). 15. The method according to claim 12, in which an anionic polyelectrolyte component is used from a, preferably water-soluble, polymer compound to produce an anionic single layer, the carboxyl groups and / or carboxylate groups and / or sulfonic acid groups and / or sulfonate groups and / or phosphonic acid groups and / or phosphonate groups and / or phosphoric acid groups and / or phosphate groups and / or sulfate groups. 16. The method according to claim 15, in which an anionic polyelectrolyte component is used to produce an anionic single layer, which has a carboxyl group and / or carboxylate groups and / or sulfonic acid and / or sulfonate groups and / or phosphonic acid and / or phosphonate groups and / or phosphoric acid and / or is a homo- and / or copolymer of olefinically unsaturated monomers containing phosphate groups and / or sulfate groups, or in which an anionic polyelectrolyte component is used to produce an anionic single layer, which is a polysaccharide containing carboxyl and / or carboxylate groups, advantageously as carboxyl groups comprising polysaccharide, a mixed cellulose ester is used, or in which an anionic polyelectrolyte component is used to produce an anionic single layer, which is a polypeptide having carboxyl and / or carboxylate groups. 17. The method according to claim 12, in which a cationic polyelectrolyte component is used from a, preferably water-soluble, polymer compound for the production of a cationic single layer, which has amino groups and / or ammonium groups and / or phosphine groups and / or phosphonium groups and advantageously polyethyleneimine or a Is polydiallyimethylammonium salt or polydimethyldiallylammonium chloride or a polyallylammonium salt or polyallylammonium chloride or polyallylamine or a polysaccharide containing amino and / or ammonium groups or a polypeptide containing amino and / or ammonium groups. 18. The method according to claim 12, wherein the application of the single layers on the carrier material from an aqueous solution of at least one of the polyelectrolyte materials or of at least one separately produced non-stoichiometric polyelectrolyte complex with a mass fraction of 0.01 to 5 mass%, preferably 0.03 to 3% by mass. 19. The method according to claim 12, wherein the application of the individual layers to the carrier material at elevated temperatures, advantageously at temperatures below the boiling point of the solvent and also advantageously in the range or above the glass transition temperature of the carrier material. 20. The method according to claim 12, wherein the solutions containing the polyelectrolyte component are additionally provided with ionic and / or nonionic additives. 21. The method according to claim 12, in which between 1 and 30 individual layers, preferably between 2 and 20 individual layers, are applied to the carrier material. 22. The method according to claim 12, in which after each application of a single layer with water and / or a mixture of water and an organic solvent, preferably alcohol, in particular in a ratio of 4: 1, is washed. 23. The method according to claim 12, in which drying is carried out after the application of each individual layer or after the application of the last individual layer. 24. The method according to claim 12, in which the application of the individual layers is carried out by alternately immersing them in a solution containing anionic or cationic polyelectrolyte materials or non-stoichiometric polyelectrolyte complex (s) and the membrane is washed and / or dried between each immersion. 25. The method according to claim 12, wherein the individual layers are applied by introducing the carrier material into a module and rinsing the carrier material with at least one solution with anionic or cationic polyelectrolyte materials or non-stoichiometric polyelectrolyte complex (s) and before the first use is washed and / or dried after each coating step.