EP1831451A1

EP1831451A1 - Textile two or three dimensional fabric containing materials that are capable of swelling

Info

Publication number: EP1831451A1
Application number: EP05823619A
Authority: EP
Inventors: Manfred Weber; Axel Weiss; Eberhard Schupp; Pulakesh Mukherjee; Ralf Mossbach; Bernd Reck; Kuno Beutler
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-12-22
Filing date: 2005-12-21
Publication date: 2007-09-12
Also published as: DE102004063004A1; US20100041291A1; US8143176B2; WO2006069689A1

Abstract

The invention relates to a textile two or three dimensional fabric made of fibers and/or strips and materials that are capable of swelling, wherein the respective amounts of fibers and/or strips and materials, that are capable of swelling, contained in said fabric are such that the fibers and/or strips are enveloped by the materials that are capable of swelling and the cavities of the fabric in a swollen state are partially or fully filled with material-bonded water and aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON are applied as materials, that are capable of swelling, to the fibers and/or strips.

Description

Textile two- or three-dimensional structures containing swellable materials

description

The present invention relates to textile two- or three-dimensional structures of fibers and / or tapes and swellable materials, wherein the fibers and / or tapes present in the structure and the swellable materials are each present in an amount such that the fibers and / or tapes of the are enveloped swellable materials and the cavities of the structures in the swollen state are partially or completely filled with material-bound water and being applied as swellable materials aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON on the fibers and / or bands.

Furthermore, the present invention relates to a method for producing the inventive two- or three-dimensional structures of fibers and / or tapes and swellable materials and their use, for example, as sealing materials for cables, especially electrical and communication cables, road, tunnel and hydraulic engineering as well as for construction pits, flood, groundwater protection and roof waterproofing, as well as the use of the aqueous emulsion of (co) polymers of at least one ethylenically unsaturated monomer MON for the production of textile two- or three-dimensional structures.

Cables, especially electrical and communications cables, are very sensitive to moisture entering the individual cable harnesses due to damage to the plastic sheathing. In such cases, the water may migrate over very long distances in the cable and damage it in its full length. To avoid this, swellable material, such as SAP powder (Super Absorbent Polymers, described, for example, in FL Buchholz, Modern Superabsorbent Technology, Wiley-VCH, 1998), alone or in combination with nonwovens or textiles as a carrier between the cable and the outer plastic shell used. If a small crack occurs in the cable sheath, even minimal amounts of water will cause the SAP to swell. The swelling pressure closes the hole and the further expansion of the water is prevented.

In many areas of the construction industry, sealing of the structures against penetrating day, ground, stratified or seepage water is required. For this purpose, u.a. Bitumen welding strips (US Pat. No. 2,015,102, US Pat. No. 2,160,342) Plastic seals (DE-A 199 30 701), foam tapes (DE-A 28 19 604, DE-B 12 23407) or clay sealing sheets for sealing.

Plastic waterproofing membranes and not fully bonded bitumen seals adheres to the disadvantage that in case of damage, the penetrating water between the sealing layer and the building can spread more or less easily. Especially in concrete structures, the water seeping under the sealing layer penetrates in porous concrete or cracks in the concrete. There arise rust damage to the reinforcement. On the inside of the walls and ceilings arise damp spots. Furthermore, the water can seep up to the building joints and escape there.

Tonseal membranes usually use bentonite as sealing material, which is not filter-stable in contrast to the geotextiles frequently used as carrier material. The bentonite can be washed out by seeping water, thus losing the sealing effect. On the other hand, clay liners prevent the longitudinal seepage of penetrated water due to bentonite passing out of the surface when it swells.

For the sealing of basements, underground garages, groundwater basins or similar buildings against water from the soil, for example, water from the ground or groundwater in building construction and civil engineering, two recognized construction methods are available.

The usual method of construction is the white tub, in which waterproof concrete, a complex additional reinforcement to avoid cracks and joint tapes between the individual components or construction joints are used. Nevertheless occurring cracks are pressed with injection resins.

The black tub has the name of the most commonly used Bitumendichtungsbahnen, but in recent times are also plastic seals used (DE-A 199 30 701).

Tondichtungsbahnen are used for so-called brown tubs. Here one uses the disadvantage of insufficient filter stability, in which the bentonite from the clay sealing membrane is flooded in porous concrete and thus leads to its sealing.

Office and industrial buildings usually have flat roofs. For residential buildings, these are less used, because the risk of leaks is still great. Because of the vapor diffusion, flat roof waterproofing is only fixed point or line. After damage to the seal, the infiltrating water spreads easily under the seal and leads to wet spots and structural damage.

In tunneling, sealing is required once to protect the structure. However, dripping water also endangers the user of the tunnel by black ice formation in road tunnels or short circuits in electrified railway tunnels.

For tunnels constructed in open-plan design, the concrete structure must be protected against the water that seeped through later recharge. Again, it can be Spread water after damage to the seal between the waterproofing and the concrete pavement. It then occurs in cracks, weak points or at the joints.

Mechanically drilled or milled or mined tunnels can run very far below the groundwater level. The seal is then loaded with very high pressure. Due to the high water pressure, the water is distributed further under the damaged seals.

In earthworks of road construction, the road body in water protection areas must be sealed against the permeable ground. In spite of the known disadvantages with regard to filter stability and the joining technique for the web joints, this is often done today with clay sealing sheets. The clay sealing membrane must be frost-proof and secured against dehydration.

Rain retention and separation basins or sludge ponds in permeable soils are sealed with plastic waterproofing membranes and so-called protective fleeces. To drive the basins with equipment during maintenance often a concrete sole must be installed.

During their production, cement sludge penetrates into the protective fleece installed above the waterproofing membrane and hardens, whereby the nonwovens partially lose their protective function. Due to the now rough structure, the fleece scratches during movements, e.g. from thermal expansion on the surface of the seal.

If such basins are sealed with clay sealing membranes, they must be sufficiently covered with earth material to ensure frost protection and to prevent them from drying out.

Irrigation or power plant sewers often incorporate concrete or asphalt seals. These receive an additional seal from plastic waterproofing membranes or clay sealing membranes. Again, the same problems arise as in the retention basin.

The individual plastic waterproofing membranes are welded overlapped at the joints during installation. Bituminous sheets are butted against each other and overlapped by a strip glued to the butt joint. Clay sheets are laid overlapped. Bentonite powder is sprinkled into the joint of the overlap or a bentonite paste is incorporated.

Seals applied to a building surface do not protect against underflow after damage to the seal. Between building surface and seals are according to the current state of the art no protective fleeces installed, because they would distribute the penetrating water due to their horizontal permeability over the entire surface damage to the seal.

Applied or embedded in the ground geomembranes with protective fleece are claimed to water pressure from above or below. Here the vertical permeability is decisive. For geomembranes of different products, e.g. Tondichtungsbahnen, care must be taken that the special sealing tone can not be washed out of the backing material of the protective fleece.

From DE-A 196 25 245 multi-layer seals for cavities such as tunnels are known, which have geomembrane made of plastics and an insert layer between the geomembranes. In the liner layer strongly swelling chemical or mineral fillers are incorporated. However, the seals described here are in need of improvement in terms of their blocking effect against penetrating water.

Furthermore, the present invention relates to a method for producing the inventive two- or three-dimensional structures of fibers and / or tapes and swellable materials and their use, for example, as Absorpti- onsmaterialien for sanitary articles, gardening and landscaping, packaging materials, general and medical waste and construction industry, and the use of the aqueous emulsion of (co) polymers of at least one ethylenically unsaturated monomer MON for the production of textile two- or three-dimensional structures.

SAP powder and nonwoven fabrics are used in many hygiene segments such as baby care, adult incontinence and feminine hygiene. The nonwoven fabric acts as a transfer layer, which distributes the liquid to be absorbed over the entire surface and thus allows optimal use of the swellable material.

Swellable materials are ideal for gardening and landscaping applications. They absorb water, can hold it and easily release it to the roots of the plants. Since water absorption and release are reversible, the swellable material maintains its properties over a long period of time. Thus, swellable materials significantly increase the plant's resistance to watering and dryness. The number of necessary irrigation is greatly reduced and less water consumption is the result. In addition, the soil remains loose due to the swelling and shrinkage in the water absorption and -abgäbe. The roots are better ventilated.

The absorption capacity can also be used to package food. Liquids escaping from food are absorbed by the swellable material. safely enclosed. By retaining the water in the polymer they remain in the same state and cool longer.

The solidification of liquid wastes, especially medical waste with absorbent material, is a clean and dry solution and makes it easier to dispose of waste liquids.

The absorption properties also make the absorbent material a very good choice in the manufacture of compresses, plasters or wound dressings to absorb all exuding secretions, thus helping to keep the wound dressings hygienically clean.

The absorption and solidification of aqueous solutions can improve their handling and reduce the risk of environmental pollution from leaks and spills during storage, transport, and ultimately disposal. Many types of waste material can be treated in this way, including sewage, sewage sludge and sludge deposits in rivers, as well as radioactive waste.

In addition to liquid treatment, the swellable material can serve as a cat litter replacement. In addition to the increase in Absorbtionskapazität a decrease in weight is recorded as an advantage.

In the construction industry, swellable material, in addition to the previously described waterproofing properties, may also be blended into building materials, e.g. Concrete lead to improved strength and durability of the resulting hardened concrete. The nature of the concrete mass can be changed by the controlled addition of swellable material.

In addition to the ability to absorb water, absorbent polymers can still absorb water vapor. This property can be used to control the humidity. Absorbent polymers can - in terms of their mass - absorb and release more moisture from the air than inorganic materials. The ability of swellable materials to regulate humidity can be used to prevent condensation on ceilings and walls in damp buildings.

Powdered swellable materials have disadvantages in the applications described above. The powders are not bound to carrier substrates and thus movable. The swellable material is not homogeneous but distributed in spots. The introduction of the swellable material in the carrier is expensive. Due to the combination of swellable polymer and nonwoven fabric, a bond of the swellable polymer to the fiber of the nonwoven fabric. The swellable polymer is thus completely immobile, which is accompanied by a uniform distribution of the absorbent material. Consequently, no powder can escape in the applications described. The material can be handled as rolled goods.

The present invention was therefore based on the object to remedy the disadvantages described and to produce a new sealing or absorbent structure. This should u.a. have a high protective function for adjacent layers, in particular made of plastic and are also distinguished by the fact that the uncontrolled spread of water below the seal causes no damage to the adjacent layers. Furthermore, the new sealing structure should be tight against perpendicular to the product surface oppressive water.

In addition, it should be able to absorb many times its own weight in liquid and store the liquid, even if a significant pressure is used. In addition to the ability to absorb water, the structure should be able to absorb water vapor.

To achieve the object according to the invention, novel textile two-dimensional or three-dimensional structures of fibers and / or tapes and swellable materials have been developed, wherein the fibers and / or tapes present in the structure and the swellable materials are each present in such an amount that the fibers and / or or bands are enveloped by the swellable materials and the cavities of the structures in the swollen state partially or completely filled with material-bound water ^• and wherein as swellable materials aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON are used, characterized in that at least one aqueous dispersion is prepared in the presence of at least one water-soluble polymer, wherein at least one water-soluble polymer is selected from

(a1) graft polymers of vinyl acetate and / or vinyl propionate on polyalkylene glycol or on one or both sides with alkyl-, carboxyl- or amino-substituted polyalkylene glycol, (a2) copolymers of alkylpolyalkylene glycol (meth) acrylates and (meth) acrylic acid,

(a3) polyalkylene glycols,

(a4) polyalkylene glycols substituted on one or both sides with alkyl, carboxyl or amino groups,

and at least one water-soluble polymer is selected from (b1) hydrolyzed copolymers of vinyl alkyl ethers and maleic anhydride as free polyacid or at least partially neutralized with alkali metal hydroxides or ammonium bases,

(b2) starch, modified or unmodified, (b3) synthetic copolymers obtainable by copolymerization of

(β1) one or more nonionic monoethylenically unsaturated monomers,

(β2) one or more cationic monoethylenically unsaturated monomers,

(β3) optionally one or more anionic monoethylenically unsaturated monomers,

wherein the molar fraction of cationic monoethylenically unsaturated monomers (β2) copolymerized in (b3) is higher than the proportion of copolymerized anionic monoethylenically unsaturated monomers (β3).

Furthermore, an improved method for producing the textile structures according to the invention was used. In addition, starting from the textile structures according to the invention, improved sealing materials were provided for road, tunnel and hydraulic engineering as well as for construction pits, flood protection and roof waterproofing. The present invention also extends to the use of the aqueous polymer emulsion for the production of the textile structures according to the invention.

Suitable two- or three-dimensional structures are i.a. corresponding nonwovens, knitted fabrics, woven or knitted or combinations thereof. A nonwoven is usually understood to mean a nonwoven and nonwoven fabric which may contain fibers or ribbons. Knitted fabrics are textile structures that are created by forming stitches that hold each other. Fabrics are textile structures made of perpendicularly crossing yarns or ribbons which are produced on looms. The two-dimensional or three-dimensional structures according to the invention are preferably in the form of nonwovens or woven fabrics. Suitable nonwovens are i.a. Spunbonded nonwovens, needled nonwovens or hydroentangled nonwovens. The solidification of the nonwovens can be done mechanically, thermally or chemically. The structures according to the invention can be both two-dimensional, that is to say flat, and moreover three-dimensional, ie be made with a corresponding thickness.

The textile two- or three-dimensional structures according to the invention may consist of ribbons or of fibers, the latter being preferably used. Suitable tapes are, inter alia, tapes, in particular those made of textile materials or foil tapes, from conventional film materials, for example from plastics such as polyethylene or polypropylene. As fibers staple fibers or filaments (filaments) can be used. The fibers may be, inter alia, synthetic, mineral or natural, in particular synthetic or mineral fibers. be set. Examples of synthetic fibers include fibers of polyethylene, polypropylene, polybutylene terephthalate, polyamide, polyethylene terephthalate, polyester, polysulfone or polyether ketone. Mineral fibers may include ceramic materials, silicon carbide or boron nitride. Also conceivable is the use of fibers made of carbon or glass fibers.

The fibers and / or bands present in the textile structures and the swellable materials are each present in such an amount that the fibers and / or bands are enveloped by the swellable materials and the cavities of the structures are completely filled with material-bound water in the swollen state , With regard to the amount of swellable materials usually 0.05 to 20 kg, in particular 0.1 to 10 kg of these swellable materials are used per m ² of finished swellable nonwoven. As regards the amount of fibers and / or bands per m ² of finished swellable nonwoven, this is usually 0.1 to 2 kg, in particular 0.15 to 1 kg.

In order to achieve the water impermeability in the horizontal plane, the textile structure according to the invention must be impregnated with the swellable materials in such a way that a complete covering of the fibers is achieved.

By impregnation of the textile structure with the emulsion according to the invention and subsequent drying at temperatures of 120 (PP nonwoven) - 160 ⁰ C, a highly absorbent swellable nonwoven, which is capable of a multiple within a short time, ie up to several 100% of its own weight to absorb water.

The aqueous emulsions used as swellable materials of

(Co) polymers of at least one ethylenically unsaturated monomer MON are characterized in that at least one aqueous dispersion is prepared in the presence of at least one water-soluble polymer and wherein at least one water-soluble polymer is selected from

(a1) graft polymers of vinyl acetate and / or vinyl propionate on polyalkylene glycol or on one or both sides with alkyl-, carboxyl- or amino-substituted polyalkylene glycol,

(a2) copolymers of alkylpolyalkylene glycol (meth) acrylates and (meth) acrylic acid,

(a3) polyalkylene glycols,

(b2) starch, unmodified or preferably cationic or anionic modified, (b3) synthetic copolymers obtainable by copolymerization of

(β1) one or more nonionic monoethylenically unsaturated monomers,

(β2) one or more cationic monoethylenically unsaturated monomers,

(β3) optionally one or more anionic monoethylenically unsaturated monomers,

The preparation of aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON used according to the invention is described below.

For the purposes of the present invention, aqueous dispersions are to be understood as meaning aqueous solutions, suspensions and, preferably, emulsions.

Suitable ethylenically unsaturated monomers MON include, for example, nitrogen-containing water-soluble ethylenically unsaturated monomers and anionic ethylenically unsaturated monomers.

Suitable nitrogen-containing water-soluble ethylenically unsaturated monomers are, for example, homopolymers of N-vinylformamide, N-vinylacetamide, N-vinylimidazole and N-vinylpyrrolidone or copolymers of at least two of the abovementioned monomers.

Suitable anionic ethylenically unsaturated monomers are, for example:

Monoethylenically unsaturated C ₃ - to C ₅ -carboxylic acids, for example monoethylenically unsaturated C ₃ - to C ₅ -mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid or fumaric acid, Vinylsulfonic acid, styrenesulfonic acid, in particular para-styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, for example

vinylphosphonic

In this case, the above-mentioned ethylenically unsaturated anionic monomers can each be used as the free acid or in the form of their alkali metal or ammonium salts.

Preferred ethylenically unsaturated anionic monomers include (meth) acrylic acid, maleic acid and acrylamidomethylpropanesulfonic acid, particularly preferred is acrylic acid.

Ethylenically unsaturated anionic monomers can be polymerized to form homopolymers or else mixed with one another or with other comonomers to give copolymers. Examples are the homopolymers of acrylic acid or copolymers of acrylic acid with methacrylic acid and / or maleic acid.

However, the (co) polymerization of the abovementioned ethylenically unsaturated anionic monomers can also be carried out in the presence of at least one ethylenically unsaturated comonomer which may be nonionic or may carry a positive charge, ie is cationic. Examples of suitable nonionic or cationic comonomers are (meth) acrylamide, acrylic esters of C ₁ -C ₄ -alkanols, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, acrylic acid iso butyl ester, sec.-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, methacrylic acid ester of methanol or ethanol, vinyl acetate, vinyl propionate, mono- or dialyl-di (C ₁ -C ₄ alkyl) ammonium salts, in particular halides of the formula

where X ^"is selected from, for example, fluoride, bromide, iodide and in particular chloride,

2- [N, N-di- (C ₁ -C ₄ alkyl) amino] ethyl (meth) acrylates, 3- [N, N-di- (C _r C ₄ alkyl) aminopropyl (meth) acrylates, where C ₁ -C ₄ -alkyl can each be different or preferably identical and selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl and preferably methyl, very particularly preferably 2- (N, N-) Dimethylamino) ethyl (meth) acrylate and 3- (N, N-dimethyl) aminopropyl (meth) acrylate.

N-vinylimidazole and N-vinylimidazole quaternized with C 1 -C 4 -alkyl or benzyl, where suitable counterions are, for example, halide, in particular bromide or chloride, or hydrogensulfate.

Basic comonomers such as 2- [N, N-di- (C ₁ -C ₄ alkyl) amino] ethyl (meth) acrylates and 3- [N, N-di- (C 1 -C ₄ alkyl) aminopropyl ( Meth) acrylates can be used both in the form of the free bases and in partially or fully buffered form in the copolymerization.

Nonionic and / or cationic comonomers can be added in the preparation of the copolymers used according to the invention preferably in amounts such that the resulting copolymers are water-soluble and have an overall anionic charge, which may be stabilized, for example, by alkali metal cations or ammonium cations which may be substituted. Based on the total amount of comonomers used in the copolymerization, the amount of nonionic and / or cationic comonomers may be e.g. 0 to 99, preferably 5 to 45 wt .-% amount.

Preferred copolymers are, for example, copolymers of 55 to 90% by weight of acrylic acid and 45 to 10% by weight of acrylamide.

In a specific embodiment of the present invention, crosslinked copolymers are used as (co) polymers of at least one ethylenically unsaturated anionic monomer.

Crosslinked copolymers can be prepared by additionally carrying out the copolymerization in the presence of at least one crosslinker. Copolymers are then obtained having a higher molecular weight than when (co) polymerizing at least one ethylenically unsaturated monomer MON in the absence of a crosslinking agent. Correspondingly prepared crosslinked copolymers have a high water absorption capacity. Crosslinkers which can be used are all compounds which have at least two ethylenic double bonds in the molecule. Such compounds are used, for example, in the preparation of crosslinked polyacrylic acids, such as used perabsorbent polymers, cf. EP-A 858 478. Examples of particularly suitable crosslinkers are:

Triallylamine, Pentaerythrittriallether, methylenebis (meth) acrylamide, N ₁ N'-divinylethyleneurea, complete with acrylic acid or methacrylic acid esterified dihydric or polyhydric alcohols containing 2 to 4 carbon atoms such as ethylene glycol di (meth) acrylate, 1, 4-butanediol di ( meth) acrylate, di (meth) acrylates of polyethylene glycols having molecular weights M _n of, for example, 300 to 600 g / mol, compounds of the general formula I

where the variables are defined as follows:

R ^{1 is the} same or different and selected from methyl and hydrogen; m is an integer from 0 to 2, preferably 1;

A ¹ CH ₂ or -CH ₂ -CH ₂ - or R ² -CH or para-C ₆ H ₄ for the case where m = 0,

CH, R ² -C or 1, 3,5-C ₆ H ₃ in the event that m = 1, and carbon in the case that m = 2; R ^{2 is} selected from C 1 -C ₄ -alkyl such as nC ₄ H ₉ , nC ₃ H ₇ , iso-C ₃ H ₇ and preferably C ₂ H ₅ and CH ₃ , or phenyl, A ² , A ³ , A ^{4 is the} same or different and chosen

C _r C ₂₀ alkylene, such as -CH ₂ -, -CH (CH ₃₎ -, -CH (C ₂ H ₅₎ -, - CH (C ₆ H ₅₎ -,

- (CH ₂ ) ₂ -, - (CH ₂ ) _S -, - (CH ₂ ) ₄ -, - (CH ₂ ) _S -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₇ -, - ( CH ₂ V, - (CH ₂ ) ₉ -,

- (CH ₂ ) ₁₀ -, -CH (CH ₃ ) - (CH ₂ ) ₂ -CH (CH ₃ ) -; cis- or fractions-C ₄ -C ₁₀ -cycloalkylene, such as, for example, c / s-1,3-

Cyclopentylidene, trans-ϊ, 3-cyclopentylidene c / s-i ^ -cyclohexylidene, trans-1, 4-cyclohexylidene;

CrC ₂₀ -alkylene, in which from one to seven are not adjacent C atoms are replaced by oxygen, such as -CH ₂ -O-CH ₂ -, -CH ₂ -CH ₂ -O, - (CHa) ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₂ - (CH ₂ ) ₂ -, - [(CH ₂ ) ₂ -O] ₃ - (CH ₂ ) ₂ -;

C _r C ₂₀ alkylene substituted with up to 4 hydroxyl groups, wherein in C ₁ -C ₂₀ - alkylene from one to seven non-adjacent C atoms by

Oxygen are replaced, such as -CH ₂ -O-CH ₂ -CH (OH) -CH ₂ -, -CH ₂ -O- [CH ₂ -CH (OH) -CH ₂ ] ₂ -, -CH ₂ -O - [CH ₂ -CH (OH) -CH ₂ ] ₃ -;

C ₆ -C ₄ -arylene, for example para-C ₆ H ₄ ,

furthermore 2,2-bis (hydroxymethyl) butanol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetraacrylate and triallylmethylammonium chloride.

If one wishes to use one or more crosslinkers in the preparation of (co) polymers of at least one ethylenically unsaturated monomer MON, the amounts of crosslinker used in each case are, for example, 0.0005 to 5.0, preferably 0.001 to 1.0,% by weight %, based on the total mass of the ethylenically unsaturated monomers MON used in the (co) polymerization.

To start the (co) polymerization is usually used polymerization initiators which form radicals under the reaction conditions. Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, redox catalysts and azo compounds, such as 2,2'-azobis (N, N-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) , 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2-amidinopropane) dihydrochloride). Polymerization initiators are used in customary amounts in (co) polymerizations. Preferably, azo initiators are used as polymerization initiators. However, it is also possible to initiate the (co) polymerization with the aid of high-energy rays such as electron beams or by irradiation with UV light.

In one embodiment of the present invention, aqueous emulsions of (co) polymers of (co) polymers of at least one ethylenically unsaturated monomer MON have a (co) polymer concentration of, for example, 1 to 50, preferably 10 to 30 and in particular 15 to 25 wt. The (co) polymer concentration can also be referred to as solids content.

Emulsions used according to the invention are prepared in the presence of at least one water-soluble polymer, at least one water-soluble polymer being selected (a1) graft polymers of vinyl acetate and / or vinyl propionate on polyalkylene glycol or on one or both sides with alkyl-, carboxyl- or amino-substituted polyalkylene glycol,

(a2) copolymers of alkylpolycylene glycol (meth) acrylates and (meth) acrylic acid,

(a3) polyalkylene glycols,

and at least one water-soluble polymer is selected from

(b1) hydrolyzed copolymers of vinyl alkyl ethers and maleic anhydride as free polyacid or at least partially neutralized with alkali metal hydroxides or ammonium bases, (b2) starch, unmodified or preferably cationic or anionic modified, (b3) synthetic copolymers obtainable by copolymerization of (β1) one or more nonionic monoethylenically unsaturated monomers,

(β2) one or more cationic monoethylenically unsaturated monomers, (β3) optionally one or more anionic monoethylenically unsaturated monomers,

Emulsions used according to the invention can also be prepared in the presence of at least two different of the abovementioned water-soluble polymers.

The amount of water-soluble polymers in aqueous dispersions used according to the invention is in total, for example, 1 to 70, preferably 5 to 50, particularly preferably 10 to 25,% by weight. The aqueous dispersions have, for example at a pH of 4.5, a dynamic viscosity in the range of 200 to 12,000 mPa · s, preferably 200 to 6000 mPa · s (measured in a Brookfield viscometer at 20 ^° C., spindle 6, 100 U / min).

Suitable water-soluble polymers of group (a1) are graft polymers of vinyl propionate or of mixtures of vinyl propionate and vinyl acetate, preferably of vinyl acetate on polyalkylene glycol, preferably polyethylene glycol or polyalkylene glycol substituted on one or both sides with alkyl, carboxyl or amino groups, preferably polyethylene glycol. Polyalkylene glycols suitable as a graft base are described, for example, in WO 03/046024, page 4, line 37 to page 8, line 9. For example, from 10 to 10,000, preferably from 30 to 300, parts by weight of vinyl propionate, a mixture of vinyl propionate and vinyl acetate or preferably vinyl acetate, are grafted onto 100 parts by weight of the grafting base. Very particular preference is given to using polyethylene glycol having a molecular weight M _{n of} from 1000 to 100 000 g / mol as the graft base.

Suitable water-soluble polymers of group (a2) are copolymers of alkylpolyalkylene glycol (meth) acrylates and (meth) acrylic acid, preference is given to copolymers of alkylpolyalkylene glycol acrylates and (meth) acrylic acid. Such compounds are known, for example, as dispersants for cement. They are prepared by first esterifying addition products of ethylene oxide and / or propylene oxide onto, for example, C ₁ -C ₁₈ -alcohols with acrylic acid and / or methacrylic acid and then copolymerizing the resulting esters with acrylic acid and / or methacrylic acid. Commonly used water-soluble polymers of group (a2) contain, for example, 5 to 60, preferably 10 to 35 wt .-% of copolymerized units of alkyl polyalkylene glycol (meth) acrylates and 95 to 40, preferably 90 to 65 wt .-% of copolymerized units of ( meth) acrylic acid. They usually have molecular weights M _w of 2,000 to 50,000, preferably 5,000 to 20,000 g / mol. Water-soluble polymers of group (a2) can be used in the form of the polyacids or else in completely or partially neutralized form in the preparation of aqueous dispersions used according to the invention. Carboxyl groups of the water-soluble polymers of group (a2) can preferably be neutralized with sodium hydroxide solution, potassium hydroxide solution or ammonia.

Suitable water-soluble polymers (a3) are polyalkylene glycols, preferably polyethylene glycols.

In one embodiment of the present invention, polyalkylene glycols used as water-soluble polymer (a3) and especially polyethylene glycols have a molecular weight M _n of 100 to 100,000, preferably from 300 to 80,000, more preferably from 600 to 50,000 and in particular from 1,000 to 50,000 g / mol, wherein the molecular structure of polyalkylene glycols is defined above. Preferred polyalkylene glycols (a3) are polyethylene glycol, polypropylene glycol and block copolymers of ethylene oxide and propylene oxide. The block copolymers may contain polymerized ethylene oxide and propylene oxide in any desired amounts and in any order and have two or more blocks.

Suitable water-soluble polymers (a4) are polyalkylene glycols substituted on one or both sides with alkyl, carboxyl or amino groups and in particular polyethylene glycols, for example having molecular weights M _n in the range from 100 to 100,000. preferably from 300 to 80,000, more preferably from 600 to 50,000 and in particular from 1,000 to 50,000 g / mol. Preferred water-soluble polymers (a4) are polyethylene glycols, polypropylene glycols and block copolymers of ethylene oxide and propylene oxide substituted on one or both sides with alkyl copolymers containing ethylene oxide and propylene oxide in copolymerized form in any amount and in any order and having two or more blocks can. Suitable alkyl groups are C _r C ₂ o-alkyl, in particular unbranched C 1 -C ₂₀ -alkyl. Suitable carboxyl groups are, for example, pivalate and propionate and in particular acetate, furthermore benzoate. Amino groups may be selected from NH ₂ , and mono- and di-CrCrAlkylaminruppen and cyclic amino groups such as

Aqueous dispersions used according to the invention comprise at least one water-soluble polymer of groups (a1), (a2), (a3) or (a4), for example in amounts of 2 to 15, preferably 5 to 12,% by weight, based on the total amount used in accordance with the invention dispersion. Water-soluble polymer of the groups (a1), (a2), (a3) or (a4) is used in the preparation of the dispersion used according to the invention, preferably in the (co) polymerization.

The water-soluble polymers of group (b1) are preferably used partially or quantitatively hydrolyzed copolymers of vinyl alkyl ethers, such as vinyl-CrC ₄ -alkylethem, and maleic anhydride. C 1 -C ₄ -alkyl is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and preferably methyl or ethyl. Water-soluble polymers of group (b1) are obtainable by copolymerizing vinyl alkyl ethers with maleic anhydride and subsequent partial or quantitative hydrolysis of the anhydride groups to carboxyl groups and optionally partial or complete neutralization of the carboxyl groups. Particularly preferred water-soluble polymers of group (b1) are hydrolyzed copolymers of vinyl methyl ether and maleic anhydride as free polyacid and in the form of at least partially neutralized with sodium hydroxide, potassium hydroxide or ammonia salts.

Suitable water-soluble polymers are (b2) starch, starch, unmodified or, preferably, cationic or anionic modified. Examples of modified starches are cationically modified potato starch, anionically modified potato starch, minced potato starch and maltodextrin. Examples of cationically modified potato starches are the commercial products Amylofax 15 and Perlbond 970. A suitable anionically modified potato starch is Perfectamyl A 4692. Here the modification consists essentially in a carboxylation of potato starch, for example benzoate, pivalate and in particular acetate. C * Pur 1906 is an example of an enzymatically modified built potato starch and maltodextrin C 01915 for a hydrolytically degraded potato starch.

Other suitable water-soluble polymers are synthetic, preferably random, copolymers (b3) obtainable by copolymerization of

(β1) at least one monomer selected from (meth) acrylamide, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam, most preferably acrylamide and N-vinylpyrrolidone, and

(β2) one or more cationic monoethylenically unsaturated monomers selected from di-C ₁ -C ₄ -alkylamino-C ₂ -C ₄ -alkyl (meth) acrylate, for example 2- (N ₁ N-dimethylamino) ethyl (meth ) acrylate, 3-dimethylamino) propyl (meth) acrylate, 2- (N ₁ N-diethylamino) ethyl (meth) acrylate, 3-diethylamino) propyl (meth) acrylate, in each case partially or quantitatively neutralized with, for example, hydrohalic acids such as for example, hydrochloric acid, quaternized with sulfuric acid, para-toluenesulfonic acid, formic acid or acetic acid, or partially or quantitatively with Ci-C ₄ alkyl or benzyl, for example by reaction with C-ι-C ₄ -AIkylhalogenid such as C ₁ -C ₄ - alkyl bromide or iodide, by reaction with di-C ₁ -C ₄ alkyl sulfate or with benzyl halide such as benzyl bromide or benzyl chloride. Further suitable monomers (β2) are dimethyldiallylammonium chloride, diethyldiallylammonium chloride, dimethyldiallylammonium bromide, diethyldiallylammonium bromide.

It is possible to copolymerize one or more anionic monoethylenically unsaturated monomers (β3) selected from (meth) acrylic acid, vinylsulfonic acid, vinylphosphonic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, in each case as free acid or as alkali metal or ammonium salt, where the molar Proportion of in (b3) polymerized cationic monoethylenically unsaturated monomers (ß2) is higher than the proportion of copolymerized anionic monoethylenically unsaturated monomers (ß3).

Copolymers (b3) can have a K value in the range from 15 to 200, preferably 30 to 150 and particularly preferably in the range from 45 to 110, determined according to H. Fikentscher (Cellulose Chemistry, Volume 13, 58-64 and 71 74, 1932) in 3 wt .-% aqueous NaCl solution at 25 ° C, a pH of 7 and a copolymer concentration of 0.1 wt .-%.

In one embodiment of the present invention, synthetic preferably random copolymers (b3) are composed of

From 2 to 90, preferably from 20 to 80, and particularly preferably from 30 to 70, mol% of at least one monomer (β1), 2 to 90, preferably 20 to 80 and more preferably 30 to 70 mol% of at least one cationic monoethylenically unsaturated monomer (ß2).

In another embodiment of the present invention, synthetic preferably random copolymers (b3) are composed of

From 2 to 90, preferably from 10 to 80, and particularly preferably from 20 to 70, mol% of at least one monomer (β1),

From 2 to 90, preferably from 10 to 80, and particularly preferably from 20 to 70, mol% of at least one cationic monoethylenically unsaturated monomer (β 2),

0.1 to 8, preferably up to 10 and particularly preferably 20 mol% of at least one anionic monoethylenically unsaturated monomer (ß3).

Preferably, the solubility of comonomers (β1) in water at 25 ° C is at least 100 g / l, most preferably they are miscible with water in any ratio.

Suitable examples of copolymers (b3) are those which are prepared by copolymerization of acrylamide and 2- (N, N-dimethylamino) ethyl acrylate methochloride, acrylamide and 2- (N, N-dimethylamino) ethyl methacrylate-methochloride, methacrylamide and 2- (N, N-dimethylamino) ethylacryIat methochloride, methacrylamide, and 2- (N, N-dimethylamino) ethyl methacrylate methochloride, acrylamide, 2- (N ₁ N-dimethylamino) ethyl acrylate methochloride and acrylic acid, acrylamide, 2- (N ₁ N-dimethylamino) ethyl methacrylate methochloride and acrylic acid.

A particularly suitable water-soluble polymer is enzymatically degraded starch, especially maltodextrin.

Aqueous dispersions used according to the invention comprise at least one water-soluble polymer of groups (b1), (b2) or (b3), for example in amounts of from 2 to 15, preferably from 5 to 12,% by weight. Water-soluble polymer of the groups (b1), (b2) or (b3) is used in the preparation of the dispersion used according to the invention. The ratio of the water-soluble polymers of groups (a1), (a2), (a3) or (a4) to water-soluble polymers of groups (b1), (b2) or (b3) in the dispersions according to the invention is, for example, 1: 5 to 5: 1 and is preferably in the range of 1: 2 to 2: 1.

Without wishing to be bound by theory, initial results indicate that water-soluble polymers of groups (a1) to (a4) and (b1) to (b3) act as stabilizers for aqueous dispersions used in the invention. Aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON used according to the invention, for example of at least one ethylenically unsaturated anionic monomer or of at least one nitrogen-containing water-soluble ethylenically unsaturated monomer preferably contain a combination of

(a1) at least one graft polymer of vinyl acetate on polyethylene glycol having a molecular weight M _{n of} from 1,000 to 100,000 g / mol

and

(b1) at least one hydrolyzed copolymer of vinyl methyl ether and maleic anhydride as the polyacid or in at least partially neutralized form with sodium hydroxide, potassium hydroxide or ammonia.

In a further preferred embodiment of the invention, the following combination of water-soluble polymers is used:

(a2) at least one copolymer of alkylpolyalkylene glycol (meth) acrylate and (meth) acrylic acid

and

(b1) at least one hydrolyzed copolymer of vinyl methyl ether and maleic anhydride as the polyacid or in at least partially neutralized with sodium hydroxide, potassium hydroxide or ammonia form.

Further combinations of stabilizers for the preparation of the aqueous dispersions of anionic polymers are, for example, mixtures of

(a3) polypropylene glycols, polyethylene glycols and / or block copolymers of ethylene oxide and propylene oxide having molecular weights M _n in the range from 300 to 50,000 g / mol and / or

(a4) Polypropylene glycols, polyethylene glycols and / or block copolymers of ethylene oxide and propylene oxide having a molecular weight M _{n of} from 300 to 50 000 g / mol and substituted by C ₁ - to C ₄ -alkyl groups on one or both sides

(b3) synthetic copolymers obtainable by copolymerization of (β1) one or more nonionic monoethylenically unsaturated monomers,

wherein the molar fraction of cationized monoethylenically unsaturated monomers (β2) polymerized in (b3) is higher than the proportion of copolymerized anionic monoethylenically unsaturated monomer (β3).

In one embodiment of the present invention, aqueous dispersions of (co) polymers of at least one ethylenically unsaturated monomer MON _1, for example of at least one ethylenically unsaturated anionic monomer or of at least one nitrogen-containing water-soluble ethylenically unsaturated monomer, have an average particle diameter in the range of 0 , 1 to 200 μm, preferably 0.5 to 70 μm.

In one embodiment of the present invention, aqueous dispersions of (co) polymers of (co) polymers of at least one ethylenically unsaturated monomer MON, for example of at least one ethylenically unsaturated anionic monomer or of at least one nitrogen-containing water-soluble ethylenically unsaturated monomer at pH values below 6 have one Solid content of about 5 to 35 wt .-%, a relatively low viscosity. However, if one sets a solids content of 2 wt .-%, the viscosity of the relevant aqueous dispersion according to the invention increases sharply.

In one embodiment of the present invention, aqueous dispersions of at least one (co) polymer of at least one ethylenically unsaturated monomer MON, for example, of at least one ethylenically unsaturated ^'anionic monomer has a content of inorganic salts in the range of 0.001 to 15 wt .-% to, preferably 0.1 to 5 wt .-%, based on the solids content of the respective aqueous dispersion. In another embodiment of the present invention, aqueous dispersions of at least one (co) polymer of at least one ethylenically unsaturated monomer MON, for example of at least one ethylenically unsaturated anionic monomer, have no measurable content of inorganic salts.

Furthermore, the emulsions to be used according to the invention may contain customary additives depending on the intended use. For example, they may contain bactericides or fungicides. In addition, they may contain water repellents to increase the water resistance of the treated substrates. Suitable water repellents are customary aqueous paraffin dispersions or silicones. Furthermore, the compositions may contain wetting agents, thickeners, dispersions, plasticizers, retention aids, pigments and fillers. The mixing in of these fillers can also be done by induction heating, which facilitates curing.

The emulsions of organic solvents, water and the dispersions of the invention used for introducing the swellable materials can be stabilized by surface-active auxiliaries. Typically, emulsifiers or protective colloids are used for this purpose. There are anionic, nonionic, cationic and amphoteric emulsifiers into consideration. Anionic emulsifiers are, for example, alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates. Examples of nonionic emulsifiers which can be used are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides. Examples of cationic or amphoteric emulsifiers used are: quaternized aminal alkoxylates, alkyl betaines, alkylamido betaines and sulfobetaines.

Typical protective colloids are, for example, cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ethers, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-one. Methylsuccinimide, polyvinyl-1,3-oxazolidone-2, polyvinyl-2-methylimidazoline and maleic acid or maleic anhydride containing copolymers, such as in DE-A 25 01 123 are described.

The emulsifiers or protective colloids are usually used in concentrations of 0.05 to 20 wt .-%, based on the monomers.

Combinations of aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON on the one hand and granular superabsorbent polymers based on partially neutralized crosslinked polyacrylic acids on the other hand can also be present in the textile structures of the invention. The superabsorbent partially neutralized polyacrylic acids can be crosslinked with conventional crosslinkers which preferably have at least two ethylenically unsaturated double bonds, one ethylenically unsaturated double bond and one further functional group or else two functional groups. The functional groups of these crosslinkers should be able to react with the acid groups of the acrylic acid. Suitable functional groups are, for example, hydroxyl, amino, epoxy and aziridino groups. The granular superabsorbent polymers based on partially neutralized crosslinked polyacrylic acids usually have particle sizes of 200 to 800 mm.

It may also be advisable to use fibers and / or tapes as well as swellable materials on the side of the textile structures according to the invention facing away from the water. terialien a mixture of granular, superabsorbent polymers based on partially neutralized crosslinked polyacrylic acids on the one hand and a powder of polymers on the other hand apply. For this purpose, in particular thermoplastic powders of polyolefins such as polyethylene or polypropylene are suitable. In this case, a mixing ratio between the granular superabsorbent polymer and the polymer powder of about 0.5: 1 to 5: 1, in particular from 1: 1 to 3: 1 should be maintained. The resulting mixture of granular superabsorbent polymers and the polymer powder can then be covered with a textile structure having an effective opening width of less than 0.12 mm and having a thickness of about 50 to 80 g / m ² , followed by heat and pressure with the inventive textile structures are connected. In this way, in the installed state, the swollen swellable material of the textile structure according to the invention can be supported against the likewise swollen granular, superabsorbent polymer. As a result, flushing of the swellable material from the textile structure is avoided.

The textile structures according to the invention can i.a. be prepared by coating the fibers and / or tapes with the swellable materials, impregnated, patted, foamed or sprayed.

If the fabric is a non-woven fabric, a method known as Maliwatt can also be used. In this method, a nonwoven, which consists of fibers deposited transversely to the production direction, is solidified by sewing the fiber layers with foreign threads in the longitudinal direction at a distance of about 1 mm. This fiber layer is then impregnated with the swellable material.

Instead of the nonwoven fabric, the textile structure may also be a textile fabric.

The textile structures according to the invention may be constituents of likewise seals according to the invention which, in addition to the textile structure, also have at least one sealing sheet of plastics. In this case, preference is given to such an arrangement in which the seal has a textile structure which is arranged between two sealing webs made of plastics. The textile fabric can be linked by conventional fastening methods such as by hooking, gluing, tying or calendering / welding under pressure and temperature with the geomembranes.

The textile structure of the invention can be used, inter alia, as a sealing material for road, tunnel and hydraulic engineering as well as for excavations, flood protection and roof waterproofing. Especially in construction pits, road construction and flood protection, the textile structure according to the invention can either alone or in combination with mixtures of granular, superabsorbent Polymers and powders of other polymers are used.

Conceivable here are in particular the installation of the textile structure under a waterproofing membrane made of plastic against the structure to be protected to prevent inaccuracy in damage to the geomembrane, for example, for flat roofs in building construction, tunnels in open design as well as for waterproofing basements or underground garages.

Other uses of the textile structure relate to its installation between two geomembranes as so-called self-healing seals in tunneling (according to DE-A 196 25 245) and as part of a membrane tub in the traffic route construction (according to DE-A 199 30 701) or in Hoch- and industrial construction.

Further applications of the textile structure according to the invention relate to its installation under the concrete protection layer for a plastic waterproofing membrane in basins and channels to prevent seepage under the concrete slabs to damage in the plastic seal and reduce the stress in the concrete slabs by reduced friction. Examples of this would be u.a. the installation of textile structures in rainwater retention basins, landscape ponds, sludge basins and in irrigation and power station sewers on coarse-grained soils.

Also conceivable is the incorporation of the textile structure either alone or in conjunction with other waterproofing membranes in earthworks instead of Tondichtungsbahnen, especially in irrigation or drainage channels, for sealing landscape ponds, storage ponds or protected areas, to create artificial aquifers and the first seal of membrane tubs and pits ,

The textile structures according to the invention can also be used in combination with protective fleeces which serve to protect seals. Such protective fleeces do not slow down the influx of water to the point of damage in case of damage in the seal in granular soils (vertical permeability). For more cohesive soils they encourage the collection and distribution of the water flowing through the damaged area (horizontal permeability). The textile structure according to the invention increases safety through its sealing function.

Another possibility of using the textile structure according to the invention is to use this as a covering and sealing in wire baskets, which can be quickly set up as a temporary flood protection or hydraulic engineering and then mechanically filled with grit, gravel or recycled material.

Other possibilities of using the textile structures according to the invention are as cable sheathing; in packaging, eg. B. as insertion pads for liquid for frozen goods, for "fresh products" as moisturizers, in garbage bags, as "liners" for bio-containers or trashcans, as filter materials, for example as filter mats for air conditioners or for drainage of oil in gasoline tanks or for hydraulic oils or fuel filters; for geotextiles or in the agro-area, for example as a cover for landfills, for abandoned mines, as greening for flat roofs, embankments or noise barriers; for embankment and dyke construction, in the hygiene or medical sector, in the textile or fire protection sector.

The textile structures according to the invention have u.a. Compared to the known from the prior art textile webs or fabrics. a better processability (mechanical laying possible) and swellability and a higher water impermeability, especially in the horizontal direction. If the textile structure is installed as a protective layer, it prevents the spread of the water and gives by its buffering effect greater security against common damage. This results from the fact that the existing fibers or ribbons are completely covered with water bound to them, so that no water-bearing layers are formed. Furthermore, they can be laminated very well with geomembranes.

example

I. Preparation of an Aqueous Emulsion to be Used According to the Invention Examples

The water-soluble polymers used in the examples according to the invention had the following composition:

Stabilizer 1: graft polymer of vinyl acetate on polyethylene glycol of molecular weight M _N 6000, polymer concentration 20%

Stabilizer 2: Hydrolysed copolymer of vinyl methyl ether and maleic acid in the form of the free carboxyl groups, polymer concentration 35%

Stabilizer 3: Copolymer of methyl polyethylene glycol methacrylate and methacrylic acid of molecular weight M _w 1500, polymer concentration

40%

Stabilizer 4: polypropylene glycol having a molecular weight MN of 600

Stabilizer 5: polypropylene glycol with a molecular weight MN of 900 Stabilizer 6: Polypropylene glycol endblocked on one side with a methyl group and having a molecular weight M _N of 1000

Stabilizer 7: Block copolymer of polyalkylene glycols having a molecular weight M _N of 1000

Stabilizer 8: Maltodextrin (C-PUR01910, 100%)

Stabilizer 9: Polypropylene glycol endblocked on one side with a methyl group and having a molecular weight M _N of 2000

In the examples, the following polymerization initiators were used:

Azostarter VA-044: 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride azo starter V-70: 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile)

Azostarter V-65: 2,2'-azobis (2,4-dimethylva! Eronitrile)

example 1

In a 250 ml four-necked flask equipped with a Teflon stirrer and a device for working under nitrogen, 90.0 g of stabilizer 1, 51, 4 g of stabilizer 2 and 28.6 g of deionized water were introduced while passing nitrogen through and stirred at a speed of 300 rpm. To this solution was added dropwise g of acrylic acid over 5 to 10 minutes, 30, the mixture was heated to 5O ⁰ C, added 0.03 g of 2,2'-azobis (N, N'-dimethylenisobutyramidine) dihydrochloride (VA-044 azo initiator) to and the mixture was polymerized for 5 hours at 50 ⁰ C. the reaction mixture was then treated with 0.05 g of azo initiator VA-044 and merized 1 hour at 60 ° C nachpoly-. An aqueous dispersion having a solids content of 33% was obtained. It had a pH of 4 and a viscosity of 5950 mPas. The polymer had a K value of 120.7. By adding water to the dispersion, a 2% aqueous solution was prepared which had a viscosity of 2640 mPas at a pH of 7.

The particle size distribution of the dispersed particles of the polymer dispersion was 3 to 8 μm. Example 2

In the device indicated in Example 1 were 90.0 g of stabilizer 1, 51, 4 g stabilizer 2 and

28.6 g of fully demineralized water submitted and stirred while passing nitrogen at a speed of 300 rpm. To this solution was added dropwise within 5 to 10 minutes, a mixture of 30 g of acrylic acid and 0.09 g of triallylamine as a crosslinking agent and the mixture was heated within 5 to 10 minutes at a temperature of 40 ⁰ C. Then 0.03 g 2,2'-

Azobis (4-methoxy-2,4-dimethylvaleronitrile) (azo starter V-70) and polymerized the mixture for 5 hours at a temperature of 40 ⁰ C. Then, for post-polymerization, 0.05 g of azo starter V-70 and heated the Dispersion for one hour to a temperature of 50 ° C. An aqueous dispersion having a viscosity of 2700 mPas was obtained. It had a pH of 4. By adding water to the aqueous dispersion, a 2% aqueous solution was prepared. It had a viscosity of 39000 mPas at pH 7.

The particle size distribution of the dispersed particles of the polymer dispersion was 5 to 60 μm.

Example 3

Example 2 was repeated except that in the polymerization

12 g stabilizer 4

51.4 g stabilizer 2 and

106.6 g of fully desalinated water submitted and waived the use of triallylamine. An aqueous emulsion was obtained which had a viscosity of 2240 mPas at a pH of 4.

Example 4

In the apparatus given in Example 1, 1, 5 g of stabilizer 5 were placed

16.5 g stabilizer 4 18.0 g stabilizer 8 and

104.0 g of completely desalted water, the mixture was stirred continuously at 300 rpm and continuously added 30 g of acrylic acid within 5 to 10 minutes. Then adjusted the pH of the reaction mixture by adding 30 g of 32% hydrochloric acid of 4.5 to 3 and the emulsion was heated to a temperature of 50 ⁰ C. After addition of 0.03 g Azostar- ter VA-044, the emulsion was polymerized for 5 hours at 5O ⁰ C, then added 0.05 g of azo starter VA-044 and polymerized for 1 hour at 50 ⁰ C after. An aqueous dispersion having a viscosity of 208 mPas was obtained.

Example 5

Example 1 was repeated with the exceptions that in the polymerization a mixture of

45 g stabilizer 3 51, 4 g stabilizer 2 and

73.6 g of fully desalinated water submitted. An aqueous emulsion having a viscosity of 3650 mPas was obtained.

The particle size distribution of the dispersed particles of the polymer dispersion was

3 to 10μm.

Example 6

28.6 g of fully demineralized water submitted and stirred while passing nitrogen at a speed of 300 rpm. To this solution was added dropwise within 5 to 10 minutes, a mixture of 30 g of acrylic acid and 0.22 g of pentaerythritol triallyl ether (70%) as a crosslinker and the mixture was heated within 5 to 10 minutes at a temperature of 40 ⁰ C. Man gave then 0.03 g of azo initiator V-70 and the mixture is polymerized for 5 hours at a temperature of 40 ⁰ C. then was added 0.05 g of azo initiator for the postpolymerization VA 044 and to the dispersion was heated for one hour at a temperature of 5O ⁰ C. An aqueous dispersion having a viscosity of 2900 mPas was obtained. By adding water and adjusting the pH to 7, a 2% aqueous solution having a viscosity of 10,000 mPas was prepared. The particle size distribution of the dispersed particles of the polymer dispersion was 5 to 70 μm.

Example 7

In a 250 ml four-necked flask equipped with a Teflon stirrer and a device for working under nitrogen, while passing nitrogen were 90.0 g of stabilizer i, 18.0 g of stabilizer 8 and

62.0 g of completely demineralized water submitted and stirred at a speed of 200 rpm. 30 g of acrylic acid were added dropwise to this solution over 5 to 10 minutes, the mixture was warmed to 50 ^° C., 0.03 g of azo starter VA-044 was added, and the mixture was polymerized at 50 ^° C. for 5 hours , 05 g of azo starter VA-044 and postpolymerized at 6O ⁰ C for 1 hour. An aqueous dispersion having a solids content of 33% was obtained. It had a pH of 2 and a viscosity of 10500 mPas. A 2% solution prepared therefrom by the addition of water had a viscosity of 2000 mPas at a pH of 7. The particle size distribution of the dispersed particles of the polymer dispersion was 5 to 40 μm.

Example 8

28.6 g of fully desalinated water and stirred while passing nitrogen at a speed of 300 rpm. To this solution was added dropwise within 5 to 10 minutes, a mixture of 30 g of acrylic acid and 0.09 g of triallylamine as a crosslinking agent and the emulsion was heated within 5 to 10 minutes at a temperature of 50 ⁰ C. Then 0.03 g Azostarter V-65 and polymerized the mixture for 5 hours at a temperature of 50 ° C. Then 0.05 g of azo starter VA-044 was added to the postpolymerization and the dispersion was heated for one hour to a temperature of 60 ° C. An aqueous dispersion having a viscosity of 3700 mPas was obtained. It had a pH of 4. By adding water to the aqueous dispersion, a 2% aqueous solution was prepared. It had a viscosity of 29000 mPas at pH 7. The particle size distribution of the dispersed particles of the polymer dispersion was 5 to 30 μm.

Example 9

In the apparatus given in Example 1, 90.0 g of stabilizer 1,

45.7 g stabilizer 2 and

34.3 g of fully deionized water and stirred while passing nitrogen at a speed of 300 rpm. To this solution was added dropwise within 5 to 10 minutes, a mixture of 30 g of acrylic acid and 0.09 g of triallylamine as a crosslinker and heated the mixture within 5 to 10 minutes at a temperature of 40 ° C. Was added then 0.03 g of azo initiator V-70 and the mixture is polymerized for 5 hours at a temperature of 40 ⁰ C. For the postpolymerization was put 0.05 g of azo initiator VA-044 was added and the dispersion was heated for one hour at a temperature of 50 an aqueous dispersion ⁰ C. was obtained having a viscosity of 2300 mPas. By adding water and adjusting the pH to 7, a 2% aqueous solution was prepared which had a viscosity of 32,000 mPas.

Example 10

In the apparatus given in Example 1 was set

18.0 g stabilizer 9

18.0 g stabilizer 8 and

90.0 g of completely desalted water before, the mixture was stirred continuously while passing nitrogen at 300 rpm and continued within 5 to 10 minutes 30 g of acrylic acid continuously. The pH of the reaction mixture was then adjusted from 4.5 to 3 by addition of 30 g of 32% strength hydrochloric acid and the emulsion was heated to a temperature of 50 ^° C. After addition of 0.03 g of azo starter VA-044, polymerization was carried out the emulsion for 5 hours at 50 ⁰ C, then gave 0.05 g of azo starter VA-044 and polymerized for 1 hour at 50 ⁰ C after. An aqueous dispersion having a viscosity of 320 mPas was obtained.

Example 11

In the apparatus given in Example 1, 63.0 g of stabilizer 7 9.0 g of stabilizer 8 400 g of water and 45 g of acrylic acid were introduced and stirred while passing nitrogen at a speed of 100 rpm. To this solution, 0.45 g of sodium persulfate and 14.4 g of water were added and grafted at 25 ° C for 15 minutes. Then, 135 g of acrylic acid and 27 g of stabilizer 8 in 2 hours at 25 ° C closed. At the same time, 0.18 g of ascorbic acid were added in 7 hours. Subsequently, polymerization was continued for one hour. An aqueous dispersion having a viscosity of 800 mPas and a pH of 1.5 was obtained. By adding water and sodium hydroxide, a 2% dispersion having a pH of 7 was prepared. The viscosity of the dispersion was 5000 mPas.

Example 12

Polymerization of crosslinked acrylic acid in the presence of maleic acid / vinylmethylether copolymer and vinyl acetate / PEG 6000 copolymer

449 g of co-polymer of maleic acid and vinyl methyl ether (20 wt .-% in water), 257 g copolymer of vinyl acetate and polyethylene glycol 6000 (35 wt .-% in water) and 102.5 g of water are combined and stirred with 10 minutes

Flooded with nitrogen. Then within 10 minutes and stirring 60g acrylic acid (100%) was added and the reaction mixture heated to 60 ⁰ C under a permanent nitrogen atmosphere.

After reaching the desired internal temperature, a solution of 90 g of acrylic acid (100%) and 1, 5g Laromer® 9015x (ETMPTA) (Fa.

BASF) and simultaneously starting a solution of radical initiator (VA-044, 0.15 g) and 40 g of water added in 4.0 hours.

After the end of half an hour at 60 ⁰ C is stirred and then by adding more free radical initiator (VA-044; 0.015 g) post-polymerized for one hour at 6O ⁰ C.

After cooling to room temperature, a slightly yellow-colored, viscous, milky cloudy emulsion with 15% polymer content and a viscosity of 5350 mPas.

Example 13

449 g co-polymer of maleic acid and vinyl methyl ether (20 wt .-% in water), 257 g copolymer of vinyl acetate and polyethylene glycol 6000 (35 wt .-% in water) and 102.5 g of water are combined and flooded with stirring for 10 minutes with nitrogen.

Then within 10 minutes and with stirring, 60 g of acrylic acid (100%) and is radical initiator (VA-044; 0.015 g) was added and the reaction mixture heated under nitrogen atmosphere to perma- Nenter 6O ⁰ C.

After the desired internal temperature has been reached, a solution of 90 g of acrylic acid (100%) and 1.5 g of Laromer 9015x (ETMPTA) is started within 3.5 hours and, at the same time, a solution of free-radical initiator (VA-044, 0.135 g) and 40 g is started Water added in 4.0 hours.

After the end of half an hour at 60 ⁰ C is stirred and then by adding more free radical initiator (VA-044; 0.015 g) post-polymerized for one hour at 60 ⁰ C.

After cooling to room temperature, a slightly yellow-colored, viscous, milky cloudy emulsion with 15% polymer content and a viscosity of 5550 mPas.

Example 14

449g co-polymer of maleic acid and vinyl methyl ether (20 wt .-% in water), 257g copolymer of vinyl acetate and polyethylene glycol 6000 (35 wt .-% in water) and 102.5g of water are combined and flooded with nitrogen for 10 minutes.

Then within 10 minutes and with stirring, 60 g of acrylic acid (100%) and is radical initiator (VA-044; 0.015 g) was added and the reaction mixture heated under constant nitrogen atmosphere at 60 ⁰ C.

After reaching the desired internal temperature, a solution of 90 g of acrylic acid (100%) and 1, 5 g of triallylamine and simultaneously starting a solution of free-radical initiator (VA-044, 0.135 g) and 40 g of water in 4, within 3.5 hours, 0 hours added.

After cooling to room temperature, a slightly yellow-colored, highly viscous, milky cloudy emulsion with 15% polymer content and a viscosity of 10250 mPas.

Example 15

After reaching the desired internal temperature, a solution of 75 g of acrylic acid (100%) within 3.5 hours; 15 g of methyl methacrylate (100%) and 1, 5 g of triallylamine and simultaneously starting a solution of free-radical initiator (VA-044, 0.135 g) and 40 g of water added in 4.0 hours.

After cooling to room temperature, a slightly yellow-colored, viscous, milky cloudy emulsion with 15% polymer content and a viscosity of 5800 mPas. Example 16

Then within 10 minutes and with stirring, 60 g of acrylic acid (100%) and is radical initiator (VA-044; 0.015 g) was added and the reaction mixture heated under perma- Nenter nitrogen atmosphere at 60 ⁰ C.

After reaching the desired internal temperature, a solution of 82.5 g of acrylic acid (100%) within 3.5 hours; 7.5 g of methyl acrylate (100%) and 1.5 g of triallylamine and at the same time starting a solution of free-radical initiator (VA-044, 0.135 g) and 40 g of water added in 4.0 hours.

After cooling to room temperature, a slightly yellow-colored, highly viscous, milky cloudy emulsion with 15% polymer content and a viscosity of 21900 mPas

II. Use of the emulsion obtained according to Section I as a constituent of a swellable fiber web

With the emulsion obtained from section I, a swellable nonwoven fabric was produced by a conventional method:

Support material: a) PET needled nonwoven (Hilden felt), approx. 280 - 300 g / m ² b) PES - nonwoven, thermally bonded, approx. 100 - 110 g / m ²

The swellable nonwoven obtained in this way can i.a. be used as a seal for a tunnel. The fleece is shrink-wrapped in PVC or PET film and fixed with plastic disks on a fleece of the same type already laid on the mountain side but not impregnated with swelling agent (solidified by means of mechanical needling). The inner concrete is then pumped behind this sandwich (film / swellable nonwoven).

Claims

claims

1. Textile two- or three-dimensional structures of fibers and / or tapes and swellable materials, wherein the fibers present in the structure and / or bands and the swellable materials are each present in an amount such that the fibers and / or tapes of the swellable materials are enveloped and the cavities of the structures in the swollen state are partially or completely filled with material-bound water and being used as swellable materials aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON, which on the fibers and / or tapes be applied.

2. Textile two- or three-dimensional structures according to claim 1, character- ized in that at least one aqueous dispersion is prepared in the presence of at least one water-soluble polymer, wherein at least one water-soluble polymer is selected from

(a1) graft polymers of vinyl acetate and / or vinyl propionate on polyalkylene glycol or on one or both sides with alkyl-, carboxyl- or amino-substituted polyalkylene glycol, (a2) copolymers of alkylpolyalkylene glycol (meth) acrylates and

(Meth) acrylic acid, (a3) polyalkylene glycols, (a4) substituted on one or both sides with alkyl, carboxyl or amino groups

polyalkylene

and at least one water-soluble polymer is selected from

(b1) hydrolyzed copolymers of vinyl alkyl ethers and maleic anhydride as free polyacid or at least partially neutralized with alkali metal hydroxides or ammonium bases, (b2) starch, modified or unmodified,

(β2) one or more cationic monoethylenically unsaturated monomers,

(β3) optionally one or more anionic monoethylenically unsaturated monomers, where the molar fraction of canonical monoethylenically unsaturated monomers (β2) copolymerized in (b3) is higher than the proportion of copolymerized anionic monoethylenically unsaturated monomers (β3).

3. Textile structure according to claim 1 or 2, wherein the structures are in the form of fleeces or fabrics.

4. Textile structure according to one of claims 1 to 3, wherein the structures have as fibers filaments or staple fibers.

5. Textile structure according to one of claims 1 to 4, wherein the structures contain as fibers mineral, natural or synthetic fibers.

6. Textile structure according to claims 1 to 5, wherein the structures as swellable materials combinations of aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON on the one hand and granular superabsorbent polymers based on partially neutralized crosslinked polyacrylic acids on the other.

7. A process for the production of textile structures according to claims 1 to 6, characterized in that the two- or three-dimensional textile structures by coating, impregnation, patting, foaming or spraying of the fibers and / or ribbons are obtained with the swellable materials.

8. Use of the textile structure according to claims 1 to 6 as a sealing material.

9. Use of the textile structure according to claim 8, characterized in that the textile structures are used in combination with mixtures of granular, superabsorbent polymers and powders of other polymers.

10. Use of the textile structure according to one of claims 1 to 6 as Ab- sorption material.

11. Use of the textile structures according to claim 10, characterized in that the textile structures are used in combination with mixtures of granular, superabsorbent polymers and powders of other polymers.

12. seal, containing in addition to at least one geomembrane made of plastics, a textile structure according to one of claims 1 to 6.

13. A seal according to claim 12, wherein the textile structure according to any one of claims 1 to 6 is arranged between two sealing webs made of plastics.

14. Use of aqueous emulsions of (co) polymers of at least one ethylenically unsaturated monomer MON, for the production of textile two- or three-dimensional structures, wherein at least one water-soluble

Polymer is chosen from

(a2) Copolymers of alkylpolyalkylene glycol (meth) acrylates and

(Meth) acrylic acid, (a3) polyalkylene glycols,

and at least one water-soluble polymer is selected from

(β2) one or more cationic monoethylenically unsaturated monomers, (β3) optionally one or more anionic monoethylenically unsaturated

monomers