EP1771504A1

EP1771504A1 - Modified open-cell foams, and method for the production thereof

Info

Publication number: EP1771504A1
Application number: EP05761030A
Authority: EP
Inventors: Andreas FECHTENKÖTTER; Michael Ehle; Stefan Frenzel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-07-16
Filing date: 2005-07-14
Publication date: 2007-04-11
Also published as: US20080300329A1; WO2006008054A1; JP2008506797A; DE102004034604A1; CN1984946A

Abstract

Disclosed are modified open-pore foams having a density ranging from 5 to 1000 kg/m3 and an average pore diameter ranging from 1 µm to 1 mm. Said modified open-pore foams contain 1 to 2,500 percent by weight, relative to the weight of the non-modified open-pore foam, of at least one polymer which is solid at room temperature, contains carboxyl groups and/or carboxylic acid ester groups, and has a molecular weight Mn ranging between 1000 and 1,000,000 g/mole.

Description

Modified open-cell foams and process for their preparation

description

The present invention relates to modified open-cell foams having a density in the range of 5 to 1000 kg / m ³ and an average pore diameter in the range of 1 .mu.m to 1 mm, containing in the range of 1 to 2.500 wt .-%, based on the Weight of the unmodified open-cell foam, at least one at room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing polymer having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol.

The present invention further relates to a process for the production of modified open-cell foams according to the invention and to the use of modified open-cell foams according to the invention for the production of cleaning materials, filters, humidifiers, water distributors, packaging elements, soundproofing elements or building insulation.

Foams, especially so-called open-cell foams, find uses in numerous fields. In particular, open-cell foams made of synthetic materials have proven to be versatile. Examples include seat cushions, Fil¬ termaterialien, air conditioning and automotive parts, continue cleaning materials.

For cleaning materials, which are made of foams, it is observed that after a relatively short period of use, for example, after about 10 minutes, they are so far destroyed that no cleaning effect can be achieved. Manufacturers of cleaning materials such as plaster sponges therefore recommend to dispose of cleaning materials after appropriate and generally quite short period of use, for example, 10 minutes.

In EP 0922563 that melamine resin foam is shown with thin reiß¬ solid outer layers such as nonwoven fabrics, for example for 2 minutes at pressures of 2 to 5 to 200 bar and temperatures in the range 80 can encrypt presses up to 250 ⁰ C. , This gives dimensionally stable components.

In US Pat. No. 6,608,118 it is proposed to compress foams of melamine under the influence of heat in order to obtain better mechanical properties, for example to compress for 4 minutes at 270 ^° C.

In EP 0 633 283 and DE 100 11 388 it is recommended to reinforce melamine resin foams by impregnating them, for example, with a silicone emulsion. However, silicone-impregnated foams are not useful as cleaning materials, leaving streaks and oily surfaces in use. In the 100 11 388 is also recommended to spray melamine resin foams with monomeric fluoroalkyl esters to make them oil repellent.

However, the technical properties of the foams or foams known from the prior art can be improved with respect to cleaning action, stability, and water or oil absorption.

It was therefore an object to provide foams which avoid the disadvantages of the known from the prior art materials. It was also the task to provide a process for the production of new foams. Another object was to provide uses for foams and to provide processes for using foams.

Accordingly, the initially defined modified foams were found, which are also referred to below as foams according to the invention.

Modified foams of the invention are open-celled foams, i. to those foams in which at least 50% of all lamellae are open, preferably 60 to 100% and particularly preferably 65 to 99.9%, determined according to DIN ISO 4590.

The modified foams according to the invention are preferably hard foams, which in the sense of the present invention are foams which have a compression hardness of 1 kPa or more at a compression of 40%, determined in accordance with DIN 53577.

Modified foams according to the invention have a density in the range of 5 to 1000 kg / m ³ , preferably 6 to 500 kg / m ³ and particularly preferably in the range of 7 to 300 kg / m ³ .

Modified foams according to the invention have a mean pore diameter (number average) in the range from 1 .mu.m to 1 mm, preferably 50 to 500 .mu.m, determined by evaluating microscopic images of sections.

In one embodiment of the present invention, modified foams according to the invention have a BET surface area in the range from 0.1 to 50 m ² / g, preferably from 0.5 to 20 m ² / g, determined to DIN 66131.

In one embodiment of the present invention, modified foams according to the invention have a sound absorption coefficient of more than 50%, preferably at least 90%, in special cases up to 100%, measured according to DIN 52215 in one Frequency of 2000 Hz and a thickness of the respective foam of 50 mm.

In a specific embodiment of the present invention, modified foams according to the invention have a sound absorption factor of more than 0.5, in special cases up to 1, measured according to DIN 52212 at a frequency of 2000 Hz and a layer thickness of the foam in question of 40 mm ,

Modified foams according to the invention preferably contain in the range from 1 to 2.500 wt.%, Preferably 20 to 500 wt.%, Based on the weight of the corresponding unmodified foam (a), at least one carboxyl group-containing and / or solid at room temperature Carboxylic ester group-containing polymer (b) having a molecular weight M _n in the range from 1,000 to 1,000,000, preferably 1,500 to 500,000 g / mol, more preferably 2,000 to 200,000 g / mol and very particularly preferably up to 50,000 g / mol ,

Under at room temperature solid carboxyl groups and / or Carbonsäu¬ ester group-containing polymers (b) are in one embodiment of vorlie¬ ing invention such polymers to understand that have a melting point of about 25 ° C, preferably above 5O ⁰ determined through DSC.

Solid carboxyl-containing and / or carboxylic acid ester group-containing polymers (b) at room temperature may be homopolymers or copolymers of ethylenically unsaturated mono- or dicarboxylic acids.

In a preferred embodiment of the present invention, at least one carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) which is solid at room temperature is a copolymer which is obtainable by copolymerization of

(A) ethylene,

(B) at least one ethylenically unsaturated carboxylic acid,

(C) optionally further comonomers.

In one embodiment, these are copolymers selected from styrene-acrylonitrile-CrC ₁₀ -alkyl (meth) acrylate terpolymers,

Other comonomers (C) can be selected, for example, from the group of C 1 -C ₁₀ -alkyl esters of ethylenically unsaturated mono- and dicarboxylic acids, vinyl, allyl and methallyl esters of C 1 -C ₁₀ -alkylcarboxylic acids or of formic acid, vinylaromatic compounds such as styrene, isobutene and α-olefins such as CH ₂ = CH-HC ₁₆ H ₃₃₁ CH ₂ = CH-HC ₁₈ H ₃₇ , CH ₂ = CH-nC ₂₀ H ₄₁ and CH ₂ = CH-Ii-C ₂₂ H ₄₅ and mixtures of the above comonomers.

In one embodiment of the present invention, open-cell modified foams according to the invention are those based on synthetic organic foam, for example based on organic unmodified foams, for example foams based on polyurethane foams or aminoplast foams, for example aus Urea-formaldehyde resins, furthermore foams based on phenol-formaldehyde resins and in particular foams based on polyurethanes or aminoplast-formaldehyde resins, in particular melamine-formaldehyde resins, foams based on polyurethanes being used in the context of Present invention also be referred to as polyurethane foams and foams based on melamine-formaldehyde resins as melamine foams.

This is to be understood as meaning that foams according to the invention are produced from open-cell foams which comprise synthetic organic materials, preferably polyurethane foams or aminoplast foams and in particular melamine foams.

In another embodiment of the present invention, open-cell modified foams according to the invention are those based on inorganic materials such as, for example, metals or glass, in particular in the form of glass wool or metal foam.

A further subject of the present invention is a process for the production of modified foams according to the invention, also referred to below as the production process according to the invention. The preparation process according to the invention is characterized in that

(A) open-cell foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 micron to 1 mm

(b) contacted with at least one fixed at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymer having a Molekularge¬ weight M _n in the range of 1,000 to 1,000,000 g / mol in molten, dissolved o- or dispersed form.

The unmodified open-cell foams (a) used for carrying out the process according to the invention are generally also used in the context of the present invention as unmodified foams (a) or open-cell foams (a). designated. The unmodified open-cell foams (a) used for carrying out the process according to the invention are described in more detail below.

To practice the manufacturing method according to the invention is based on open-cell foam (a), in particular of foams in which at least 50% of all lamellae are open, preferably 60 to 100% and particularly preferably 65 to 99.9%, determined according to DIN ISO 4590th

Foams (a) used as starting material are preferably hard foams, which in the context of the present invention are foams which have a compression hardness of 1 kPa or more at a stowage of 40%, determined in accordance with DIN 53577.

Foams used as starting material (a) have a density in the range of 5 to 500 kg / m ³ , preferably 6 to 300 kg / m ³ and particularly preferably in the range of 7 to 300 kg / m ³ .

Open-celled foams (a) used as starting material have an average pore diameter (number average) in the range from 1 μm to 1 mm, preferably from 50 to 500 μm, determined by evaluating microscopic images of sections.

In one embodiment of the present invention, open-cell foams (a) used as starting material may have a maximum of 20, preferably a maximum of 15 and more preferably a maximum of 10 pores per m ² , which have a diameter in the range of up to 20 mm. The remaining pores usually have a smaller diameter.

In one embodiment of the present invention, open-cell foams (a) used as starting material have a BET surface area in the range from 0.1 to 50 m ² / g, preferably 0.5 to 20 m ² / g, determined according to DIN 66131.

In one embodiment of the present invention, foams (a) used as starting material have a sound absorption coefficient of more than 50%, measured according to DIN 52215 at a frequency of 2000 Hz and a layer thickness of the relevant foam (a) of 50 mm.

In a specific embodiment of the present invention, open-cell foams (a) used as starting material have a sound absorption factor of more than 0.5, measured according to DIN 52212 at a frequency of 2000 Hz and a layer thickness of the relevant foam (a) of 40 mm. Open-celled foams (a) used as starting material may have any desired geometric shapes, for example plates, spheres, cylinders, powders, cubes, flakes, cuboids, saddles, rods or square columns. The size dimensions of foams (a) used as starting material are not critical. In one embodiment of the present invention, one starts from open-cell foams (a) of synthetic organic material, preferably of polyurethane foams or of melamine foams.

Polyurethane foams which are particularly suitable as starting material for carrying out the process according to the invention are known as such. Their preparation succeeds, for example, by implementing

i) one or more polyisocyanates, i. Compounds with two or more isocyanate groups, ii) with one or more compounds having at least two groups which are reactive toward isocyanate, in the presence of iii) one or more blowing agents, iv) one or more initiators v) and one or more initiators several catalysts and vi) so-called cell openers.

Starter iv) and propellant iii) may be identical.

Examples of suitable polyisocyanates i) are known aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyvalent compounds having two or more isocyanate groups.

Specific examples are:

C ₄ -C ₁₂ -alkylene diisocyanates, preferably hexamethylene-1,6-diisocyanate; Cycloaliphatic diisocyanates, such as cyclohexane-1, 3- and cyclohexane-1, 4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI )

preferably aromatic di- and polyisocyanates, e.g. 2,4- and 2,6-toluene diisocyanate and corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and corresponding isomer mixtures, mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates, polyphenyl polymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (crude MDI) and mixtures of crude MDI with toluene diisocyanates. Polyisocyanates can be used individually or in the form of mixtures.

Examples of ii) compounds having at least two groups which are reactive toward isocyanate are di- and polyols, in particular polyether polyols (polyalkylene polyols). glycols) which are prepared by methods known per se, for example by alkali metal hydroxide-catalyzed polymerization of one or more alkylene lenoxiden such as ethylene oxide, propylene oxide or butylene oxide are available. Very particularly preferred compounds ii) are ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, pentaethylene glycol, hexadecyl ethylene glycol ,

Suitable blowing agents iii) are: water, inert gases, in particular carbon dioxide, and so-called physical blowing agents. Physical blowing agents are compounds which are inert to the starting components and which are usually liquid at room temperature and vaporize under the conditions of the urethane reaction. Preferably, the boiling point of these compounds is preferably below 110 ° C, especially below 80 ⁰ C. Physical blowing agents also include inert gases which are introduced into the starting components i) and ii) or dissolved therein, for example carbon dioxide, nitrogen or noble gases.

Suitable compounds which are liquid at room temperature are for the most part selected from the group comprising alkanes and / or cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes having 1 to 8 carbon atoms, and tetraalkylsilanes having 1 to 3 carbon atoms the alkyl chain, in particular tetramethylsilane.

Examples which may be mentioned are: propane, n-butane, iso- and cyclobutane, n-, iso- and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl tert-butyl ether, methyl acetate, acetone and fluorinated alkanes, which are described in can be degraded and are therefore harmless to the ozone layer, such as trifluoromethane, difluoromethane, 1, 1, 1, 3,3-pentafluorobutane, 1, 1, 1, 3,3-pentafluoropropane, 1, 1, 1, 2- Tetrafluoroethane, 1,1,1-trifluoro-2,2,2-trichloroethane, 1,1,2-trifluoro-1, 2,2-trichloroethane, difluoroethane and heptafluoropropane. The said physical blowing agents can be used alone or in any combination with each other.

The use of perfluoroalkanes for producing fine cells is known from EP-A 0 351 614.

Suitable starters iv) are, for example: water, organic dicarboxylic acids, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical, such as, for example, N- mono- and N, N-dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1, 2-, 1, 3-, 1, 4-, 1 , 5- and 1, 6-hexamethylenediamine, aniline, phenylenediamines, 2,3-, 2,4-, 3,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'- diaminodiphenylmethane.

As catalysts v) the catalysts known in polyurethane chemistry are suitable, for example tertiary amines, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) -octane and the like, and in particular organic metal compounds such as titanic acid esters, iron compounds such as e.g. Iron (III) acetylacetonate, tin compounds, e.g. Tin diacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate and dibutyltin dilaurate.

The cell openers vi) are exemplified by polar polyether polyols (polyalkylene glycols), ie those having a high content of ethylene oxide in the chain, preferably at least 50% by weight. These act by segregation and influence on the surface tension during the foaming line-opening.

i) to vi) are used in the ratios customary in polyurethane chemistry.

Melamine foams which are particularly suitable as starting material for carrying out the preparation process according to the invention are known as such. They can be prepared, for example, by foaming vii) a melamine-formaldehyde precondensate which, in addition to formaldehyde, may contain further carbonyl compounds such as aldehydes, viii) one or more blowing agents, ix) one or more emulsifiers, x) one or more hardeners.

Melamine-formaldehyde precondensates vii) may be unmodified, but they may also be modified, for example, up to 20 mol% of the melamine may be replaced by other known durolast agents, for example alkyl-substituted melamine, urea, urethane, carboxamides, dicyandiamide , Guanidine, sulfurylamide, sulfonic acid amides, aliphatic amines, phenol and phenol derivatives. As further carbonyl compounds in addition to formaldehyde, modified melamine-formaldehyde precondensates may comprise, for example, acetaldehyde, trimethylolacetaldehy, acrolein, furfurol, glyoxal, phthalaldehyde and terephthalaldehyde in condensed form.

As propellant viii) one can use the same compounds as described under iii) be¬ written. As emulsifiers ix) can use conventional non-ionic, anionic, cationic or betainic surfactants, in particular C ₂ -C ₃₀ alkyl sulfonates, preferably C ₂ - Cis-alkyl sulfonates and poly-ethoxylated Cio-C ₂ o-alkyl alcohols, in particular of the formula R ^ O (CH ₂ -CH ₂ -O) _x -H, wherein R ^{6 is} selected from C _1o -C ₂ o-alkyl and x may, for example, an integer in the range of 5 to 100 mean.

Suitable hardeners x) are, in particular, acidic compounds, such as, for example, inorganic Brønsted acids, e.g. Sulfuric acid or phosphoric acid, organic Brønsted acids such as acetic acid or formic acid, Lewis acids and so-called latent acids.

Examples of suitable melamine foams can be found in EP-A 0 017 672.

Of course, as starting material used foams (a) contain additives and additives which are common in foam chemistry, for example, anti-oxidants, flame retardants, fillers, colorants such as pigments or dyes and biocides, for example

Furthermore, the practice of the present invention is followed by at least one carboxyl group-containing and / or carboxylic acid ester-containing polymer (b) having a molecular weight M _n in the range from 1,000 to 1,000,000 g / mol in molten or preferably dissolved form or dispersed form, hereinafter also referred to as solid polymer (b) at room temperature. Carboxylate-containing and / or carboxylic acid ester group-containing polymer (b) which is solid at room temperature and is used according to the invention is described in more detail below.

In accordance with the invention, the above-described open-cell foams (a) are contacted with at least one carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) having a molecular weight M _n in the range from 1,000 to 1,000,000 g / mol. preferably 1,500 to 500,000 g / mol, more preferably 2,000 to 200,000 g / mol and most preferably up to 50,000 g / mol in molten or preferably dissolved or dispersed form.

After contacting according to the invention, modified foams according to the invention preferably contain in the range from 1 to 2.500% by weight, preferably from 10 to 1000% by weight, based on the weight of the corresponding unmodified Foam (a), at least one film-forming carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) having a molecular weight M _n in the range of 1,000 to 1,000,000, preferably 1,500 to 500,000 g / mol, more preferably 2,000 to 200,000 g / mol and most preferably up to 50,000 g / mol. In accordance with the invention used at room temperature solid carboxyl group-containing and / or carboxylic acid ester group-containing polymers (b) are organic polymers or copolymers. In accordance with the invention used at room temperature solid carboxyl group-containing and / or Carbonsäu¬ ester group-containing polymers (b) may be homopolymers or copolymers of ethylenically unsaturated mono- or dicarboxylic acids.

In one embodiment of the present invention, polymers (b) which are solid at room temperature and contain carboxyl group-containing and / or carboxylic acid ester groups are organic polymers which are different from the material made from the open-cell foam (a) are.

In accordance with the invention used at room temperature solid carboxyl group-containing and / or carboxylic acid ester group-containing polymers (b) may be polymers having a glass transition temperature T ₉ in the range of -50 to 15O ⁰ C, preferably - 25 to 12O ⁰ C and particularly preferably - 20 to 100 ⁰ C act.

In a preferred embodiment of the present invention, at least one carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature is a copolymer of at least one ethylenically unsaturated carboxylic acid selected from ethylenically unsaturated mono- and dicarboxylic acids and in particular one Copolymer of (meth) acrylic acid.

(A) ethylene,

(B) at least one ethylenically unsaturated carboxylic acid,

(C) optionally further comonomers.

Particularly preferred carboxyl-containing and / or carboxylic acid ester group-containing polymers (b) which are solid at room temperature are described in more detail below. It is particularly preferred for polymer (b) containing carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) which is solid at room temperature to comprise ethylene copolymers which are copolymerized as comonomers:

(A) 60 to 95 wt .-%, preferably 65 to 85 wt .-% of ethylene and

(B) 5 to 40 wt .-%, preferably 15 to 35 wt .-% of at least one ethylenically unsaturated carboxylic acid with statements in wt .-% on total at room temperature solid carboxyl group-containing and / or carboxylic ester group-containing polymer (b) are related.

Preferably, at least one ethylenically unsaturated carboxylic acid is a carboxylic acid of the general formula I.

In formula I, the radicals are defined as follows:

R ¹ selected from hydrogen and

C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

R ^{2 is} selected from hydrogen,

C 1 -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

COOH ₁ COOCH ₃ , COOC ₂ H ₅ ,

Most preferably, R ^{2 is} hydrogen and R ^{1 is} hydrogen or methyl.

According to the invention, ethylene copolymers which are solid at room temperature and contain carboxyl group-containing and / or carboxylic ester group-containing polymer (b) may contain up to 40% by weight, preferably up to 35% by weight, based in each case on in copolymerized form the sum of ethylene and polymerized or copolymerized ethylenically unsaturated ethylenically unsaturated carboxylic acid (s) of one or more further comonomers (C), for example

Vinyl, allyl and methallyl esters of C 1 -C 10 -alkylcarboxylic acids or of formic acid, for example vinyl formate, vinyl propionate and in particular vinyl acetate,

one or more ethylenically unsaturated carboxylic acid esters, preferably of the formula II

R ³ is selected from Ci-Ci _o alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-

Butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec. Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

R ^{4 is} selected from hydrogen, C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl ; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

R ^{5 is} selected from hydrogen, d-do-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,

Butyl, sec-butyl and tert-butyl; COOCH ₃ , COOC ₂ H ₅ ,

furthermore - vinylaromatic compounds such as, for example, α-methylstyrene and, in particular, styrene,

Isobutene and α-olefins such as CH ₂ = CH-HC ₁₆ H ₃₃₁ CH ₂ = CH-DC ₁₈ H ₃₇ , CH ₂ = CH-n-C ₂₀ H ₄₁ and CH ₂ = CH-Ii-C ₂₂ H ₄₅

In formula II, R ⁵ is very particularly preferably hydrogen and R ^{4 is} hydrogen or methyl.

In formula II, R ⁵ is very particularly preferably hydrogen and R ^{4 is} hydrogen or methyl and R ^{3 is} selected from methyl, ethyl, n-butyl and 2-ethylhexyl.

The ethylene copolymers of ethylene and at least one ethylenically unsaturated carboxylic acid described above can advantageously be prepared by free-radically initiated copolymerization under high-pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tubular reactors. Production in stirred high pressure autoclave is preferred. High pressure autoclaves are known per se, a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. With them predominantly the ratio length / diameter at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1 behaves. The equally applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.

Suitable pressure conditions for the polymerization are 500 to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures are in the range 170-300 ⁰ C, preferably in the range of 200 to 28O ⁰ C.

The copolymerization can be carried out in the presence of a regulator. The regulator used is, for example, hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula IV

or mixtures thereof.

The radicals R ⁶ and R ^{7 are} identical or different and selected from hydrogen;

C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n- Butyl, iso-butyl, sec-butyl and tert-butyl; C ₃ -C ₂ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; be¬ preferred are cyclopentyl, cyclohexyl and cycloheptyl.

In a particular embodiment, the radicals R ⁶ and R ⁷ are covalently bonded together to form a 4- to 13-membered ring. Thus, R ⁶ and R ⁷ may be bei¬ play together: - (CH ₂₎ ₄ -, - (CH ₂₎ S-, - (CH ₂₎ 6, - (CH ₂₎ 7, -CH (CH _S) -CH ₂ -CH ₂ -CH (CH ₃ ) - or -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -.

Other well-suited regulators are alkylaromatic compounds, for example toluene, ethylbenzene or one or more isomers of xylene. Preference is given to the use of aldehydes and ketones of the general formula IM as a regulator. With particular preference, no further regulators are metered, with the exception of the so-called phlegmatizers, which can be added to organic peroxides for better handling and can likewise have the function of a molecular weight regulator.

As initiators for the radical polymerization, the customary free radical initiators such as organic peroxides, oxygen or azo compounds can be used. Also mixtures of several radical starters are suitable.

Suitable peroxides selected from the commercially available substances are, for example

Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-A-mylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert Butyl peroxydiethyl isobutyrate, 1,4-di (tert-butyl peroxycarbonyl) cyclohexane as mixture of isomers, tert-butyl perisononanoate 1, 1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1 Di- (tert-butylperoxy) cyclohexane, tert-amyl peroxypivalate, methyl isobutyl ketone peroxide, tert-butyl peroxyisopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate; tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butylcumyl peroxide, 2, 5-dimethyl-2,5-di (tert-butylperoxy) -hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or dimeric or trimeric ketone peroxides of the general formula IV a to IV c.

IV a IV b IV c

The radicals R ⁸ to R ^{13 are} identical or different and selected from

C ₁ -C ₈ -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, iso-pentyl , n-hexyl, n-heptyl, n-octyl; preferably linear C 1 -C ₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, particularly preferably linear C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl or n-butyl most preferred is ethyl;

Ce-Cu-aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl , 1-naphthyl and 2-naphthyl, more preferably phenyl.

Peroxides of the general formulas IV a to IV c and processes for their preparation are known from EP-A 0 813 550.

As peroxides, di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxy isononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable. As an azo compound, azobisisobutyronitrile ("AIBN") is mentioned as an example Radical starters are metered in amounts customary for polymerizations.

Many commercially available organic peroxides are added to so-called phlegmatizers before they are sold to make them easier to handle. For example, white oil or hydrocarbons, in particular isododecane, are suitable as phlegmatizers. Under the conditions of radical high-pressure polymerization, such phlegmatizers can have a molecular-weight-regulating effect. For the purposes of the present invention, the use of molecular weight regulators should be understood to mean the additional use of further molecular weight regulators beyond the use of phlegmatizers.

The quantitative ratio of the comonomers ethylene and ethylenically unsaturated carboxylic acid (s) in the dosage usually does not correspond exactly to the ratio of the units in the copolymer used according to the invention of at least one ethylenically unsaturated carboxylic acid as solid at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) because ethylenically unsaturated carboxylic acids are generally more readily incorporated than ethylene. The comonomers are usually dosed together or separately.

The comonomers can be compressed in a compressor to the polymerization pressure. In another embodiment of the method according to the invention, the monomers are first brought by means of a pump to an elevated pressure of for example 150 to 400 bar, preferably 200 to 300 bar and in particular 250 bar and then pressure with a compressor to the actual polymerization.

The copolymerization can optionally be carried out in the absence and in the presence of solvents, mineral oils, white oil and other solvents which are present in the reactor during the polymerization and used for the phlegmatization of the radical initiator or initiators not being solvents in the sense of the present invention be valid.

In one embodiment, the copolymerization is carried out in the absence of solvents.

Of course, it is also possible to use a copolymer of at least one ethylenically unsaturated carboxylic acid which is solid at room temperature to prepare a carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) in such a way that ethylene with at least one ethylenically unsaturated carboxylic acid ester of the general Copolymerize formula II and then to esterify the ester groups in a polymer-analogous reaction, for example with potassium hydroxide or sodium hydroxide solution.

Other well-suited at room temperature solid carboxyl-containing and / or carboxylic acid ester-containing polymers are, for example, selected from

Styrene-acrylonitrile-CrC ₁₀ -alkyl (meth) acrylate terpolymers, styrene-butadiene-n-butyl acrylate terpolymers,

Styrene-maleic anhydride copolymer, preferably alternating styrene-maleic anhydride copolymers, which can be partially or completely hydroxylated, (meth) acrylic acid-α-olefin copolymers, wherein α-olefins are as defined above, poly (meth) acrylic acid , Polymethyl (meth) acrylate.

In accordance with the invention, open-cell foam (a) is contacted with carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature, solid polymer containing carboxyl groups and / or containing carboxylic acid ester groups (b) at room temperature in molten or preferably molten state. may be present dissolved or dispersed, in particular emulsified form. Ins¬ particular, if it is at room temperature solid Carboxylgruppen- containing and / or carboxylic acid ester group-containing polymer (b) is a copolymer of an ethylenically unsaturated carboxylic acid, it is preferred at room temperature solid carboxyl groups and / or Carbonsäureestergrup ¬ pen-containing polymer (b) in dissolved or dispersed, in particular emulsified form. Particular preference is given at room temperature to solid carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) dissolved or dispersed in water, in particular emulsified in water. Contacting may be accomplished, for example, by immersing open-celled foam (a) in room temperature solid carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b), by impregnating open cell foam (a) with carboxyl group solid at room temperature. containing and / or carboxylic acid ester group-containing polymer (b), by preferably complete spraying of open-cell foam (a) with fes¬ at room temperature fes¬ tem carboxyl-containing and / or carboxylic acid ester groups-containing Polymeri¬ sat (b), or by Aufkalandrieren from at room temperature solid carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) on open-cell foam (a).

If solid polymer (b) is dissolved or dissolved in water at room temperature, it can be used in the form of aqueous formulations which contain solid carboxyl groups-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature.

Aqueous formulations which are used according to the invention and contain solid carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature preferably contain from 0.05 to 40% by weight, preferably from 10 to 35% by weight, of one or more Room temperature solid polymers (b), preferably in completely or partially neutralized form.

In one embodiment of the present invention ein¬ set aqueous formulations containing at room temperature solid Carboxylgruppen- containing and / or carboxylic acid ester group-containing polymer (b) for the purpose of partial or complete neutralization usually contain one or more basic substances, such as hydroxides and / or carbonates and / or bicarbonates of alkali metals, ammonia, organic amines such as triethylamine example, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine. Preference is given to aqueous formulations which are used according to the invention and which contain solid carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature Substantially basic substance or substances having a basic action, that at least one quarter, preferably at least half, of the carboxyl groups of the polymer (s) which are solid at room temperature and which contain carboxyl groups and / or carboxylic acid ester groups are neutralized. Basic-acting substances can be used according to the invention formulations, for example during the

Dispersing or dissolving at room temperature solid Carboxylgruppen- containing and / or carboxylic acid ester group-containing polymer (b) add.

In one embodiment of the present invention, aqueous formulations employed according to the invention which contain at room temperature solid carboxyl groups-containing and / or carboxylic acid ester group-containing polymer (b) contain so much basic substance or basic substances that the carboxyl groups of the or the solid at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymers (b) are quantitatively neutralized.

Aqueous formulations which are used according to the invention and contain solid carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature usually have a basic pH, determined, for example, according to DIN 19268. Preference is given to pH values of 7 , 5 to 14, more preferably from 8 to 10 and most preferably from 8.5 to 10.

If it is desired to use solid carboxyl group-containing and / or carboxylate-containing polymer (b) at room temperature in solution, suitable solvents besides water are also organic solvents. Suitable organic solvents are, for example

aromatic hydrocarbons such as toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene;

aliphatic hydrocarbons such as n-dodecane, isododecane (2,2,4,6,6-pentamethylheptane), n-tetradecane, n-hexadecane, n-octadecane and isomers, individually or in admixture, of the abovementioned aliphatic hydrocarbons, in particular the commercially available as a solvent naphtha mixture of different Ci ₂ -Ci ₈ hydrocarbons;

Ethers, especially cyclic ethers such as tetrahydrofuran (THF) and 1, 4-dioxane,

Mixtures of the abovementioned aliphatic or aromatic hydrocarbons with 0.1 to 10% by weight of alcohols or ethers, for example n-hexanol, n-octanol, n-pentanol, tetrahydrofuran or 1,4-dioxane, chlorinated hydrocarbons such as chlorobenzene, ortho-dichlorobenzene, meta-dichlorobenzene.

Suitable concentrations of solid at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) in solvent or mixture of solvents are for example 0.001 to 75 wt .-%, preferably 0.01 to 28 wt .-%.

In one embodiment of the present invention, it is possible to act on one another after contacting (a) and (b), for example over a period of time in the range from 1 second to 24 hours, preferably 5 seconds to 10 hours, and particularly preferably 10 seconds to 6 hours.

In one embodiment of the preparation process according to the invention is contacted open-cell foam (a) and at room temperature solid Carboxylgruppen- containing and / or carboxylic ester group-containing polymer (b) at temperatures in the range of ^{0 0} C to 250 ⁰ C, preferably 5 ⁰ C to 19O ⁰ C and more preferably 10 to 165 ° C.

In one embodiment of the preparation process according to the invention is contacted open-cell foam (a) and at room temperature solid Carboxylgruppen- containing and / or carboxylic acid ester group-containing polymer (b) initially at temperatures in the range of 00 ⁰ C to 50 ⁰ C and then changes the temperature at ¬ game example by heating to temperatures ranging from 60 ⁰ C to 25O ⁰ C, preferably from 65 ^° C to 180 ° C.

In another embodiment of the inventive production process, open-cell foam kontak¬ one advantage (a) and solid at room temperature xylgruppen carbonyl-containing and / or Carbonsäureestergruppen-containing polymer (b) zu¬ next at temperatures in the range from 0 ⁰ C to 12O ⁰ C and then changes the temperature, for example, heated to temperatures in the range of 30 ⁰ C to 250 ⁰ C, preferably from 125 ⁰ C to 200 ⁰ C.

In a preferred embodiment of the process according to the invention, the solvent and temperature control are selected so that most structural parameters of open-cell foam (a) used as starting material are not substantially changed.

In another preferred embodiment of the present invention, the amounts of starting materials are selected from open-cell foam (a), solid carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature and, if appropriate, additives (c) such that the product according to the invention has a significantly higher density than the relevant used as a single-component open-cell foam (a).

In one embodiment of the present invention, the process of the invention is carried out at atmospheric pressure. In another embodiment of the present invention is carried out for carrying out the inventive manufacturing process under elevated pressure, for example at pressures in the range of 1, 1 bar to 10 bar. In another embodiment of the present invention, the inventive production process is carried out under reduced pressure, for example at pressures in the range from 0.1 mbar to 900 mbar, preferably up to 100 mbar.

In one embodiment of the present invention, open-cell foam (a) is contacted with polymer (b) which is solid at room temperature and contains carboxylic acid ester group-containing polymer (b) at room temperature as evenly as possible in all dimensions over open-cell foam (a ) is distributed. Suitable methods are methods with an order efficiency. Examples include: complete soaking, dipping, flooding, drumming, spraying, e.g. Compressed air spraying, airless spraying, further high-speed atomization, coating, knife coating, calendering, brushing, rolling, wiping, rolling.

In another embodiment of the present invention, open-cell foam (a) is contacted with polymer (b) which is solid at room temperature and contains carboxyl group-containing polymer (b) in such a way as to obtain an uneven distribution of carboxyl group-containing and solid at room temperature / or carboxylic acid ester group-containing polymer (b) on open-cell foam (a) causes. Thus, in one embodiment of the present invention, for example, open-cell foam (a) can be sprayed unevenly with polymer (b) which is solid at room temperature and contains carboxyl group-containing and / or carboxylic acid ester group-containing polymer and subsequently left to act. In another embodiment of the present invention, open cell foam (a) may be incompletely saturated with room temperature solid polymer (b). In another embodiment of the present invention, one part of open-cell foam (a) may be used once and another part of open-cell foam (a) at least twice with a carboxyl-containing and / or carboxylic acid ester group-containing polymer (b ) to contact. In another embodiment, one soaks open-cell foam (a) and flushes the topmost layer with, for example, water again cleanly. Then let it work. As a result, open cell foam (a) is coated in the core; the outer surface remains uncoated. If open-cell foam (a) is contacted with polymer (b) containing carboxyl groups containing carboxylate groups and / or carboxylic acid groups at room temperature in such a way that an uneven distribution of polymer-containing carboxyl groups and / or carboxylic acid ester groups at room temperature is obtained sat (b) has reacted on open-cell foam (a), for example by allowing it to act on each other for a period of 2 minutes or more, it is possible to obtain not only the outermost layer of open-cell foam (a) with carboxyl groups which are solid at room temperature containing and / or carboxylic acid ester group-containing polymer (b) is contacted.

If open-cell foam (a) is contacted with polymer (b) which is solid at room temperature and contains carboxylic acid ester groups and / or carboxylic acid ester groups in such a way that an uneven distribution of polymer-containing carboxyl groups and / or carboxylic acid ester groups at room temperature is obtained - sat (b) has caused on open-cell foam (a), so according to the invention modi¬ fizierter foam over its cross-section inconsistent mechanical properties th. For example, it is possible that, according to the invention, at the sites where it has been contacted with larger amounts of at least one carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature is harder than at the sites Sites where he has been contacted with less solid at room temperature carboxyl groups and / or Carbonsäu¬ ester group-containing polymer (b).

In one embodiment of the present invention, it is possible to rinse following contacting, for example with one or more solvents and preferably with water.

In one embodiment of the present invention, following the contacting and optionally rinsing, it is possible to dry, for example mechanically by e.g. B. wringing or calendering, in particular by squeezing by two rollers, or thermally, for example in microwave ovens, hot air blowers or in drying cabinets, in particular vacuum drying cabinets, where Trocken¬ cabinets, for example, at temperatures in the range of 25 to 10 ⁰ C below the Er¬ sofungspunkt or ., the melting point of solid at room temperature carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) can operate. In the context of vacuum drying cabinets, vacuum can be understood as meaning a pressure, for example in the range from 0.1 to 850 mbar.

By definition, the time spent on drying steps, if desired, is not part of the reaction time in the sense of the present invention. In one embodiment of the present invention, one can accomplish thermal drying by heating to temperatures in the range of 2O ⁰ C to 150 ⁰ C, for example, over a period of 10 seconds to 20 hours. Preferably er¬ is heated to a temperature, the temperature at least 2O ⁰ C above the glass transition containing carboxyl group-solid at room temperature and / or carboxylic säureestergruppen-containing polymer (b) is preferably heated to a temperature at least 30 ⁰ C above the glass transition temperature of employed polymer which is solid at room temperature (b). Preference is given to heating to a temperature which is below the melting or dropping point of employed carboxyl-containing and / or carboxylic ester-containing polymerizate (b) at room temperature, for example at least 5 ° C. below the melting or Dripping point of used at room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing polymer (b).

If one containing carboxyl groups, a mixture of at least two different solid at room temperature and / or Carbonsäureestergruppen-containing Polyme¬ risaten (b) used and wishes to thermally to dry, we heated to a temperature, preferably at least 20 ⁰ C of at least 3O ⁰ C above the glass transition temperature of that at room temperature solid carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b), which has the hö¬ here glass transition temperature. If a mixture of at least two different carboxyl group-containing and / or carboxylic acid ester group-containing polymers (b) is used at room temperature and if it is desired to dry it thermally, it is preferable to heat to a temperature below or above the melting point Dripping point of all employed at room temperature solid carboxyl-containing and / or carboxylic acid ester group-containing polymers (b), for example at least 5 ° C below the melting or dropping point of that at room temperature solid carboxyl groups and / or carboxylic acid ester groups containing polymer (b), which has the lowest melting or dripping point.

In one embodiment of the present invention, at least one open-celled foam (a) can be obtained not only with at least one carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b) at room temperature, but also with at least one additive (c). contact, chosen

Biocides, for example silver particles or monomeric or polymeric organic biocides, for example phenoxyethanol, phenoxypropanol, glyoxal, thiadiazines, 2,4-dichlorobenzyl alcohols and preferably isothiazolone derivatives, for example MIT (2-methyl-3 (2H) - isothiazolone), CMIT (5-chloro-2-methyl-3 (2H) -isothiazolone), CIT (5-chloro-3 (2H) -isothiazolone), BIT (1,2-benzisothiazol-3 (2H) -one ), continue to polymers of N, N-di-C ₁ -C 10 -alkyl-ω-amino-C ₂ -C ₄ -alkyl (meth) acrylate, in particular copolymers of ethylene with N, N-di-methyl-2-aminoethyl (meth) acrylate .

Solid, z. As abrasive materials such as sand, silicates with a mean particle diameter (number average) in the range of 1 .mu.m to 1 mm, or colloidal silicic acid, one or more surfactants, which may be anionic, cationic or nonionic dissolved Materials as constituents of room-temperature-fixed carboxyl group-containing and / or carboxylic acid ester group-containing polymer (b), activated carbon,

Colorants such as dyes or pigments,

Fragrances such as perfume,

Odor scavengers, for example cyclodextrins, and

Microcapsules filled with at least one active ingredient such as care oil, one or more biocides, perfume, odor traps, wherein microcapsules for the purposes of the present invention may be, for example spherical interior hollow particles having an average outer diameter in the range of 1 to 100 microns ¬ can be constructed of melamine-formaldehyde resin or polymethyl methacrylate.

This can be done, for example, that at least one open-cell foam (a) in different operations or preferably simultaneously with at least one fixed at room temperature carboxyl-containing and / or carboxylic acid ester group-containing polymer (b) and at least one addition impact (c ) contacted.

In one embodiment of the present invention ein¬ set aqueous formulation containing at room temperature solid Carboxylgruppen- containing and / or carboxylic acid ester group-containing polymer (b), one or more additives (c) enforce, for example, in amounts of 0 to ¬ including 50 wt .-%, based on (b), preferably 0.001 to 30 wt .-%, particularly preferably from 0.01 to 25 wt .-%, most preferably 0.1 to 20 wt .-%.

In one embodiment of the present invention, modified foams according to the invention or produced by the process according to the invention are produced

Foams essentially open-cell foams, i. those foams in which at least 50% of all lamellae are open, preferably 60 to 100% and more preferably 65 to 99.8%, determined according to DIN ISO 4590.

Modified foams according to the invention or foams produced by the process according to the invention are distinguished by overall advantageous properties. They show improved cleaning performance or cleaning effect, good hydration resistance to hydrolysis, improved acid resistance, good sound absorption and are particularly durable, for example when used for the production of cleaning materials. They pollute very slowly. Any contaminated erfindungsge¬ Permitted foams can be easily cleaned non-destructive. Furthermore, according to the invention, modified foams or modified foams according to the invention are distinguished by high resistance to oxidants, in particular gaseous oxidants such as, for example, ozone and oxygen.

In one embodiment of the present invention, it is possible to produce modified foams according to the invention in such a way that unmodified open-celled fibers are obtained

Foam (a) not only treated with at least one carboxyl group-containing or Car¬ bonsäureestergruppen-containing polymer (b) and optionally with min¬ least one additive (c), but additionally with at least one crosslinker (d). Preferred crosslinkers (d) are selected from metal alcoholates and polybasic epoxies.

As the metal alkoxide, one or more alkoxides of polyvalent metals are preferred, preferably of di- or tri-valent metals, more preferably of trivalent metals. As its divalent metals its for example called: Zn ²⁺ , Ca ²⁺ , Mg ²⁺ , Cu ²⁺ . Suitable trivalent metals are, for example, Fe ³⁺ , Cr ³⁺ , Ti ³⁺ , V ³⁺ and very particularly preferably Al ³⁺ .

The metal alcoholate used may be mixed alcoholates, such as, for example, mixed ethanolates / methanolates or else mixtures of various alcoholates, for example mixtures of ethanolates and methanolates or ethanolates and isopropylates. However, preference is given to using pure alcoholates.

The metal alkoxide used may be metal alkoxides, such as, for example, metal methoxides, metal ethanolates, isopropylates, metal tert-butylates, and also metal phenates and in particular metal enolates. Preferably, metal alcoholates are derived from those alcohols which have a boiling point at atmospheric pressure of up to 15O ⁰ C. Very particular preference is given to enolates of the general formula III

where the variables are defined as follows: M ⁺ "is a cation of an n-valent metal, for example Na ⁺ , K ⁺ , preferably Ca ²⁺ , Mg ²⁺ , Fe ³⁺ , Cr ³⁺ , Ti ³⁺ , V ³⁺ and most preferably Al ³⁺ , n is an integer in the range from 1 to 4, preferably 2 to 3 and very particularly preferably 3, R ^{15 is} hydrogen or methyl,

R ¹⁴ , R ¹⁶ different or preferably the same and selected from

C ₁ -C ₄ -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, especially methyl; Phenyl, C ₁ -C ₆ -alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-

Butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, preferably methoxy, ethoxy, n-propoxy and n-butoxy and particularly preferably ethoxy.

Most preferably, R ¹⁴ and R ^{16 are the} same and methyl.

Crosslinker (d) and in particular metal alcoholate are preferably used in one or more solvents. Particularly suitable solvents for crosslinkers (d) are aprotic organic solvents. Particularly suitable are cyclic and non-cyclic ethers, for example tetrahydrofuran, 1,4-dioxane, tetrahydropyran, diisopropyl ether, di-n-butyl ether and mixtures of the abovementioned solvents, very particularly tetrahydrofuran.

In one embodiment of the present invention, from 1 to 10% by weight of metal alcoholate are used, based on carboxyl group-containing or carboxylic acid ester group-containing polymer (b), preferably from 2 to 5% by weight.

In a specific embodiment of the present invention, it is possible to use metal alcoholate and carboxyl group-containing polymer (b) in amounts such that the molar ratio of COOH groups of carboxyl group-containing polymer (b) to Metal cation in the range of 1: 1 to 1: 6.

In another embodiment of the present invention, first polymer (b) containing carboxyl groups or carboxylic acid ester groups is mixed with metal alcoholate and then admixed with one or more of the abovementioned solvents, it being possible for the proportions to be as mentioned above.

Subsequently, the solvent is evaporated or is slowly, for example at room temperature or at slightly elevated temperature such as 30 or 35 C. During ⁰ the solvent or solvents evaporate, a homogeneous aus¬ sighted film is formed. In order to facilitate the evaporation, one can work under reduced pressure, for example at pressures in the range of 100 to 990 mbar.

According to the invention, the evaporation residue is then treated thermally.

In one embodiment of the present invention can be the residue Verdampfungs¬ 5 to 48 hours, preferably 12 to 36 hours at a temperature in Be¬ ranging from 45 to 13O ⁰ C, preferably from store 60 to 120 ⁰ C.

In another embodiment of the present invention, the evaporation residue can be heated gradually. So you can, for example, first heat to 70 to 90 ⁰ C, then stored for 1 to 5 hours at 70 to 9O ⁰ C, and then heated to 110 to 130 ° and stored for another 1 to 5 hours.

It is believed, without any preference being given to a particular theory, that at least two acid radicals, which belong to different molecules of carboxyl-containing polymer (b), attach in deprotonated form to a polyvalent metal cation.

In another embodiment, carboxyl-containing or carboxylate-containing polymer (b) is mixed with one or more polybasic epoxides and at least one solvent, which may be chosen as above.

Suitable polyfunctional epoxides are, for example, dendrimeric epoxides having at least two epoxide groups, furthermore hyperbranched polymers having at least two epoxide groups, so-called hyperbranched polymers differing from dendrimers due to their molecular nonuniformity, see, for example, News from Chemistry, Technology and Laboratory, 2002, 50, 1218th

Particularly suitable polyfunctional epoxides are polyfunctional epoxides of the general formula VI:

where A can be chosen as follows: Ci-C ₂ o-alkylene, unsubstituted or substituted by one or more CVC ₄ -

Alkyl groups, one or more C ₆ -C ₁₄ aryl groups, one or more OH groups which may be etherified with C ₁ -C ₆ alkanol or glycidyl alcohol, wherein one or more nonadjacent C atoms may also be replaced by oxygen; preferred are -CH ₂ -, -CH ₂ -CH ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, -

-CH (CH ₃ ) -, -CH (C ₂ H ₅ ) -, -CH (C ₆ H ₅ ) -, -CH (OH) -, - [CH (OH) J ₂ -, -CH (OCH ₃ ) -, -CH (OC ₂ H ₅ ) -, -CH (O-glycidyl) -;

-O- (CH ₂ ) ₂ -O-, -O- (CH ₂ ) ₄ -O-, - [O- (CH ₂ ) ₂ ] ₂ -O-, - [O- (CH ₂ ) ₂ ] ₃ -O-, - [O- (CH ₂ ) ₂ ] ₄ -O-, C ₄ -Cio-cycloalkylene, for example cis- or trans-1,3-cyclobutylene, cis- or trans-1,3-cyclopentylene, or trans-1,4-cyclohexylene,

C ₆ -C ₄ -arylene, for example meta-phenylene, para-phenylene, 4,4'-bipenylene

Nitrogen, substituted with C 1 -C ₁₀ -alkyl, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-butyl Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably -C ₄ - alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular methyl;

Nitrogen substituted with C ₆ -C ₁₄ -aryl, which in turn may be substituted with one or more dC ₄ alkyl groups, one or more C ₆ -Cu-aryl groups, one or more OH groups, the with dC ₆ -alkanol or

Glycidyl alcohol can be etherified.

Particularly preferably used polyvalent epoxides correspond to the formulas VI a to VI h

VI b

VI e

VI f

VI g VI h

For the preparation of materials for material separation, for example, polyvalent epoxide and ethylene copolymer are combined in amounts such that the MoI ratio of COOH groups of ethylene copolymer to epoxide groups is in the range from 100: 1 to 1: 1, preferably 30: 1 to 10: 1.

In one embodiment of the present invention, carboxyl-containing or carboxylic acid ester group-containing polymer (b) and polybasic epoxide are dissolved in at least one solvent, preferably THF. The solvent (s) are allowed to evaporate. It is then treated thermally at temperatures in the range of 70 to 15O ⁰ C, preferably from 90 to 120 ⁰ C, and receives a special embodiment of inventive modified foam. A further subject of the present invention is the use of modified open-cell foams according to the invention or of open-cell foams modified according to the invention for the production of

Cleaning materials such as plaster sponges, brushes, cleaning cloths or plaster granules,

Filters such as air filters, pond filters, aquarium filters, water filters, or as a matrix for ceramic filters, humidifiers, water distributors,

Packaging elements, in particular for shock-sensitive or water-sensitive goods, sound insulation elements, building insulation, in particular roof insulation and wall insulation.

Another object of the present invention is a process for the preparation of cleaning materials using modified open-cell foam according to the invention or modified open-cell foam according to the invention. A further subject of the present invention is a process for the production of filters using modified open-cell foams according to the invention or open-cell foams modified according to the invention. Another object of the present invention is a process for the production of humidifiers using modified open-cell foams according to the invention or modified open-cell foams according to the invention. A further subject of the present invention is a process for the preparation of water distributors using modified open-cell foams according to the invention or of open-cell foams modified according to the invention. A further subject of the present invention is a process for the production of packaging elements using modified open-cell foams according to the invention or modified open-cell foams according to the invention. Another object of the present invention is a process for the preparation of sound insulation elements using düng of modified modified open-cell foams according to the invention or of er¬ inventively modified open-cell foams. Another object of the present invention is a process for the production of building insulation using modified open-cell foams according to the invention or modified open-cell foams according to the invention.

If it is desired to use modified foams according to the invention for the production of filters, tubular filters and martices of ceramic filters are preferred. If it is desired to use modified foams according to the invention for the production of automotive parts, ventilation units are particularly preferred.

A further subject matter of the present invention is cleaning materials, filters, air humidifiers, water distributors, packaging elements, soundproofing elements and Building insulation, prepared using or containing erfindungsge¬ Permitted modified open-cell foam or inventively modified open-celled foams.

For example, modified foams according to the invention can be mechanically combined with other materials, for example with stems, basic bodies for brooms and brushes, for example, with textiles, leather, polyurethane or wood. The invention will be explained by working examples.

working examples

I. Preparation of a Solid Carboxyl Group-Containing and / or Carboxylic Ester Group-Containing Polymer (b.1) in Dispersed Form 1.1. Preparation of a solid at room temperature copolymer of methacrylic acid

In a high-pressure autoclave, as described in the literature (M. Buback et al., Chem. Ing. Tech., 1994, 66, 510), ethylene and methacrylic acid were copolymerized. For this purpose, ethylene (12.3 kg / h) was fed under the reaction pressure of 1700 bar in the autoclave. Separately, 1.10 l / h of methacrylic acid were first compressed to an intermediate pressure of 260 bar and then fed under the reaction pressure of 1700 bar. Separately, 2 l / h of an initiator solution, consisting of tert-amyl peroxypivalate (0.13 mol ^-1 in isododecane), was fed into the autoclave under the reaction pressure of 1700 bar. The reaction temperature was 220 ⁰ C. to obtain 3.4 kg / h solid at room temperature copolymer of methacrylic acrylic acid (b.1) having the following properties: 26.2 wt .-% methacrylic acid, 73.8 wt .-% ethylene , Melting range 75-85 ⁰ C, measured according to DIN 51007, p 0.9613 g / cm ³ , MF1 10.5 g / 10 min, measured at 120 ⁰ C and a load of 325 g according to DIN 53735, acid number 170.5 mg KOH / g (determined according to ES ISO 3682).

The content of ethylene and methacrylic acid in (b.1) was determined by NMR spectroscopy or by titration (acid number). The acid number of (b.1) was determined by titrimetry according to DIN 53402. The KOH consumption corresponds to the methacrylic acid content in (b.1).

I.2. Preparation of an Aqueous Dispersion of Carcyl Group-Containing and / or Carboxylic Ester Group-Containing Polymer (b.1) at Room Temperature

1.2.1 Preparation of an aqueous dispersion D1 250 g of ethylene copolymer (b.1) according to Example 1.1, 34 g of 25% by weight aqueous ammonia solution and 716 ml of deionized water were placed in a 2 liter stirred tank with anchor stirrer and reflux condenser. The mixture was heated with stirring to 95 ° C and stirred for three hours at 95 ° C after. Aqueous dispersion D1 with a pH of 8.5 was obtained. The solids content of D1 was 25.3% by weight.

1.2.2 Preparation of an aqueous dispersion D2

In a 2-liter stirred tank with anchor stirrer and reflux condenser, 206.8 g of ethylene copolymer (b.1) according to Example 1.1, 34.9 g of Λ /, / V-dimethylethanolamine and 758.3 ml of deionized water were initially charged. The mixture was heated with stirring to 95 ° C and stirred for three hours at 95 ° C after. Aqueous dispersion D2 having a pH of 8.5 was obtained. The solids content of D2 was 21% by weight.

1.2.3 Preparation of dilute aqueous dispersions

Dispersion D1 or D2 were diluted with deionized water at room temperature in each case to solids contents of 10%, 5%, 2% and 1%. The dilute aqueous dispersions D1.10, D1.05, D1.02 and D1.01 or D2.10, D2.05, D2.02 and D2.01 were obtained.

II. Representation of a modified foam according to the invention

11.1 Representation of unmodified foam (a)

In an open vessel, a spray-dried melamine / formaldehyde precondensate (molar ratio 1: 3, molecular weight about 500) was added to an aqueous solution containing 3% by weight of formic acid and 1.5% of the sodium salt of a mixture of alkylsulfonates with 12 to 18 carbon atoms in the alkyl radical (emulsifier K 30 from Bayer AG), the percentages being based on the melamine / formaldehyde precondensate. The concentration of Meiamin / formaldehyde precondensate, based on the total mixture of melamine / formaldehyde precondensate and water, was 74%. The mixture thus obtained was vigorously stirred, then 20% of n-pentane were added. The mixture was stirred further (about 3 minutes) until a homogenous dispersion was obtained. This was knife-coated onto a Teflon coated glass fabric as support material, and ruled in a drying cabinet in which an air temperature of 150 ⁰ C, foamed and cured. The boiling point of n-pentane turned a mass temperature in the foam, which lies under these conditions at 37.0 ⁰ C. After 7 to 8 minutes, the maximum height of rise of the foam was reached. The foam was left for a further 10 minutes at 150 ^° C. in a drying oven; It was then tempered for 30 minutes at 180 ° C. Unmodified foam (a.1) was obtained. 11.2 Preparation of Modified Foams S1 According to the Invention

The following properties were determined on unmodified foam (a.1) from Example 11.1: 99.6% open-cell according to DIN ISO 4590,

Compression hardness (40%) 1, 3 kPa determined according to DIN 53577, density 10.0 kg / m ³ determined according to EN ISO 845, average pore diameter 210 μm, determined by analysis of microscopic images on sections, BET surface area of 6.4 m ² / g, determined according to DIN 66131, sound absorption of 93%, determined according to DIN 52215, sound absorption of more than 0.9, determined according to DIN 52212.

Unmodified foam (a.1) from example 11.1 was cut into foam cubes measuring 9 cm-4 cm-4 cm. The foam cubes weighed in the range of 1.20 to 1.33 g. Subsequently, it was contacted with aqueous dispersion D1.10 by immersing a foam block in each case completely in the aqueous dispersion D1.10 and allowed to cover for 10 seconds with aqueous dispersion D1, 10. Subsequently, the foam cuboids were removed from the relevant aqueous dispersion and excess excess aqueous dispersion was squeezed off by passing through two counter rotating rolls having a diameter of 150 mm and a spacing of 5 mm and running at a speed of 32 revolutions / min turned.

Then it was dried for 10 hours at 6O ⁰ C in a drying cabinet. Inventive modified foam S1.10 was obtained according to the invention.

11.3 Presentation of further modified foams according to the invention

The experiment according to II.2 was repeated, but using in each case dispersion according to Table 1. Inventive modified foams were obtained.

Table 1: Inventive modified foams

Use of modified foams according to the invention and non-modified foams as plaster sponges

Modified foams and unmodified foam according to the invention were each used as plaster sponges.

Each of the modified foams and unmodified foam according to the invention was moistened with water.

Man cleaned over a period of 2 minutes manually each about 1 m ² a streaked plasterboard wall (rough), which was contaminated with strips of rubber abrasion, shoe polish and waste oil, with one of the modified foams according to the invention from II.2 or II. 3 and with unmodified foam according to III.1. It obtained plastered walls according to Table 2, in which the quality of the plaster were assessed on visual impression. Furthermore, the dimensional stability of the plaster sponges was visually assessed.

Table 2: Unmodified foam (a.1) from 11.1, modified foams according to the invention and their use as plaster sponges

Claims

Patentansprüche1. Modified open-cell foams with a density in the range of 5 to

1,000 kg / m ³ and an average pore diameter in the range from 1 μm to 1 mm, in the range from 1 to 2,500% by weight, based on the weight of the unmodified open-cell foam, of at least one carboxyl group-containing and solid at room temperature or carboxylic acid ester group-containing polymer having a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol.

2. A process for the preparation of modified open-cell foams, da¬ characterized in that one

(A) open-celled foams having a density in the range of 5 to 500 kg / m ³ and an average pore diameter in the range of 1 .mu.m to 1 mm (b) with at least one solid at room temperature carboxyl groups and / or containing carboxylic acid ester group-containing polymer a molecular weight M _n in the range of 1,000 to 1,000,000 g / mol contacted in molten, dissolved or dispersed form.

3. The method according to claim 2, characterized in that it is at least one at room temperature solid carboxyl group-containing and / or carboxylic acid ester-containing polymer (b) is a copolymer of an ethylenically unsaturated carboxylic acid.

4. The method according to claim 2 or 3, characterized in that it is at least one solid at room temperature carboxyl-containing and / or carboxylic acid ester-containing polymer (b) is a Copolymeri¬ sat, which is obtainable by copolymerization of

(A) ethylene,

(B) at least one ethylenically unsaturated carboxylic acid,

(C) optionally further comonomers.

5. The method according to any one of claims 2 to 4, characterized in that at least one solid at room temperature carboxyl-containing and / or carboxylic ester group-containing polymer (b) first dispersed in aqueous medium and then with unmodified foam (a) kontak ¬ tiert.

6. The method according to any one of claims 2 to 5, characterized in that it is foams made of synthetic organic foam in open-cell foams (a).

7. The method according to any one of claims 2 to 6, characterized in that it is foamed materials (a) polyurethane foams or aminoplast foams.

8. The method according to any one of claims 2 to 7, characterized in that at least one open-cell foam (a) contacted with at least one Zu¬ schlagstoff (c), selected from biocides, solids, dissolved Materia¬ lien as components of solid at room temperature Carboxyl-containing and / or carboxylic ester-containing polymer (s), surfactants, colorants, activated carbon, fragrances, odor scavengers and microcapsules, filled with at least one active ingredient.

9. Use of modified open-cell foams according to claim 1 or of modified open-cell foams, produced by a process according to one of claims 2 to 8, as or for the production of cleaning materials, filters, humidifiers, water distributors, packaging elements,

Sound insulation elements or building insulation.

10. A method for the production of cleaning materials, filters, humidifiers, Wasser¬ distributors, packaging elements, sound insulation elements or Gebäudeisolie- ments using modified open-cell foam after

Claim 1 or of modified open-cell foams, produced by a process according to one of claims 2 to 8.

11. Cleaning materials, filters, humidifiers, water distributors, packaging elements, sound insulation elements and building insulation, prepared using modified open-cell foams according to claim 1 or modifi¬ ed open-cell foams, prepared by a method according to ei¬ nem of claims 2 to 8.

12. cleaning materials, filters, humidifiers, water distributors, packaging elements, sound insulation elements and building insulation, containing modified open-cell foam according to claim 1 or modified open-cell Schaumstof¬ Fe, prepared by a method according to any one of claims 2 to 8.