DE10050418A1 - Polyurethane foam for adsorbing chemicals or gases or for purifying waste water contains immobilized ethyleneimine, polyethyleneimines and/or alkali(ne earth) hydroxides - Google Patents

Abstract

Polyurethane foams contains (i) ethyleneimine, polyvinyl amines or their copolymers or optionally carboxymethylated-, phosphonomethylated-, quaternized- and/or dithiocarbamatized-polyethyleneimine and/or (ii) alkali(ne earth) hydroxides. An Independent claim is also included for the preparation of the foam.

Description

The invention relates to polyurethane foams, for example Soft, semi-rigid or rigid foams, preferably open-celled Foams containing (i) ethyleneimine, polyethyleneimine, poly vinylamine, carboxymethylated polyethyleneimines, phosphonomethy lated polyethyleneimines, quaternized polyethyleneimines and / or dithiocarbamitized polyethyleneimines, or (ii) alkali or alkaline earth metal hydroxides, the use of which for the adsorption of Ge olfactory substances and processes for their production.

Fragrances are mostly organic sub punch mixes that are already in exceptionally low concentration ions lead to considerable odor nuisance. For assignment A large number of sorbents are available for these odorants Available, for example, activated carbons, silica gels, toners or molecular sieves are used. Generally will these sorbents on polymeric frameworks such as white foams supported.

JP 03009950 describes a deodorising polyurethane foam that binds a large number of odorous substances. As Deodorising components are, for example, connections based Phosphoric acid, phosphoric acid, hypophosphorous acid, salt acid and its salts (alkaline earth and alkali metal salts) ver applies. In addition, the active ingredients are preferred to one Carrier (silica or alumina) applied.

No. 4,877,816 describes a foam cloth that contains fine particles Contains deodorants and a disinfectant. As Desodo zinc carbonate or iron sulfate is not described as desin a phthalimide. A polyurethane is preferred foam used.

JP 49131986 discloses polyurethane foams with a Lö solution or suspension impregnated with metallic compounds become. Then these compounds with alkaline, oxidizing or reducing compounds treated to metals, metal oxides or metal complexes are added to the foam put. The foams can be used for odor adsorption become.  

JP 09057050 describes a deodorant filter made from a Polyurethane foam that contains an active ingredient, e.g. activated carbon, contains an ion exchange resin, or a catalyst.

The object of the present invention was to provide a foam develop that removes odors reliably and quickly, preferably without the odoriferous gas flowing through it to become.

The object of the present invention was achieved using polyurethane foams are dissolved, which the compounds (i) and / or (ii) included.

The invention therefore relates to polyurethane foams containing

• a) ethylene imine, polyethylene imine, polyvinylamine, carboxy methylated polyethyleneimines, phosphonomethylated poly ethyleneimines, quaternized polyethyleneimines and / or dithiocarbamitized polyethyleneimines or
• b) alkali and / or alkaline earth metal hydroxides or

a mixture of (i) and (ii).

Another object of the invention is a process for the manufacture position of the polyurethane foams according to the invention and their Use for the adsorption of odorous substances and for production of moldings.

According to the invention, ethyleneimine, poly ethyleneimine, polyvinylamine, carboxymethylated polyethyleneimines, phosphonomethylated polyethyleneimines, quaternized poly ethyleneimine and / or dithiocarbamitized polyethyleneimine used.

Examples include: ethyleneimine, polyethyleneimines with an average molecular weight of 500 to 800,000 g / mol, carboxymethylated polyethyleneimines with a medium mole Specular weight from 1000 to 50,000 g / mol, phosphonomethylated poly ethyleneimines with an average molecular weight of 1000 to 100,000 g / mol, acidified polyethyleneimines with medium Molecular weight from 1000 to 100,000 g / mol, dithiocarbamitized Polyethyleneimines with an average molecular weight of 1000 up to 100,000 g / mol, polyvinylamines with an average molecular weight  weight from 1000 to 1 500 000 g / mol. All information relates here on the number average molecular weight.

Preferred as (i) are polyethyleneimine and / or polyvinylamine.

As alkali or alkaline earth metal hydroxides (ii) according to the invention Sodium hydroxide and potassium hydroxide preferred.

The production of the polyurethane foams according to the invention is carried out by reacting polyisocyanates with compounds at least two hydrogen atoms reactive with isocyanates, wherein the compounds (i) or (ii) on the surface of the Foam are applied. The compounds (i) and (ii) can by two preferred methods on the polyurethane foam fabric are applied.

On the one hand, the production of the polyurethane foam can be carried out by Reaction of polyisocyanates with compounds with at least two hydrogen atoms reactive with isocyanates in the presence of (i) or (ii). From the connections (i) but also produced by reaction with isocyanate prepolymers become. This means the reaction products of compounds (i) and polyisocyanates, which preferably free iso at the chain end have cyanate groups. The prepolymers and quasi-prepolymers and their manufacture is well known.

On the other hand, you can make the polyurethane foam according to its manufacture Soak the position with solutions of compounds (i) or (ii). By soaking the foam with the liquid compound (i) or a solution of the solid or liquid compound (i) or (ii) in a suitable solvent, (i) or (ii) impregnated with the foam. Protic solvents are suitable Solvents, for example water, acetone, ethanol, i-propanol, Methyl ethyl ketone or haloalkanes such as 1,2-dichloromethane. Out the foams soaked with compound (i) or (ii) the solvent can then be removed. This can done by applying a vacuum or by drying Temperatures up to max. 50 ° C. By temperature treatment at Temperatures between 50 and 150 ° C over a period of 4 to The compounds (i) can be applied to the foam for 72 hours react and thus be covalently connected.

Furthermore, the support of the compounds (i) or (ii) for example by spraying. The solvent must in this case, be removed. For example by applying vacuum and / or temperature.  

With a subsequent impregnation of the foams with a The solution of compounds (i) or (ii) is the absorption capacity of the foam also on the type and polarity of the solvent dependent, in which the active ingredient was dissolved. Especially the ver use of acetone as the preferred solvent for the Ver bindings (1) increases the capacity of the foam for (i). For the compounds (ii) is preferably alcohol, such as. B. ethanol, used.

The compounds soaked on the foam (i) or (ii) can optionally be carried out in a further step crosslink the foam. Suitable crosslinkers are all commonly known, for example, are non-volatile PEG-bis glycidyl ether or polycarboxylic acids, such as tetra suitable carboxylic acid. The temperatures required for networking for the ethers at 80 ° C for the polycarboxylic acids at 120 to 130 ° C.

The polyurethane foams according to the invention preferably have a content of (i) or (ii) or mixtures of (i) and (ii) of 0.1 to 80% by weight, preferably 20 to 70% by weight, especially before adds 25 to 6% by weight, based on the weight of the foam, on.

The polyurethane foams according to the invention are preferred Application in the adsorption of odorous substances. Indeed the foams can also be used to adsorb harmful substances such as for example heavy metals or dyes from liquids be used. The foams can also be used for gas laundry can be used, for example, as an ozone filter in motor vehicles.

The polyurethane foams of the invention can in all generally used in the form of foam pads. Can also they for the production of molded articles and articles of daily use be used. Examples of this include shoe soles, Hangers and upholstery for clothing. The production this molded article also includes the back-foaming of counter stands, such as hangers, closet doors or Fittings in vehicles.

The adsorbent foams used according to the invention are preferred can be used in a temperature range from <0 ° C to 110 ° C, with a limited service life at temperatures <90 ° C is expected.  

The polyurethane foams according to the invention are preferred wise open-celled to have the largest possible surface for the contact between compounds (i) and / or (ii) and to ensure the odorants to be adsorbed.

The polyurethane foams produced by the process according to the invention preferably have a density of 10 to 800 kg / m ³ , particularly preferably 20 to 700 kg / m ³ and in particular 40 to 60 kg / m ³ .

To produce the polyurethanes of the invention Isocyanates in the usual way with the compounds with at least two active hydrogen atoms in the presence of blowing agents and optionally catalysts and / or auxiliaries and / or Additives brought to reaction. Here, the ver bonds with at least two reactive with isocyanate groups Hydrogen atoms and the blowing agents mentioned below, Catalysts and auxiliaries and / or additives often before Implemented into a so-called polyol component and brought these together with the isocyanate component.

The following can be said in detail about the possible starting products for carrying out the process according to the invention, ie the isocyanates, the compound having at least two active hydrogen atoms, the blowing agents and, if appropriate, the catalysts and / or the auxiliaries and / or additives:
The usual and known (cyclo) aliphatic and aromatic polyisocyanates can be used as isocyanates, preferably polyisocyanates, particularly preferably diisocyanates, preferably organic diisocyanates. Examples of aromatic poly isocyanates are 2,4- and 2,6-tolylene diisocyanate (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate (MDI), polyphenylene polymethylene polyisocyanates (raw MDI ), 1,5-naphthylene diisocyanate.

Examples of (cyclo) aliphatic di- or tri-isocyanates are 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, iso phorone diisocyanate, 2-methyl-pentamethylene diisocyanate, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2-butyl-2-ethyl pentamethylene diisocyanate, 1, 4-diisocyanatocyclohexane, 3-iso cyanatomethyl-1-methyl-1-isocyanatocyclohexane, isocyanatopropyl- cyclohexyl isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, lysine ester isocyanates, 1,3- or 1,4-bis (isocyanatomethy1) cyclohexane, 4-iso cyanatomethyl-1,8-octamethylene diisocyanate and mixtures thereof or the oligo- or polyisocyanates prepared therefrom.  

The oligo- or polyisocyanates can be produced from the mentioned di- or triisocyanates or mixtures thereof Linkage using urethane, allophanate, urea, biuret, Uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxa diazintrione or iminooxadiazinedione structures.

The isocyanates mentioned can also be modified, for example wise by incorporating carbodiimide groups. Often they are Polyisocyanates also used in the form of prepolymers. there are reaction products of the poly mentioned isocyanates with polyol components. Usually so-called Isocyanate prepolymers used, that is, such implementation Products of polyols and polyisocyanates that are at the chain end have free isocyanate groups. The prepolymers and quasi prepolymers and their preparation are generally known and described many times. For the method according to the invention especially prepolymers with an NCO content in the range of 25 to 3.5 wt .-% used.

In a preferred embodiment of the Ver are used as isocyanate component MDI and / or raw MDI as well Biurets, isocyanurates, and allophanates based on aliphatic Isocyanates used.

As a compound with at least two active hydrogen atoms are preferably polyester alcohols and particularly preferred Polyetherols with a functionality of 2 to 8, in particular from 2 to 4, preferably 2 to 3 and an average molecular weight in the range of 1000 to 8500 g / mol, preferably 1000 to 6000 used. Connections with at least two active Hydrogen atoms also include the chain extension and ver wetting agents that can be used if necessary. Preferred as chain extenders and crosslinking agents as 2- and 3-functional alcohols with molecular weights less than 1000 g / mol, in particular in the range from 60 to 150. Examples are ethylene glycol, propylene glycol, diethylene glycol, Dipropylene glycol, polyethylene glycol with a molecular weight less than 1000, polypropylene glycol with a molecular weight less than 1000 and / or 1,4-butanediol. Can be used as a crosslinking agent diamines can also be used. If chain extension and Crosslinking agents are used, the amount is preferred up to 5 wt .-%, based on the weight of the isocyanates.

As catalysts for the preparation of the invention Polyurethane foams can be the usual and known poly urethane formation catalysts are used. For example organic tin compounds, such as tin diacetate, tin dioctoate,  Dialkyltin dilaurate and / or strongly basic amines such as triethyl amine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, 1,2-dimethylimidazole, dimethylcyclohexylamine, dimethylbenzylamine or preferably triethylenediamine. The catalysts are before preferably in an amount of 0.01 to 5% by weight, preferably 0.05 up to 2% by weight, based on the weight of the isocyanates.

As a blowing agent for the production of polyurethane foams preferably water used with the isocyanate groups under Release of carbon dioxide reacts. Together with or at Instead of water, physically active blowing agents, for example hydrocarbons, such as n-, iso- or cyclopentane, or halogenated hydrocarbons, such as tetrafluoroethane, penta fluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane, Dichloro-monofluoroethane or acetals such. B. methylal used become. The amount of physical blowing agent lies there preferably in the range between 1 to 15% by weight, in particular 1 to 10 wt .-%, the amount of water preferably in the range between 0.5 to 10% by weight, in particular 1 to 5% by weight on the weight of connections with at least two active Hydrogen atoms.

As auxiliaries and / or additives, for example surface-active substances, foam stabilizers, cell regulators, external and internal release agents, fillers, pigments, hydrolysis protective agents as well as fungistatic and bacteriostatic Substances are used.

In the production of the polyurethane foams according to the invention the polyisocyanates and the compounds with at least two preferred hydrogen atoms reactive with isocyanate groups reacted in such an amount that the Equivalence ratio of isocyanate groups to the sum of the active ones Hydrogen atoms 0.7 to 1.8: 1, preferably 0.7 to 1.2: 1 is.

The production of polyurethane foams is preferred wise according to the one-shot process, for example with the help high pressure or low pressure technology. The foams can in open or closed metal molds or by continuously applying the reaction mixture Belt lines for the production of foam blocks are produced.  

It is particularly advantageous after the so-called two component process, in which, as explained above, a polyol and an isocyanate component produced and with be foamed on each other. The components are preferred at a temperature in the range between 15 to 90 ° C, preferably 20 to 60 ° C and particularly preferably 20 to 35 ° C mixed and in the mold, or brought to the belt line. The temperature in the mold is usually in the range between 20 and 110 ° C, preferably 30 to 60 ° C and particularly preferred 35 to 55 ° C.

With the direct addition of compounds (i) or (ii) already these can be used in the production of polyurethane foams both the polyol component and the isocyanate component be added. Preferred is (i) or (ii) the polyol component added.

The invention is illustrated by the following examples become.

Examples

For the adsorption of odorous substances according to the invention various, possibly modified polyurethane foams posed and deployed. The scents were sour Odorants, such as simulated acetic acid. The The model compounds were adsorbed in a 560 l comprehensive climate chamber at 25 ° C. Inside the climate cabinet concentrations of approx. 140 to 160 ppm V / V (V / V = volume related concentrations) of model substance. After Foam addition was the decrease in concentration by means of Gas chromatography determined. The lupranols are different polyetherols with different starters were produced and in the amount of ethylene oxide / propylene oxide differ, the Lupranaten are different MDI-based products.

example 1

Production of an aromatic flexible polyurethane foam, hereinafter referred to as comparison system 1, by intensive Mix 105.2 g A component with 100 g B component (index 100) with the help of a stirrer at a speed of 1250 rpm and converting the foaming mixture into a plastic vessel with a volume of 5 l, the components being as follows build up:  

Polyol Component

97 parts of Lupranol 2040 (BASF Aktiengesellschaft)
3 parts Lupranol 2047® (BASF Aktiengesellschaft)
3.3 parts water
0.6 parts of Lupragen N 107® (BASF Aktiengesellschaft)
0.8 parts of aminopropyliminedazole
0.5 parts Tegostab B 8631® (Goldschmidt)

Component B

42 parts of Lupranat M 20 W®
11 parts of Lupranat MES®
47 parts of Lupranat MI®

Example 2

Production of an aromatic flexible polyurethane foam, hereinafter referred to as comparison system 2, by intensive Mix 115.24 g A component with 100 g B component (Index 100) using a stirrer at a speed of 1250 rpm and transferring the foaming mixture into one Plastic container with a volume of 5 l, with the components build as follows:

Polyol Component

95 parts of Lupranol 2045® (BASF Aktiengesellschaft)
5 parts of Lupranol 2047® (BASF Aktiengesellschaft)
10.71 parts of Lupranol 2030® (BASF Aktiengesellschaft)
3.45 parts of water
0.48 parts of Lupragen N 201® (BASF Aktiengesellschaft)
0.13 parts of Lupragen N 206® (BASF Aktiengesellschaft)
0.37 parts of tetramethylhexamethylene diamine (BASF Aktiengesellschaft)
0.1 part Tegostab B 8680® (Goldschmidt)

Component B

75 parts of Lupranat M 20 W®
25 parts, Lupranat MP 111®

Example 3

Production of an aliphatic flexible polyurethane foam, hereinafter referred to as comparison system 3, by intensive Mixing 110 g A component with 100 g B component (index 110) with the help of a stirrer at a speed of 1250 rpm and converting the foaming mixture into a plastic vessel with a volume of 5 l, the components being as follows build up:  

Polyol Component

56 parts of Lupranol 2042® (BASF Aktiengesellschaft)
35 parts of Lupranol 2045® (BASF Aktiengesellschaft)
2 parts of water
3 parts Lupragen N 209® (BASF Aktiengesellschaft)
2 parts Lupragen N 201® (BASF Aktiengesellschaft)
1 part Lupragen N 206® (BASF Aktiengesellschaft)
1 part Kosmos 29 (Goldschmidt) 1 part Tegostab B 8680® (BASF Aktiengesellschaft)

Component B

100 parts of Basonat HI 100® (BASF Aktiengesellschaft)

Example 4

To modify the polyurethane foams of Examples 1 to 3 were the foams with an ethanolic KOH solution (KOH content = 5%) soaked and then annealed at 100 ° C.

Example 5

To modify the polyurethane foams of Examples 1 to 3, the foams were made with an acetone 5% poly impregnated ethyleneimine solution and then annealed at 100 ° C.

Example 6

A sheet measuring 20.30.1 cm ^{3 was} cut out of the foam produced in Example 2. This was then placed in a 560 l climatic cabinet in which an acetic acid concentration of approximately 140 to 160 ppm V / V was set beforehand (V / V = volume-related concentrations). The decrease in acetic acid concentrations was monitored every five minutes with a gas chromatograph and is shown graphically in FIG. 1. For comparison, the acetic acid concentrations obtained by Basotect® (melamine-formaldehyde foam from BASF Aktiengesellschaft) and an open-cell polystyrene foam are shown as a function of time.

Example 7

Sheets of dimensions 20.30.1 cm ^{3 were} cut out of the foam materials produced in Examples 1, 2 and 3. These were then placed in a 560 l climate cabinet in which an acetic acid concentration of approx. 140 to 160 ppm V / V was set beforehand (V / V = volume-related concentrations). The decrease in acetic acid concentrations was monitored every five minutes with a gas chromatograph and is shown graphically in FIG. 2.

Example 8

Two sheets measuring 20.30.1 cm ^{3 were} cut out from the aromatic polyurethane foam produced in Example 1. One of these plates was also treated as described in Example 4. The results in Fig. 3 show the gas chromatographically monitored decrease in acetic acid concentration for the modified and unmodified foam. For the time t = 0, the acetic acid concentration was set to 100%.

Example 9

From the aliphatic polyurethane foam produced in Example 3, two sheets measuring 20.30.1 cm ^{3 were} cut out. One of these plates was also treated as described in Example 4. The results in FIG. 4 show the gas chromatographically monitored decrease in the acetic acid concentration for the modified and the unmodified foam.

Example 10

Two sheets measuring 20.30.1 cm ^{3 were} cut out of the aromatic polyurethane foam produced in Example 1. One of these plates was also treated as described in Example 5. The results in FIG. 5 show the gas chromatographically monitored decrease in the acetic acid concentration for the modified and the unmodified foam.

Example 11

Panels of various dimensions were cut out of the aromatic polyurethane foam produced in Example 1, and the panels were treated as described in Example 5. The results in FIG. 6 show the gas chromatographically monitored decrease in the acetic acid concentration for the modified foam pads of different dimensions.

Claims (9)

1. Containing polyurethane foams

• a) ethylene imine, polyethylene imine, polyvinylamine, carboxy methylated polyethylene imines, phosphonomethylated poly ethylene imines, quaternized polyethylene imines and / or dithiocarbamitized polyethylene imines or
• b) alkali and / or alkaline earth metal hydroxides or

a mixture of (i) and (ii). 2. Polyurethane foams according to claim 1, containing (i) covalently bound to the polymer of the foam. 3. polyurethane foams according to claim 1, containing as Alkali and / or alkaline earth hydroxides (ii) sodium hydroxide and / or potassium hydroxide. 4. polyurethane foams according to one of claims 1 to 3, containing 0.1 to 80 wt .-% of (i) and / or (ii), based on the weight of the foam. 5. Use of polyurethane foams according to one of the Claims 1 to 4 for the adsorption of odorous substances. 6. Use of polyurethane foams according to one of the Claims 1 to 4 for the production of moldings. 7. A process for the preparation of polyurethane foams by reacting polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanates, characterized in that

• a) ethylene imine, polyethylene imine, polyvinylamine, carboxy methylated polyethylene imines, phosphonomethylated poly ethylene imines, quaternized polyethylene imines and / or dithiocarbamitized polyethylene imines or
• b) alkali and / or alkaline earth metal hydroxides or a mixture of (i) and (ii)
  on the surface of the foam.

8. The method according to claim 7, characterized in that one the reaction in the presence of compounds (i) and / or (ii) performs. 9. The method according to claim 7, characterized in that one the polyurethane foam after its manufacture with the Compounds (i) or solutions of the compounds (ii) saturated.