DE102007062525A1 - New polyurethanes containing cyclodextrins in chemically bonded form, show complexing power and are useful e.g. in producing filter materials or protective clothing - Google Patents

Abstract

New polyurethanes (I), prepared from polyols and polyisocyanates, contain cyclodextrins and/or cyclodextrin derivatives in chemically bonded form, in an amount of 0.1-45 (preferably 1-12.5) wt. % based on the polyol components. An independent claim is included for a support material (II) coated with (I).

Description

The The invention relates to a process for the preparation of polyurethanes, preferably Polyurethane flexible foams and polyurethane adhesives, by Reaction of organic polyisocyanates with polyether polyols or polyester polyols with the simultaneous use of cyclodextrins and / or its derivatives, optionally in the presence of adsorber materials such as Activated carbon / zeolites, water and / or other propellants, Catalysts and / or other auxiliaries and additives.

Polyurethane foams have been known for a long time. Their synthesis and uses are widely described in the literature (see, for example: Plastics Handbook, Volume VII, "Polyurethane", 1st edition 1966 (publisher: Dr. R. Vieweg and Dr. A. Höchtlen) and the second edition (1983) and the third edition (1993) (publisher: Dr G. Oertel, Carl Hanser Verlag, Munich ).

The use of activated carbon / zeolites as filter materials for filtering out pollutants from fluid media has also been described in many cases (see, for example, US Pat. H. Marsh, Activated Carbon, Publisher Elsevier (2006) ,

Cyclodextrins are macrocyclic molecules composed of six, seven or eight α-D-glucose units. They are well-defined circular molecules with a hydrophobic cavity (see 1 : "Structures of cyclodextrins and their dimensions (in pm)). Cyclodextrins are able to store a large number of organic molecules in this cavity. They are used industrially in the field of pharmacy and cosmetics ( J. Szejtli, Cyclodextrin Technology, Kluwer, Dordrecht 1988 ).

There the hydroxyl groups of the cyclodextrin molecules to the outside oriented, they are water-soluble. The cavity becomes surrounded by nonpolar groups so that he himself is nonpolar and preferably nonpolar molecules or parts of molecules be stored. By the complex formation of organic molecules in the cavity of the cyclodextrins decreases the water solubility the complexes formed. In addition, the trapped Molecules stabilized against light or oxygen. Of the Vapor pressure of volatile substances is due to complex formation significantly reduced. For technical applications are the following effects of complex formation with cyclodextrins of crucial importance: Stabilization light, oxidation, heat and / or hydrolysis sensitive Substances, reducing the vapor pressure of volatile Substances, delay the drug release of pharmaceutical Active substances and a resulting longer effectiveness, Increase in solubility and bioavailability poorly water-soluble substances, separation of individual Components of mixtures and masking of odorants and flavorings.

The permanent fixation of the cyclodextrins on different textile materials is known (see, for example, BH -J Buschmann, D. Knittel, E. Schollmeyer, DE 4036328 ; DE 4035378 and DE 10060710 ). The binding of the cyclodextrins takes place in such a way that their removal by washing processes is not possible. Through the washing process, the cavities of the fixed cyclodextrin molecules are emptied.

The removal of odors or the scenting of textile materials with the aid of cyclodextrins or cyclodextrin derivatives is likewise known (see, for example, BT Trinh, JM Gardlik, TJ Ranks and F. Benvegnu US 5094761 , JM Gardlik, T. Trinh, TJ Ranks and F. Benvegnu US 5234610 , T. Trinh, JM Gardlik, TJ Ranks and F. Benvegnu EP 0392607 and JM Gardlik, T. Trinh, TJ Ranks and F. Benvegnu EP 0392606 ).

Since cyclodextrins are water-soluble, a series of work has been undertaken so far to immobilize cyclodextrins and thus also to be able to use them as complexing agents in water. For this purpose, a large number of cyclodextrin-containing polymers have been synthesized (see, for example, US Pat. DE 196 12 768 or WO 97/36948 and the references and patents cited therein). However, all synthetic routes have the distinct disadvantage that the cyclodextrins must be derivatized for use in making the polymers, often under anhydrous conditions. Also, an application difficulty is that polymers were synthesized by crosslinking exclusively cyclodextrins. These products are available as powders and can only be used in one column as complexing agent. The powder can also be added directly to the water (eg waste water) from which substances are to be removed by complexation. However, the polymer must then be filtered off again.

Solms and Egli synthesized a resin by cross-linking cyclodextrins with epichlorohydrin ( J. Solms and RH Egli, Hel. Chim. Acta 48 (1965), pp. 1225-1228 ). They were able to show that the cyclodextrins in the resin are accessible to a number of substances and can be complexed.

Szejtlj et al. have patented a process for the preparation of cyclodextrin foam polymers in 1982 ( DD 202295 ). However, polymers were synthesized by reacting cyclodextrins with epichlorohydrin. The foam was formed by, before and during the reaction, an overpressure of a gas used for foaming which was pressed into the reaction solution and re-expanded before curing. This process is industrially inapplicable compared to polyurethane foams as produced today since this process can not be realized in batch operation. In addition, those of Szejtlj et al. foams produced after the synthesis are washed neutral, which is not necessary in the case of polyurethane foams and is likewise not feasible in the production today.

Ma describes in his patent the preparation of cyclodextrin-containing polymers, which are synthesized inter alia by reaction of cyclodextrins with diisocyanates ( WO 98/22197 ). However, Ma obtains in this way polymeric solids or powders which are suitable for applications for the complexation of substances from solution only as a filling for columns or as an additive for aqueous solutions.

Sreenivasan describes mixtures of polyurethanes and β-cyclodextrin ( K. Sreenivasan: Effect or Added β-Cyclodextrin to the Biostability of Polyurethane, Polymer Engineering and Science, 36 (1996), pp. 262-264 ). However, he is only concerned with improving the biodegradability of cyclodextrin-containing polyurethanes. Investigations into the complexing behavior or the release of fragrances were not carried out.

Nußstein et al. describe in their patent the preparation of cyclodextrin gels which swell in water ( DE 4009840 , 1991). However, the synthesis must be considered relatively expensive and too complicated for industrial use. Anhydrous solvents are technically acceptable only in syntheses with a high degree of added value. The same applies to Huff et al. synthesis described in their patent for the preparation of a cyclodextrin-containing gel ( DE 19612768 , 1997). Again, anhydrous solvents must be used.

According to the invention it has now been found that a synthesis of polyurethanes using cyclodextrins or cyclodextrin derivatives, optionally with simultaneous use of adsorber materials such. As activated carbon / zeolites is possible. The cyclodextrins or cyclodextrin derivatives can be mixed in a single process step with a polyol and crosslinked as usual with an isocyanate. The hydroxyl groups of the cyclodextrins react like the polyols with the isocyanate and thus become part of the polymer (see 2 : Schematic representation of the hydroxyl groups of cyclodextrins). Since the cyclodextrins become part of the polymer, they can not be washed out.

According to the invention the polyurethanes of polyols and polyisocyanates together with cyclodextrins produced. The cyclodextrins become reactive in the polymer backbone involved. Polyols and cyclodextrins make up the polyol component The polyisocyanates are used as crosslinking agent or polyisocyanate component designated.

in the In general, the proportion of cyclodextrins and / or Cyclodextrin derivatives 0.1 to 45 wt .-%, based on the total Polyol. Preferably, their weight fraction 0.2 to 20 wt .-% and particularly preferably 1.0 to 12.5 wt .-%.

As the polyol component in addition to the cyclodextrins especially polyester polyols, polyether polyols, glycols and C ₁ -C ₆ alkanediols, alone or in admixture with each other and in any case with the cyclodextrins in question. As a polyisocyanate component are primarily MDI, TDI, HDI and EPDI in question. In principle, however, it is possible to use all polyols and polyisocyanates known in polyurethane technology. It is understood that the polyisocyanates can also be used in the form of their dimeric and oligomeric derivatives.

Of the Content of other adsorber materials can be up to 50 wt .-%, based on the total weight of the polyurethane.

For the preparation of polyurethanes with additions of activated carbon, Zeolites or other adsorbing additives are the Polyols presented with the adsorber and with the crosslinker added. It is also possible to add polyols and crosslinkers mix and immediately afterwards the reaction mixture with the adsorber to move. It may be appropriate, the To heat polyol or the mixture of polyol / adsorber, to reduce the viscosity of the polyol and a more homogeneous To achieve distribution of polyol / adsorbent. The adsorber materials such as B. activated carbon or zeolites are thereby in the polymeric Material incorporated.

Despite the formation of a chemical bond between the cyclodextrins used and the isocyanates, the effectiveness of cyclodextrins as complexing agents for organic substances such. As odors or cosmetic active substances, hardly affected. This is achieved by a suitable selection and use of such starting materials, which guarantee the product as an open-cell flexible foam or, in the case of adhesives, the accessibility of the cyclodextrin cavities. The polyurethanes produced with cyclodextrins therefore have in principle the properties that previously described for use with textile substrates.

Of the Advantage according to the invention of the described synthesis route It also consists of synthesizing polyurethanes that act as one the synthesis components cyclodextrins or their derivatives, also contained in mixtures, but otherwise from the hitherto industrially used synthesis blocks are produced. Because the selection the educts is such that, inter alia, an open-pored soft foam arises, the thus synthesized polyurethane by complexation Absorb substances. In addition, the cyclodextrins in form the polyurethane odor deposits and then under defined Release conditions again. This is also in analogy to the textiles anchored cyclodextrins.

For the production of polyurethanes in non-foamed form polyols are used in anhydrous form. For the foaming, however, the presence of a foaming agent is required, for example in the form of a customary propellant gas or in the form of water, which leads to the formation of foam-forming CO ₂ . The water can be added separately, but is often already included in the commercial polyols in suitable amounts.

For The realization of the polyurethanes will be the appropriate amounts to polyether polyol or polyester polyol (polyol component) with cyclodextrins mixed. This mixture can be heated for better homogenization but often mixing with a stirrer is sufficient at high speed. Then add with further stirring the crosslinker (polyisocyanate component) added.

at the production of PU foams it plays for the Properties of the products does not matter if a mixture of polyol and cyclodextrins and then cross-linked with isocyanate or whether to present the isocyanate and a mixture of polyol / cyclodextrin allowed to react with stirring. Which variant is chosen is more about the handling of the components aligned.

Derivatizations show that cyclodextrins are always substituted at OH-6. Thus, a tosylation occurs at this position ( T. Seo, T. Kajihara and T. Iijima, Makromol. Chem 188 (1987), pp. 2071-2082 ). The same applies to the reaction of cyclodextrins with isocyanates. Bachmann was able to show by NMR measurements that a derivatization of cyclodextrin with an isocyanate takes place at position OH-6 ( Bachmann et al., J. Carbohydrate Chemistry 17 (1998), pp. 1359-1375 ). It can therefore be assumed that the crosslinking of the cyclodextrin in the polyurethane takes place at this position.

It is not necessary, a special preparation or processing make the synthesis components. Moisture does not matter, the Purity of industrially produced cyclodextrins is for the polymerization is sufficient. Additives such as flame retardants or stabilizers usually do not become negative affected. The UV resistance of appropriately synthesized Polyurethanes also remains.

The can be prepared with cyclodextrins polyurethanes z. B. used for wastewater treatment. Polyurethanes themselves are able to adsorb substances. Investigations of films from mixtures of polyurethanes with cyclodextrins, however, that the equilibration in the absorption of pollutants such as As toluene in the presence of cyclodextrins to about the Factor 30 occurs faster than polyurethanes that are not cyclodextrin (Sreenivasan, Polymer International, 34 (1994), p.221, 223). In addition, the final concentrations to be achieved are substances to be removed in the water when using cyclodextrinhaltigen Polymers significantly better than z. B. when using activated carbon.

Activated carbon (A coal) is a fine-grained coal with a highly porous structure and a very large surface area. Due to the pore structure and large surface area, which is usually 300 to 2000 m ² / g coal is, activated carbon can adsorb a variety of organic substances.

activated carbon becomes predominantly unwanted for removal Accompanying substances from gases or liquids used. So can be z. As organic pollutants such as pesticides or Remove perfluorinated surfactants from water. Likewise Gasoline fumes from the exhaust air from tank systems to activated carbon adsorbed.

The Adsorption on activated carbon is a reversible process. An increase the temperature leads to a desorption. This one uses for the regeneration of activated carbon, but for use in filters and protective clothing, this effect is undesirable.

Like activated carbon, zeolites have a microporous structure. They have pores or channels in which substances can be adsorbed. They have a large internal surface of more than 1,000 m ² / g. Zeolites have an anionic framework charge, so that ionic or polar compounds can be bound. Due to the good adsorptive properties zeolites are used in addition to activated carbon as a sorbent. The adsorption by zeolites is like the active coal is a reversible process. Increasing the temperature also leads to desorption.

By the combination of the properties of activated carbon and / or zeolites With cyclodextrins it is possible to take advantage of the substances for the separation of pollutants. So The activated carbon and zeolites have a high adsorption capacity. Cyclodextrins form predominantly 1: 1 complexes and possess Therefore, compared to the activated carbon or zeolites a lower Binding capacity. However, the complexed substances can be removed not by a temperature increase, but only by Release water again. Humidity is not sufficient.

A further advantage of the combination of cyclodextrins and carbon to remove unwanted substances is that the attainable final concentrations of the substances to be removed are significantly lower with cyclodextrins than with carbon or zeolites. For example, Ma [30] describes in a patent that cyclodextrins can remove substances from the aqueous phase so effectively that their concentration is only in the ppt range (ppt = parts per trillion), while in the case of A carbon, the concentration is in the ppm range. Range (ppm = parts per million). This corresponds to an increase in efficiency by a factor of 10 ⁶ .

As It has also shown according to the invention, it is also possible cyclodextrins, which are already complexed substances included, for the synthesis of PU foams use. The complex remains intact during synthesis. The complexed Substances can be recovered by water after synthesis released from the PU foam.

It it is also possible to use a mixture of cyclodextrins, on the one hand contain already complexed substances, on the other hand but still have an accessible cavity and complexes can form. The advantage is that the unloaded Cyclodextrins e.g. B. can form unpleasant odors. Then, in the application case in the PU foam, a mixture of the complexed Odors and already used in the polymerization Complexes ago. If the PU foam is brought into contact with water, not only is the unpleasant odor released, but also the substance contained in the PU foam by the complex with cyclodextrin. These substances can be flavorings, which then cover the unpleasant smell. The relationship of cyclodextrin and complex can vary between 0% and 100% be and depends on the requirements and application areas of PU foam.

The polyurethanes according to the invention can, in particular in connection with carrier materials, for various purposes are used, in particular for Filtering purposes, for odor binding and for the production of protective clothing in toxic environment. In this case, such support materials themselves consist of a polyurethane according to the invention or be equipped with or coated with it, but also contain multiple layers, in particular two layers. One of these Layer can for example consist of an inventive Polyurethane foam or glue. The other layer can For example, consist of a polyurethane foam or adhesive, which is mixed with another adsorbent or coated is without necessarily containing cyclodextrin.

The The present invention will now be described by way of example explained in more detail the manufacturing, the application areas and the effectiveness of cyclodextrin-containing polyurethanes with adsorbing Additives such. B. show activated carbon.

Under Cyclodextrins and cyclodextrin derivatives are in the following text both α-, β- and γ-cyclodextrin, whose Mixtures and cyclodextrin derivatives which can be prepared therefrom, such as z. B. partially methylated cyclodextrins, prepolymers based on cyclodextrins or cyclodextrin derivatives.

For the synthesis of polyurethane foams with and without cyclodextrins the following products were used: Elastoflex W 5516/115 (polyol component, Elastogran GmbH, Lemförde), Iso 145/8 (isocyanate on Based on MDI, Elastogran GmbH, Lemförde), Bayfit VP.PU 90WF99 (polyol component, Bayer AG, Leverkusen), Desmodur PU 2320 (isocyanate component based on MDI, Bayer AG, Leverkusen), SR-Pol 3900 and SR-Pol 3550 (polyol components from SRS Meeder, Poppenbüll), Petol 36-3BR and Petol 56-2 (polyol components from OLTCHIM, Romania), Cavamax W6 (α-cyclodextrin from Wacker Chemie AG, Burghausen), CAVATEX W7 (β-cyclodextrin from Wacker Chemie AG, Burghausen), GAMMA W8 (γ-cyclodextrin from Wacker Chemie AG, Burghausen), BETA W7 M1.8 (partially methylated β-cyclodextrin from Wacker Chemie AG, Burghausen), CAVASOL W7 HP (hydroxypropylated β-cyclodextrin the company Wacker Chemie AG, Burghausen).

In addition, the following diols, crosslinkers, catalysts and other auxiliaries were used for the syntheses: 1,4-butanediol (Merck Schuchardt, Hohenbrunn), 1,5-pentanediol (Merck Schuchardt, Hohenbrunn), ethylene glycol (Sigma-Aldrich GmbH, Steinheim), Diphenylmethane-4,4'-diisocyanate (MDI, Merck Schuchardt, Hohenbrunn), 2,4-toluene diisocyanate (TOI, Sigma-Aldrich GmbH, Steinheim), He xamethylene diisocyanate (HDI, Merck Schuchardt, Hohenbrunn), 1,4-diazabicyclo [2.2.2] octane (DABCO, Sigma-Aldrich GmbH, Steinheim), Tegomer H-SI 2111 (Degussa), demineralized water (Millipore Milli-Q _plus 185 )

The following reagents were used for the detection of complexations:
4-nitrophenol (p-nitrophenol, Merck Schuchardt, Hohenbrunn), phenol red (Sigma-Aldrich GmbH, Steinheim), toluene (Riedel-de-Haen, Seelze)

example 1

40 g of polyol are initially charged and mixed with 21 g of crosslinker. After this the mixture was stirred, the reaction mixture is followed About 15 seconds and forms a soft foam. This foam corresponds to those foams produced industrially become. It serves as reference material for investigations for the characterization of foams with cyclodextrins.

Example 2

35 g of polyol are mixed with 5 grams of cyclodextrin and stirring 21 g of crosslinker added. The reaction mixture goes to about 15 Seconds and forms a soft foam.

Detection of the complexing power of cyclodextrin is possible with the aid of an alkaline solution of phenolphthalein ( K. Beermann, H. -J. Buschmann, D. Knittel, E. Schollmeyer, Textilveredlung 37, 17 (2002) , A drop of this solution is quickly decolorized after application to the surface of the PU foam, even if the foam itself is alkaline. After washing the PU foam twice in distilled water and then drying, the detection of cyclodextrins with phenolphthalein remains positive.

Example 3

40 g of polyol, 3 g of 1,4-butanediol and 5 g of cyclodextrin are mixed and added with stirring 24.4 g of crosslinking agent. The reaction begins after about 15 seconds, it forms a soft foam.

Example 4

40 g of polyol, 3 g of 1,4-butanediol and 5 g of cyclodextrin are mixed and 33.1 g of crosslinker were added with stirring. The reaction starts after about 15 seconds and forms a soft foam.

Example 5

40 g of polyol, 3 g of 1,4-butanediol and 10 g of cyclodextrin mixed and under Stir 33 g of crosslinker added. After about 15 seconds begins the reaction and it forms a soft foam.

Example 6

20 g of polyol, 5 g of 1,4-butanediol and 20 g of cyclodextrin mixed and under Stirring 30 g of crosslinker added. After about 15 seconds begins the reaction, and it forms one in comparison to the other Foaming a little hard soft foam.

Example 7

For Evidence of complexations of cyclodextrin in PU foam were initially 2 foams from the same starting materials, but once with and once without cyclodextrins produced. For a 41.4 g of polyol with 19 g of crosslinker mixed and on the other hand, a mixture of 36.6 g of polyol and 5 g of cyclodextrin and also crosslinked with 19 g of crosslinker.

From Both foams were each weighed 1.52 g of foam and with 50 ml of a solution of 5.7 mg p-nitrophenol in least. 250 ml of water are added. It was expected that the over a solution of p-nitrophenol which is present in the foam with cyclodextrin greater concentration decrease than the without cyclodextrin.

After this the solution for two days over the foams had become the supernatant solutions decanted and measured photometrically. The stock solution showed an extinction coefficient, measured at 400 nm, from 2,244 units to (with dilution). The solution over the Foam without cyclodextrin had 0.9099 units and over the foam with cyclodextrin 0.4099 units. The concentration to p-nitrophenol was so clear in the sample with cyclodextrin taken off as without.

Example 8

In In another qualitative test, 3.6 mg of p-nitrophenol in Dissolved 250 ml of water and with 1.0 N aqueous sodium hydroxide solution adjusted to a pH of 11. Of the foams with and without cyclodextrin (see Example 7) were respectively 1.16 g weighed into an Erlenmeyer flask, with 40 ml of the solution spiked with p-nitrophenol and shaken for one day. Subsequently Extinctions of supernatant solutions became measured.

The extinction (400 nm) of the stock solution was 0.3775 units, that of the foam without cyclodextrin 0.3373 units and the foam with cyclodextrin 0.3282 units, whereby it can be seen that the latter, although not very pronounced, more p Nitrophenol from solution ent than the one without cyclodextrin.

Example 9

For the proof that for the production of PU foams Cyclodextrins can be used that are already complexed Substances containing β-cyclodextrin was mixed with a commercial deodorant added. The mixture was stirred. Then the cyclodextrin became initially at 70 ° C for four hours and then dried at 120 ° C for 2 hours. The cyclodextrin was almost odorless.

For the preparation of the PU foam was 36 g of polyol with 3 g of deodorant Complexed containing cyclodextrin mixed and intensively with 21 g of crosslinking agent stirred After a short time, a soft foam formed, which smelled slightly of deodorant.

Of the Foam was left open for 45 days. After that there was no smell more noticeable. The foam was cut open. Even then was still no smell perceptible. The foam was mixed with water and subjected to an odor measurement. All six subjects stated that with the dry foam no smell and with the moistened a smell of deodorant could be perceived. Accordingly, you can for the synthesis of cyclodextrin-containing PU foams complexes from cyclodextrins and complexed substances without loss of function be used.

Example 10

For the same reasoning was made with 40 g of polyol and 2 g of cyclodextrin, which already complexed the fluorescent dye rhodamine B Form, mixed intensively with 21 g of crosslinker. It formed while a soft foam under the usual conditions. The foam was cut open and placed under a UV lamp (365 nm). It showed that the polyurethane foam had fluorescent properties, as well as the starting complex of cyclodextrin and the dye.

Example 11

Also for the same reasoning, 39.9 g of polyol were used and 2 g of cyclodextrin, which already contains the dye Resolin red FB in Complexed form, mixed intensively with 21 g of crosslinking agent. It formed a soft foam under the usual conditions. Two samples of identical weight were taken from this foam. One sample was mixed with 50 ml of dry acetone and the other with Acetone / water (40 ml / 10 ml). After appropriate reaction time the solutions were measured photometrically. It showed itself, that the solution with water / acetone is almost twice as much Resolin red FB contained as the sample with pure, dried Acetone.

Example 12

to Representation of a PU foam with a significant proportion of Activated carbon was 40 g of polyether polyol with 60 g of activated carbon beads mixed and heated in a drying oven to about 60 ° C. The Heating caused a significant decrease in viscosity of the polyether polyol and allowed for better mixing with the activated carbon beads. Then 21 g of isocyanate were added with stirring. After about 15 seconds, the foam went on and formed a soft foam.

Example 13

to Representation of a PU foam with a significant proportion of Activated carbon and cyclodextrin were 35 g polyether polyol with 60 g activated carbon beads and 5 g of β-cyclodextrin mixed and in the oven on heated to about 60 ° C. The warming caused a significant decrease in the viscosity of the polyether polyol and allowed better mixing with the activated carbon beads. Then 21 g of isocyanate were added with stirring. After approx. 15 seconds went on the reaction mixture and formed a soft foam.

Example 14

To the Evidence that the cyclodextrin is a nearly temperature independent Complexing, PU foams were used for a qualitative test, containing both activated carbon and activated carbon / cyclodextrins, mixed with toluene-containing water in an Erlenmeyer flask and let one day stand. Then the solution was decanted off and the foams in the oven at 110 ° C a Day dried. Then the foams were transferred into an Erlenmeyer flask, each with Water and extracted with diethyl ether. The extracts were over Dried magnesium sulfate and analyzed by GC / MS. It showed itself that only from the foam that contained activated carbon / cyclodextrin, was detectable within the detection limit of the GC / MS instrument toluene. For the foam containing only activated carbon, no toluene was detectable.

Example 15

For the mechanical immobilization of activated carbon, 37 g of polyol, 5 g of 1,4-butanediol and 2 g of water were mixed. After brief homogenization, 21 g of crosslinker were added with vigorous stirring. After about 15 seconds, 70 g activated charcoal were added with slight stirring and stirred briefly. It forms a mass that initially looked only to activated carbon. Then it forms a high viscosity mass. After a short time, the reaction started and a soft foam was formed.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 4036328 [0006]
• - DE 4035378 [0006]
• - DE 10060710 [0006]
• US 5094761 [0007]
• - US 5234610 [0007]
• - EP 0392607 [0007]
• EP 0392606 [0007]
• - DE 19612768 [0008, 0013]
• WO 97/36948 [0008]
• - DD 202295 [0010]
• WO 98/22197 [0011]
• - DE 4009840 [0013]

Cited non-patent literature

• - Kunststoff-Handbuch, Volume VII, "Polyurethane", 1st edition 1966 (publisher: Dr. R. Vieweg and Dr. A. Höchtlen) and the second edition (1983) and the third edition (1993) (publisher: Dr. G. Oertel, Carl Hanser Verlag, Munich [0002]
• - H. Marsh, Activated Carbon, Elsevier Publishers (2006) [0003]
• - J. Szejtli, Cyclodextrin Technology, Kluwer, Dordrecht 1988 [0004]
• - J. Solms and RH Egli, Hel. Chim. Acta 48 (1965), pp. 1225-1228 [0009]
• K. Sreenivasan: Effect or Added β-Cyclodextrin to the Biostability of Polyurethane, Polymer Engineering and Science, 36 (1996), pp. 262-264 [0012]
• T. Seo, T. Kajihara and T. Iijima, Makromol. Chem 188 (1987), pp. 2071-2082 [0025]
• Bachmann et al., J. Carbohydrate Chemistry 17 (1998), pp. 1359-1375 [0025]
• - K. Beermann, H. -J. Buschmann, D. Knittel, E. Schollmeyer, Textilveredlung 37, 17 (2002) [0044]

Claims (19)

Polyurethanes produced on the basis of polyols and polyisocyanates, characterized in that the polyurethanes contain 0.1 to 45% by weight, based on the weight of the polyol component, of cyclodextrins and / or cyclodextrin derivatives in chemically bound form. Polyurethanes according to claim 1, characterized in that that they are 0.2 to 20 wt .-%, preferably 1.0 to 12.5 wt .-%, based on the weight of the polyol component, cyclodextrins in chemically bound Form included. Polyurethanes according to one of the preceding claims, prepared using polyester polyols, polyether polyols, glycols and / or C ₁ -C ₆ alkanediols. Polyurethanes according to one of the preceding claims, prepared using MDI, TDI, HDI and / or IPDI in monomeric or oligomeric form. Polyurethanes according to one of the preceding claims, prepared using α-, β- and / or γ-cyclodextrin in monomeric, dimeric, primer or higher oligomeric form. Polyurethanes according to one of the preceding claims, characterized in that the cyclodextrins wholly or partly loaded with active ingredients. Polyurethanes according to claim 6, characterized in that that the active ingredients are odors, insecticides, fungicides or dyes are. Polyurethanes according to one of the preceding claims, characterized in that it admixed further adsorbents contain. Polyurethanes according to claim 8, characterized in that that the other adsorbents activated carbon, zeolites, silica gel and / or alumina. Polyurethanes according to Claim 8 or 9, characterized that they add the adsorbent (s) in an amount of up to 50 wt .-%, based on the total weight. Polyurethanes according to one of the preceding claims in the form of a foam or an adhesive. Carrier material coated with a polyurethane according to one of claims 1 to 11. Support material according to claim 12 with two-layered Structure, wherein the one layer of cyclodextrinhaltigem polyurethane according to one of claims 1 to 11 and the second layer from a polyurethane containing another adsorbent consists. Carrier material according to claim 12, characterized in that the carrier material consists of a cyclodextrin-containing Polyurethane exists or is equipped with it and one another adsorbent-containing polyurethane applied thereto is. Carrier material according to claim 12, characterized in that that another adsorbent on the substrate with a cyclodextrin-containing polyurethane adhesive according to one of Claims 1 to 11 is applied. Support material according to claim 15, characterized in that that the activated carbon is applied to a carrier material is that with a cyclodextrin-containing polyurethane according to one of Claims 1 to 11 is equipped or from it consists. Support material according to one of the claims 12 to 16, characterized in that the carrier material is permeable to air. Use of a polyurethane according to any one of the claims 1 to 11 or a carrier material according to claim 12 to 17 as or for the production of filter material. Use of a polyurethane according to any one of the claims 1 to 11 or a carrier material according to one of the claims 12 to 17 for the production of protective clothing.