DE19824134A1 - Foamed polyurethanes containing saccharide useful for production of shaped parts - Google Patents

Abstract

Reaction of acidified saccharide with an alkaline reagent and an alkylene oxide results in surface etherification or partial alkoxylation of the saccharide, whereby cleavage and side reactions are avoided. Combination of the alkoxylation product with sugar-based polyetherpolyol gives foamed polyurethane of increased heat resistance and profile stability on storage and decreased shrinkage. Compact or cellular oligo- and/or polysaccharide containing polyurethane is prepared by reaction of (a) high molecular compounds having at least two reactive H with (b) organic and/or inorganic modified organic di- and/or polyisocyanates; (c) a chain lengthening- and/or crosslinking agent; (d) a propellant; (e) catalysts; and (f) adjuvants. The high molecular compound (a) comprises (wt.%): (a1) saccharide containing compounds (1-100) and (a2) at least one polyol (0-99), relative to the total weight of (a). The saccharide containing compound (a1) comprises (wt.%): (a11) an alkoxylation component (1-99) and (a12) a polyoxyalkylenepolyol (1-99) of an oligo- and/or polysaccharide, relative to the total weight of alkoxylation component (a11), defined and prepared as below. Independent claims are included for: (1) An oligo- and/or polysaccharide alkoxylation component obtained by reaction of (wt.%): (a111) at least one oligo- and/or polysaccharide product (5-70) of pH 3.5-6 with (a112) an alkylene oxide (20-94.9), (a113) an alkali (0.1-10), relative to the total weight of alkoxylation component; (2) an oligo- and/or polysaccharide containing polyurethane prepared as above; a (3) shaped polyurethane parts obtained as above;

Description

The present invention relates to a method for producing a sac charide-containing oxalkylation component, a process for the preparation of Polyurethanes using and from the oxyalkylation component manufactured molded parts.

Polysaccharides, especially starch, have always been used not only as Food, but also as an industrial raw material, e.g. B. in chemical Industry. Representations of polysaccharides and starch included: R. L. Whistler et al., In: Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., 1983, volume 21, pp. 492-507, "Starch"; P.A. Sandford et al., In: Polysaccharides, Academic Press, 1983, Volume 2, pp. 411-490, "Industrial utilization of polysaccharides "; and A. Guilbot et al., in: Polysaccharides, Academic Press, 1985, volume 3, pp. 209-282, "Starch".

Basically, starch has been made in two different ways used for the production of polyurethanes. On the one hand, the strength served as a raw material source for the synthesis of low molecular weight starting materials Manufacture of polyurethane building blocks. On the other hand became native strength also not dismantled and incorporated as a solid in polyurethane.  

It is known to use starch as a building block by this is broken down to glucosides especially in the acidic medium and the polyols produced in this way by subsequent oxalkylation or Esterification can be modified. Such a process is described in US-A- 3, 165.508 and US-A-3,541,034, in the starch with a Polyol is reacted in the presence of an acid, with the starch by the acid is practically completely hydrolyzed, and at the same time or is then alkoxylated with an alkylene oxide. The resulting poly oxyalkylene ether is then added with an organic polyisocyanate Polyurethane foams implemented. A similar process is also used in US-A- 3,457,178, in which phosphoric acid for the hydrolysis of the starch is used. The phosphorus thus present gives the manufactured Polyurethane foam non-burning properties. In US-A-3,957,702 Polyurethane foams with organic polyisocyanates Phosphorus-containing starch polyethers or starch polyether hydrolyzates, manufactured. The phosphor is made by implementing the appropriate starch materials with polyphosphoric acid introduced. That way you can flame retardant foams are produced.

As described above, the incorporation of phosphorus into polyurethane foams to improve the fire behavior of the starchy polyurethane lead foams. This effect can be enhanced if the strength is in Combination with synergistic flame retardants is used. The disadvantage of incorporating starch in polyurethanes is often poor tter mechanical properties of the polyurethane parts, because the starch particles mostly only act as a filler and not chemically into the polyurethane matrix to be built in. US-A-3,405,080 describes the pressing of an un foamed diisocyanate prepolymers with starch under high pressure (10,000 psi = 700 bar) and at temperatures between 70 and 100 ° C to a To bring about a reaction between the starch and the prepolymer. In GB  A-1 440 831 describes polysaccharides, such as starch, in polyurethane foams installed by using the polyisocyanate, a catalyst for the Polymerization of the isocyanate and a blowing agent are mixed. The Presence of the polysaccharide is said to result in a foam with larger foam lead stability and better fire behavior. Also in DE-OS-24 48 216 a carbohydrate such as sugar, starch or cellulose as a filler in Polyurethane foams incorporated. The foams obtained have a increased hardness and improved fire resistance and form when ver burn coal, which is the trickling of burning molten polyurethane han prevented. US-A-4,156,759 describes polyurethane foams which contain an amylose material by an antioxidant or the Removal of oxidizable substances is stabilized.

EP-A-0 003 160 discloses semi-flexible, starch-containing polyurethane foams known with an open cell structure, which at a 20-25% lower density show good mechanical properties than conventional polyurethane foams. DE-OS-31 06 246 rigid polyurethane foams filled with starch are open beard, where to improve the application properties granular starch is at least partially replaced by so-called "swelling starch", whose natural grain structure is destroyed by heat treatment of moist starch has been. GB-A-2 094 315 relates to highly elastic polyurethane foams which using starch as a charring element and an intu measuring catalyst (e.g. ammonium polyphosphate). In the event of a fire, these foams charred. That described in US-A-4,458,034 A flame-retardant, non-dripping soft foam contains in addition to the Common ingredients with a flame retardant and a polyol the isocyanate component of non-reactive hydroxyl groups, in the fire the flame retardant and the (unreacted) polyol fall together react to form a non-dripping, carbon-rich layer. In DE-OS-38 44 048 are flame-retardant, elastic polyurethane soft  foams made using flame retardants that Melamine and possibly starch and an additional flame retardant. WO 91/16403 discloses fire retardants containing a carbohydrate or a Starch as a binder and a dehydrating agent, e.g. B. phosphate salts, contain. These fire protection agents are either added to the desired substance itself, e.g. B. by admixture as a filler in polyurethane nen, or by subsequent treatment of a raw material by impregnation applied.

To the reaction between the numerous, however largely It has so far been possible to promote inert hydroxyl groups of the starch and of the isocyanates been proposed to dissolve the starch in water and use this solution Implement isocyanates. However, aqueous starch solutions themselves contain high starch concentrations and thus correspondingly high viscosities high excess of water, so that the desired starch Isocyanate reaction from the prevailing water-isoeyanate reaction is covered. US-A-4,291,129 describes the manufacture of flame retardant gem polyurethane foam using u. a. an aqueous coal hydrate solution, the water being the carrier for the carbohydrates and other inorganic salts present. The foams produced maintain their structural integrity in the event of a fire. In WO 83/02120 describes polyurethane foams that are made flame retardant can be made by adding a flame retardant, and by Reaction of a carbohydrate, polyisocyanate and water in the presence a surfactant and a catalyst. A procedure for Dissolve starch in various solvents used to train Hydrogen bonds are capable, is in DE-OS-41 43 132 be wrote. This is achieved by removing the chemically and physically Tied oxygen from the system and scissors, which dissolves  can be produced with up to 10% starch. However appears this process is very cumbersome and hardly feasible on an industrial scale.

In addition to the above-mentioned reactions of polyurethanes with polysaccharides or starches, the reaction of polyurethanes with esterified polysaccharides is also known. Starch and cellulose esters are low and high degrees of substitution commercially available. Acetates in particular are easily accessible via the reaction with acetic anhydride, which is usually catalyzed by pyridines, such as. B. in RL Whistler, Starch, "Starch Esters", Academic Press, 1984, pages 332 to 342. The esterification increases the reactivity of the polysaccharides or starch, improves their compatibility with other non-polar components, and polyurethanes with improved properties are obtained. A disadvantage of the methods described in the literature is that the esters have to be worked up in order to remove excess starting materials and catalysts. For example, when the reaction is carried out in solvents, these must be removed before use in polyurethane systems. In the article "Reactivity of modified starches with isocyanates" by FH Otey et al., The Starch, 1972, 24/4, pages 107 to 110, starch was modified by esterification or etherification and the influence of this modification on the reactivity of the starch examined with isocyanates. The maximum reactivity of the modified starches was at a degree of substitution of 0.7, with this degree of substitution hardened urethane plastics, which had been produced from batches with 20% of the starch derivatives, exhibiting the maximum breaking energy. DE-PS-41 14 185 describes wet-strength, thermoplastic starch materials which consist of starch acyl compounds which are obtainable from amylose-rich starches and are sparingly soluble in water, and of biodegradable plasticizers, these starch materials being biodegradable. WO 92/13894 describes a radiation-polymerizable starch ester urethane which contains an ester of a C ₁ -C ₄ carboxylic acid and an ethylenically unsaturated group bonded to the starch via a urethane bond.

DE-A-195 44 121 discloses a process for the production of poly saccharide-containing polyurethanes, in which polyester polyols based on Oligo- and / or polysaccharides can be used. To make this Polyester polyols are the usual polyester polyols with polysaccharides sets, resulting in a simple superficial esterification of the Polysac charide is coming. Usually these esterifications or transesterification gene carried out at temperatures above 200 ° C. Problematic here is that the saccharides can be split at such temperatures and can oxidize what is a targeted, reproducible polymer construction difficult. In addition, caramelization reactions with other Side reactions occur.

In summary, the disadvantages of the methods described above are Derivatization of starch is that there is a risk that on the one hand Fission reactions, isomerizations and oxidation reactions in the starch can run off, and on the other hand polyurethane foams are obtained are only unilaterally improved in their properties, e.g. B. can increase me of hardness a simultaneous drop in processing and physikome opposed to chanical properties.

The object of the present invention was a method for the production of saccharide-containing polyurethanes, in particular from to create hard polyurethane foams in which polyurethanes with good mechanical and processing properties can be obtained. Especially should have better heat resistance and lower thermal conductivity after storage with low shrinkage and at the same time good processability of the polyurethane can be achieved.  

Surprisingly, it was found that by implementing an acidified saccharides with an alkaline reagent and an alkylene oxide for a superficial etherification or partial alkoxylation of the saccharide comes, cleavage and side reactions are avoided. Through the Combination of this alkoxylation product with a polyether polyol Sugar-based products can be used to produce polyurethane usual substances made of polyurethanes, especially rigid polyurethane foams that have improved heat resistance after storage have better curing and less shrinkage.

Thus, the invention relates to a process for the preparation of an oligo- and / or polysaccharide-containing oxalkylation component, which is characterized in that

• a ₁₁₁ ) 5 to 70% by weight of at least one oligo- and / or polysaccharide product with a pH of 3.5 to 6
  a ₁₁₂ ) 20 to 94.9% by weight of at least one alkylene oxide and
  a ₁₁₃ ) 0.1 to 10% by weight of at least one alkaline agent,
  each based on the total weight of the oxyalkylation component.

In addition, the invention relates to a process for the production of compact or cellular, oligo- and / or polysaccharide-containing polyurethanes by reacting

• a) High molecular weight compounds with at least two reactive Hydrogen atoms with
• b) organic and / or modified organic di- and / or poly isocyanates
  in the presence or absence of
• c) chain extenders and / or crosslinking agents,
• d) blowing agents,  
• e) catalysts and
• f) aids,
  which is characterized in that
  the higher molecular weight compounds a)
  • a ₁ ) 1 to 100 wt .-% saccharide-containing compounds and
  • a ₂ ) 0 to 99% by weight of at least one polyol,
    each based on the total weight of a), wherein the saccharide-containing compounds a ₁ )
    • a ₁₁ ) 1 to 99% by weight of at least one oxyalkylation component and
    • a ₁₂ ) 1 to 99% by weight of at least one polyoxyalkylene polyol of an oligosaccharide and / or polysaccharide,
      each based on the total weight of a ₁ ), wherein an oxyalkylation component a ₁₁ , which can be obtained by the process described above, is used.

The invention further relates to the oxyalkyly produced according to the invention tion component, polyurethanes produced therewith and produced therefrom Molded parts. Further embodiments of the invention are as follows the description, the examples and the subclaims.

The oxyalkylation component is obtained by adding 5 to 70% by weight, preferably 10 to 60% by weight, in particular 15 to 50% by weight, of at least one oligo- and / or polysaccharide product a ₁₁₁ ) with a pH of 3.5 to 6 with 20 to 94.9% by weight, preferably 30 to 89.7% by weight, in particular 40 to 84.5% by weight, of at least one alkylene oxide a ₁₁₂ ) and 0.1 to 10% by weight, preferably 0.3 to 10% by weight, in particular 0.5 to 10% by weight, of at least one alkaline agent a ₁₁₃ ), in each case based on the total weight of the oxyalkylation component, are reacted with one another.

Particularly suitable oligosaccharide and / or polysaccharide products a ₁₁₁ ) are aqueous saccharide products with a pH of 3.5 to 6, preferably 3.5 to 5.0, in particular 3.5 to 4.5. The saccharide products are preferably oligosaccharides, starches and / or glucose syrup, which can be obtained by acidifying the saccharide with a conventional mineral acid, e.g. B. sulfuric acid, hydrochloric acid, or an organic acid, such as acetic acid, are available to the appropriate pH. Particularly suitable starches are native, pre-gelatinized and / or partially degraded starches with DE values between 1 and 90, the DE value (dextrose equivalent value) describing the degree of degradation and, for example, starch completely degraded to dextrose a DE value of 100 owns. In a preferred embodiment of the invention, the starch has a grain size of 10 to 90 microns. The starch preferably has a molecular weight of 10 ⁴ to 10 ⁸ D. The saccharide products a ₁₁₁ ) are preferably an acidified starch product and / or an acidified glucose syrup. Partial hydrolysis of the saccharide is achieved by maintaining the specified pH. In contrast to the prior art, there is therefore no complete hydrolysis of the saccharide according to the invention.

Suitable alkylene oxides a ₁₁₂ ) are alkylene oxides having 2 to 6 carbon atoms in the alkylene radical, alkylene oxides having 2 to 4 carbon atoms being particularly preferred. For example, ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide or tetrahydrofuran are suitable. Most preferred are ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures.

Basically suitable as alkaline agents a ₁₁₃ ) are all alkaline or basic compounds which increase the pH of the saccharide product a ₁₁₁ ), preferably to a pH of 6 to 9, in particular 6 to 8, and which compared to the saccharide product a ₁₁₁ ) do not undergo side-damaging side reactions and do not interfere with further conversion to polyurethane. Otherwise these alkaline agents are not subject to any particular restrictions. Appropriately, this is sodium hydroxide / sodium hydroxide solution, potassium hydroxide / potassium hydroxide solution or basic alcohols, such as, for. B. a basic alcoholate of ethylene glycol, glycerol and / or other OH-functional compounds or polyols.

The reaction of the saccharide product a ₁₁₁ ) with the alkylene oxide a ₁₁₂ ) and the alkaline agent a ₁₁₃ ) is carried out by adding the alkaline agent to the saccharide product before, simultaneously with or after the reaction with the alkylene oxide. Preferably, the saccharide product a ₁₁₁ ) is treated with the alkaline agent a ₁₁₃ ), and the alkylene oxide a ₁₁₂ ) is added simultaneously or subsequently. The reaction is preferably carried out at a temperature of 80 to 130 ° C., in particular 100 to 120 ° C. Pressures from 0.1 to 1.0 MPa, in particular from 0.2 to 0.5 MPa, are preferred. The reaction times are preferably 2 to 15 hours, particularly 2 to 10 hours. It is expedient to mix intensively during the reaction. After the reaction, any existing basic impurities, which are essentially degradation products from the alkaline agents a ₁₁₃ ), are advantageously removed by neutralization with acid, vacuum distillation and / or filtration. The oxyalkylation product can then be mixed with neutral starch products, e.g. B. native, completely and / or partially degraded starch, possibly OH-functional compounds, for. B. glycerol, and / or with further alkylene oxide.

The higher molecular weight compound a) with at least two reactive hydrogen atoms used according to the invention for producing the polyurethane contains 1 to 100% by weight, preferably 20 to 80% by weight, in particular 30 to 60% by weight, of saccharide-containing compounds a ₁ ) and 0 to 99% by weight, preferably 20 to 80% by weight, in particular 40 to 70% by weight, of at least one polyol a ₂ ), in each case based on the total weight of a).

The saccharide-containing compounds a ₁ ) contain 1 to 99% by weight, preferably 10 to 90% by weight, in particular 20 to 80% by weight, of at least one oxyalkylation component a ₁₁ ) and 1 to 99% by weight , preferably 10 to 90% by weight, in particular 20 to 80% by weight, of at least one polyoxyalkylene polyol a ₁₂ ) of an oligosaccharide and / or polysaccharide, in each case based on the total weight of a ₁ ). An oxalkylation component as described above is used as the oxalkylation component a ₁₁ ).

Suitable polyoxyalkylene polyols a ₁₂ ) are polyols which are prepared by the oxyalkylation of oligo- and / or polysaccharides. Suitable alkylene oxides are ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and tetrahydrofuran, ethylene oxide and 1,2-propylene oxide preferably being used. Otherwise, the same applies to the polyoxyalkylene polyols a ₁₂ ) as for the polyoxyalkylene polyols described below as compound a ₂ ). As polyoxyalkylene polyols a ₁₂ ) are particularly suitable reaction products of di- and / or polysaccharides, for. B. Implementation products of sucrose and / or trisaccharides and / or tetrasac charides with ethylene and / or propylene oxide, especially in the presence of low-viscosity OH-functional compounds, such as ethylene glycol or glycerol with OH numbers from 25 to 500.

The polyols or polyhydroxyl compounds a ₂ ) preferably have a functionality of 2 to 8 and a hydroxyl number of 25 to 500. They are expediently selected from the group of polythioethers, polyols, hydroxyl group-containing polyacetals, hydroxyl group-containing aliphatic polycarbonates, polyester polyols, polymer-modified polyether polyols and mixtures of at least two of the polyols or polyhydroxyl compounds mentioned.

Suitable, higher molecular weight polyhydroxyl compounds, such as those used for a ₂ ), have, as has already been stated, advantageously a functionality of 2 to 8 and a hydroxyl number of 25 to 500, polyhydroxyl compounds having a functionality preferably being used for the production of flexible PU foams of preferably 2 to 3 and a hydroxyl number of preferably 30 to 80 and for the production of hard PU foams preferably polyhydroxyl compounds with a functionality of preferably 3 to 8 and in particular 3 to 6 and a hydroxyl number of preferably 100 to 500 are advantageously used. Linear and / or branched polyester polyols and in particular linear and / or branched polyoxyalkylene polyols are preferably used as polyhydroxyl compounds, polyhydroxyl compounds from renewable natural substances and / or chemically modified renewable natural substances being particularly preferred. Also suitable as polyhydroxyl compounds a ₂ ) are polymer-modified polyoxyalkylene polyols, polyoxyalkylene polyol dispersions and other hydroxyl-containing polymers and polycondensates with the abovementioned functionalities and hydroxyl numbers, for example polyesteramides, polyacetals and / or polycarbonates, in particular those made from diphenyl carbonate and hexanediol 1.6 are produced by transesterification, or mixtures of at least two of the higher molecular weight polyhydroxyl compounds a ₂ ) mentioned.

However, poly are used in particular as polyhydroxyl compounds oxyalkylene polyols, which are prepared by known processes, at for example by anionic polymerization with alkali metal hydroxides, such as Sodium or potassium hydroxide, or with alkali alcoholates such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, as Kataly  catalysts and with the addition of at least one starter molecule which contains 2 to 8, preferably contains 2 to 3 reactive hydrogen atoms bound, for Production of polyoxyalkylene polyols for flexible PU foams, and preferably contains 3 to 8 reactive hydrogen atoms bound for forth Provision of polyoxyalkylene polyols for semi-hard and hard PU foam substances, or by cationic polymerization with Lewis acids, such as Antimony pentachloride, boron fluoride etherate and the like. a. or bleaching earth as Catalysts of one or more alkylene oxides with 2 to 4 Carbon atoms in the alkylene radical.

Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately can be used in succession or as mixtures. As starter molecules For example, water, organic dicarboxylic acids, such as Succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl substituted Diamines with 1 to 4 carbon atoms in the alkyl radical, such as optionally mono- and 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, phenylenediamines, 2,3-, 3,4-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diamino-diphenylme than.

Other suitable starter molecules are: alkanolamines, such as, for. B. Ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, such as. B. Diethanolamine, N-methyl- and N-ethyldiethanolamine and trialkanolamines, such as B. triethanolamine, and ammonia. Preferably used polyvalent, in particular two to eight, alcohols and / or Alkylene glycols such as B. ethanediol, 1,2-propanediol and 1,3, diethylene glycol,  Dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, Pentaerythritol, sorbitol and sucrose and mixtures of at least 2 polyhydric alcohols.

The polyoxyalkylene polyols, preferably polyoxypropylene and Polyoxypropylene-polyoxyethylene-polyols, have a functionality of 2 to 8 and hydroxyl numbers from 25 to 500, being for flexible PU foam polyoxyalkylene polyols with a functionality of 2 to 3 and one Hydroxyl number from 30 to 80 and for semi-hard and hard PU foams Polyoxyalkylene polyols with a functionality of 3 to 8 and one Hydroxyl number from 100 to 500 are preferably used and suitable Polyoxytetramethylene glycols have a hydroxyl number from 30 to about 280 exhibit.

Polymer-modified polyols are also suitable as polyoxyalkylene polyols Polyoxyalkylene polyols, preferably graft polyoxyalkylene polyols, in particular those based on styrene and / or acrylonitrile, which are Polymerization of acrylonitrile, styrene or preferably mixtures of Styrene and acrylonitrile, e.g. B. in a weight ratio of 90:10 to 10:90, preferably 70:30 to 30:70, expediently the aforementioned Polyoxyalkylene polyols analogous to the information in German Patent 11 11 394, 12 22 669 (US 3 304 273, 3 383 351, 3523 093), 11 52 536 (GB 10 40 452) and 11 52 537 (GB 987618) are produced, as well Polyoxyalkylene polyol dispersions, which as a disperse phase, usually in an amount of 1 to 50 wt .-%, preferably 2 to 25 wt .-%, contain ten: z. B. polyureas, polyhydrazides, tert-amino groups bound enthal tend polyurethane and / or melamine and the z. B. are described in EP-B-0 011 752 (US-A-4,304,708), US-A-4,374,209 and DE-A-32 31 497.  

The polyoxyalkylene polyols can be used individually or in the form of mixtures be used. They can also with the graft polyoxyalkylene polyols or polyester polyols and the hydroxyl-containing polyester amides, Polyacetals and / or polycarbonates are mixed.

As polyacetals containing hydroxyl groups such. B. from glycols, such as Diethylene glycol, triethylene glycol, 4,4'-dihydroxyethoxy-diphenyldimethyl Compounds that can be prepared from methane, hexanediol and formaldehyde. Suitable polyacids can also be obtained by polymerizing cyclic acetals make valley.

Polycarbonates containing hydroxyl groups are those of themselves known type into consideration, for example by reacting diols, such as B. propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), Diethylene glycol, triethylene glycol or tetraethylene glycol with Diaryl carbonates, e.g. B. diphenyl carbonate, or phosgene can.

Polyester polyols suitable as polyol a ₂ ) can be, for example, organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms and polyhydric alcohols, preferably alkane diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, dialkylene glycols and / or alkane triols having 3 to 6 carbon atoms. Examples of suitable dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used both individually and in a mixture. Instead of the dicarboxylic acids, the corresponding car bonic acid derivatives, such as. B. dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic acid anhydrides. Preference is given to using dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, 20 to 35: 35 to 50: 20 to 32 parts by weight, and in particular adipic acid. Examples of two and polyhydric alcohols, especially alkanediols and dialkylene glycols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, di-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,10-decanediol, glycerin and trimethylolpropane. Ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol or mixtures of at least two of the alkane polyols mentioned, in particular z. B. Mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. Polyester polyols made from lactones, e.g. B. ε-caprolactone or hydroxycarboxylic acids, e.g. B. ω-hydroxycaproic acid.

To produce polyester polyols a ₂ ), the organic, for. B. aromatic and preferably aliphatic dicarboxylic acids and / or their derivatives and the polyhydric alcohols and / or alkylene glycols catalyst free or preferably in the presence of esterification catalysts, advantageously in an atmosphere of inert gases, such as. B. nitrogen, helium, argon and others in the melt at temperatures of 150 to 250 ° C, preferably 180 to 220 ° C, optionally under reduced pressure to the desired acid number, which is advantageously less than 10, preferably less than 2, be polycondensed. According to a preferred embodiment, the esterification mixture is polycondensed at the above-mentioned temperatures up to an acid number of 80 to 30, preferably 40 to 30, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar. As esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation can also in the liquid phase in the presence of diluents and / or entraining agents, such as. B. benzene, toluene, xylene or chlorobenzene, for azeotropic distillation of the water of condensation. To prepare the polyester polyols, the organic dicarboxylic acids and / or their derivatives and the polyhydric alcohols are advantageously polycon densified in a molar ratio of 1: 1 to 1.8, preferably 1: 1.05 to 1.2. The polyester polyols obtained preferably have a functionality of 2 to 4, in particular 2 to 3, and a hydroxyl number of 240 to 30, preferably 180 to 40.

The following isocyanates can be used as di- and / or polyisocyanates b) to carry out the process according to the invention:
Alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as. B. 1,12-dodecane diisocyanate, 2-ethyl-tetramethylene-diisocyanate-1,4, 2-methyl-pentamethylene-diisocyanate 1,5, 2-ethyl-2-butyl-pentamethylene-dii socyanate-1,5, 1,4-tetramethylene diisocyanate and preferably 1,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates, such as. B. cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanate to 3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding Isomerege mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates, such as. B. 2,4- and 2,6-tolylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane-dii socyanate and the corresponding isomer mixtures, mixtures of 4, 4'- and 2,4'-diphenylmethane diisocyanates, polypheryl polymethylene polyisocyanates, mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (raw -MDI) and mixtures of crude MDI and tolylene diisocyanates. The organic di- and polyisocyanates can be used individually or in the form of their mixtures.

Mixtures of diphe have proven successful as organic polyisocyanates nylmethane diisocyanates and polyphenyl polymethylene polyisocyanates preferably those with a diphenylmethane diisocyanate content of at least 35% by weight, e.g. B. from 45 to 95 wt .-% and in particular from 48 to 60 Wt .-%, so that such raw MDI compositions in particular find application.

In one embodiment of the invention, a prepolymer can also be made from a reaction of the higher molecular weight compounds a) with a di and (or polyisocyanate b) are used, both components as are defined above. The prepolymer preferably has an NCO content from 30-12% by weight, in particular from 25-15% by weight. Advantageously 70 to 20% by weight, in particular 60 to 40% by weight, Ver bond a) and 30 to 80 wt .-%, in particular 40 to 60 wt .-%, iso cyanate b), based on the total weight of the prepolymer.

Alb chain extenders c) can be difunctional compounds, as Crosslinking agent c) trifunctional and higher functional compounds each with Molecular weights less than 400, preferably from 62 to about 300 be used. Examples of chain extenders d) be alkanediols, e.g. B. those with 2 to 6 carbon atoms in the alkylene radical, such as B. ethane, 1,3-propane, 1,4-butane, 1,5-pentane and 1,6-hexanediol, and dialkylene glycols, such as. B. diethylene, dipropylene and dibutylene glycol, and as crosslinking agent c) alkanolamines, e.g. B. ethanolamine, dialkanola min, e.g. B. diethanolamine, and trialkanolamines, e.g. B. triethanolamine and Triisopropanolamine, and trihydric and / or higher alcohols, such as. B. Glycerin, trimethylolpropane and pentaerythritol. As chain extension or  Crosslinking agents are also suitable for low molecular weight ethoxylation and / or propoxylation products, e.g. B. those with molecular weights up about 400 of the aforementioned polyhydric alcohols, alkylene glycols, Alkanolamines and aliphatic and / or aromatic diamines.

Preferred chain extenders c) are alkanediols, in particular 1,4-butanediol and / or 1,6-hexanediol, alkylene glycols, especially ethylene glycol and propylene glycol, and as crosslinking agent c) trihydric alcohols, especially glycerin and trimethylolpropane, Dialkanolamines, especially diethanolamine, and triacanolamines, especially triethanolamine.

Suitable blowing agents d) for producing the cellular polyurethanes Water and / or gases present in liquid form at room temperature and liquids which are compared to the compounds a) and the isocyanas ten b), their mixtures or prepolymer mixtures thereof are inert and Boiling points below 50 ° C, especially between -50 ° C and 30 ° C at Have atmospheric pressure, and mixtures of gaseous and liquid against blowing agents. Examples of such preferably usable gases and Liquids are alkanes, e.g. B. propane n- and iso-butane, n- and iso-pentane, preferably technical mixtures of n- and iso-pentane, and Cycloalkanes such as e.g. B. cyclopentane, alkyl ethers such as. B. dimethyl ether, Diethyl ether and methyl isobutyl ether, carboxylic acid alkyl esters, such as. B. Me thyl formate, and halogenated hydrocarbons, such as. B. dichlorofluorme than, trifluoromethane, 1,1-dichloro-1-fluoroethane, monochlorotrifluoroethane, mono chlorodifluoroethane, difluoroethane, dichlorotrifluoroethane, monochlorotetrafluoroethane, Pentafluoroethane, tetrafluoroethane and dichloromonofluoroethane. For the production the cellular polyurethanes, preferably PU foams, are used in particular water, linear and cyclic alkanes with 5 to 7 carbon atoms and mixtures thereof. The blowing agents mentioned by way of example can  can be used individually or as mixtures. Not used as a blowing agent Chlorofluorocarbons should be used as they affect the ozone layer damage.

Used in a mixture with liquids with boiling points below 50 ° C can also be (cyclo) alkanes, such as. B. hexane and cyclohexane and Carboxylic acid alkyl esters, such as. B. ethyl formate, with boiling points above 50 ° C, if the blowing agent mixture expediently has a boiling point below 38 ° C. having. The required amount of blowing agent or mixture can depending on the type of blowing agent or blowing agent mixture and the mixing ratios experimentally determined in a simple manner become. The blowing agents are usually used in an amount of 0.1 to 30 parts by weight, preferably from 1 to 25 parts by weight, based on 100 Parts by weight of components a) to c) used.

Catalysts e) that can be used in PU production preferably compounds which react the reaction of the higher molecular weight Ver Bonds a) with the isocyanates b) or their prepolymer mixtures speed up hard. Suitable catalysts are, for. B. organic Metal compounds, preferably organic tin compounds, such as Tin (II) salts of organic carboxylic acids, e.g. B. tin (II) diacetate, Tin (II) dioctoate, tin (II) diethylhexoate and tin (II) dilaurate and the dialkyl Tin (IV) salts of organic carboxylic acids, e.g. B. dibutyltin diacetate, Dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, and dibutyltin dimercaptid and strongly basic amines, for example amidines, such as. B. 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as. B. Triethyla min, tributylamine, dimethylbenzylamine, N-methyl, N-ethyl, N-cycloh exylmorpholine, dimorpholino-diethyl ether, N, N, N ', N'-tetramethylethylene di amine, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetramethylhexanedi amine 1,6, di- (4-N, N-dimethylaminocyclohexyl) methane, pentamethyldiethy  lentriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, Dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo [3.3.0] octane, Alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyl and N-ethyl-diethanolamine and dimethylethanolamine, tris- (N, N-dialkylamine alkyl) -s-hexahydrotriazines, especially tris- (N, N-dimethylaminopropyl) - s-hexahydrotriazine, tetraalkylammonium hydroxides, such as tetramethylammoni umhydroxide and preferably 1, 4-diaza-bicyclo [2.2.2joctan. Preferably 0.001 to 5% by weight, in particular 0.05 to 2% by weight, are used Catalyst or catalyst combination, based on the weight of the com component a).

The reaction mixture for the production of compact or cellular polyu Rethanes, preferably PU foams, can also be used if necessary Aid f) are incorporated. Surfaces are mentioned, for example active substances, foam stabilizers, time regulators, flame retardants, Fillers, dyes, pigments, antistatic agents, hydrolysis inhibitors, fungi static and bacteriostatic substances.

As surface-active substances such. B. connections into consideration which support the homogenization of the reaction mixtures serve and are also possibly suitable, the cell structure of the PU Regulate foams. Emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids, and salts of Fatty acids with amines, e.g. B. oleic acid diethylamine, stearic acid diethanola min, ricinoleic acid diethanolamine, salts of sulfonic acids, e.g. B. alkali or Aminonium salts of dodecylbenzene or dinaphthylmethane disulfonic acid, and Ricinoleic acid; Foam stabilizers, such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated Fatty alcohols, paraffin oils, castor oil or ricinoleic esters, Turkish red oil and Peanut oil and cell regulators such as pyrogenic silica, paraffins, fatty alcohols  and dimethylpolysiloxanes. To improve the emulsifying effect, the cell Structure and / or stabilization of the foam are also suitable for oligomers Polyacrylates with polyoxyalkylene and fluoroalkane residues as side groups. The Surfactants are usually used in amounts from 0.01 to 5 parts by weight, based on 100 parts by weight of component a), applied.

Suitable flame retardants are, for example, diphenyl cresyl phosphate, Tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, Tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetra kis (2-chloroethyl) ethylene diphosphate.

In addition to the halogen-substituted phosphates mentioned, inorganic cal flame retardants such. B. alumina hydrate, antimony trioxide, Arsenic oxide, ammonium polyphosphate, expandable graphite and calcium sulfate, or Cyanuric acid derivatives, such as. B. melamine, or mixtures of at least two flame retardants such as B. ammonium polyphosphates and melamine and / or expanded graphite, and optionally starch for flame retardancy the PU foams produced from isocyanate prepolymer mixtures be applied. In general, it has been found to be useful to 5 to 50 parts by weight, preferably 10 to 40 parts by weight of the above Flame retardants or mixtures for 100 parts by weight of the com components a) to c) to use.

As fillers, in particular reinforcing fillers, they are per se known, conventional organic and inorganic fillers and Understand reinforcing agents. The following are examples: inorganic fillers such as B. silicate minerals, for example Layered silicates such as antigorite, serpentine, hornblende, amphibole, chrysotile, Zeolites, talc; Metal oxides such as B. kaolin, aluminum oxides, Aluminum silicate, titanium oxides and iron oxides, metal salts such as. B. chalk,  Heavy spar and inorganic pigments such as cadmium sulfide, zinc sulfide, as well as glass particles. Organic fillers come in, for example Consideration: carbon black, melamine, rosin, cyclopentadienyl resins and Graft polymers.

The inorganic and organic fillers can be used individually or as Mixtures are used and are the reaction mixture advantageously in amounts of 0.5 to 50% by weight, preferably 1 to 10 % By weight, based on the weight of components a) to c), is incorporated.

Details of the other usual aids mentioned above f) are the specialist literature, for example the monograph by J.H. Saunders and K.C. Fresh "High Polymers" Volume XVI, Polyurethanes, Parts 1 and 2, Verlag Interscience Publishers 1962 or 1964, or the plastic hand book, Polyurethane, Volume VII, Carl-Hanser-Verlag, Munich, Vienna, 1. and 2nd edition, 1966 and 1983.

The oxyalkylation component produced according to the invention is preferred way for the production of polyurethanes, especially compact or cellular polyurethanes used.

The compact or cellular polyurethanes produced are in particular used for the production of polyurethane foams, for example soft Polyurethane foams, such as those used to manufacture furniture, e.g. B. furniture kis sen, and automobile seats or mattresses are used. Preferably the polyurethanes are used for the production of polyurethane hard foams, e.g. B. for the production of insulation materials such. B. at Refrigerators as insulation foams, or also for the production of com compact polyurethanes, e.g. B. duromers, such as those used in computers housings, window frames or integral foams (e.g. steering wheels, shoe sol  len) find use. The manufactured from the polyurethanes of the invention Molded parts show better mechanical and technical application properties Shapes as molded parts made of saccharide-free polyurethanes, especially one reduced shrinkage and improved elongation and tear resistance.

The invention enables the combined use of the acidic Pretreatment of alkoxylated saccharide products with polyoxyalkylene polyols based on oligosaccharides and / or polysaccharides, the production of polyu rethanes, especially hard polyurethane foams, which have a lower Thermal conductivity and better heat resistance after storage, one better curing during foam production and less Show shrinkage.

The process according to the invention for producing the polyurethanes offers several advantages, both in terms of the polyol manufacturing process as well concerns the polyurethane production itself. Through the use of acidic first saccharide products and their treatment with basic substances and alkylene oxides there are superficial etherifications or surface surface alkoxylation. These bring about a clear stabilization of strength products, which, when further implemented, will result in splitting and / or Ab construction reactions are avoided. This makes it easy to reproduce Manufacture polyols. In addition, the combination according to the invention of the oxyalkylation products from acid-pretreated saccharides with oxalky lated sugar-based polyols with analog saccharide alkoxylate units very good compatibility of all components in the polyol component guaranteed. This means that better-curing polyurethane foams are reduced lower shrinkable. The polyurethane components flow better, and the preferably hard polyurethane foams have better heat dimensional stability and lower thermal conductivity after storage. they are  so for special applications such. B. for insulation purposes, particularly good suitable.

The invention is illustrated by the following examples, which represent preferred embodiments of the invention.

In the examples, the viscosities at 20 and 25 ° C, as indicated ben, measured with the rotary viscometer. The OH numbers (OHZ) were according to DIN 53240 using the anhydride method and the acid numbers (SZ) measured according to DIN 53402. The water content was determined according to DIN 51777 Part 1 determined.

In Examples 1 to 3, oxyalkylation components (compound a ₁₁ )) were prepared, of which those of Examples 1 and 2 in Example 4 were used for the production of polyurethanes. The mechanical values were measured on these polyurethanes.

example 1

200 g of a glucose syrup (CAS No. 882943-4; density 1.35-1.5 g / ml at 20 ° C, viscosity 1,000-10,000 mPa; trade name Cerestar MS 01491 from Cerestar), containing hydrochloric acid or phosphoric acid was acidified to pH 3.7, was mixed with 50 g of a basic alcoholate of ethylene glycol with a total alkali content of 1.1% under nitrogen atmosphere at 110 ° C, and immediately afterwards 50 g of 1,2-propylene oxide were added . After a short pretreatment time, a further 550 g of 1,2-propylene oxide were metered in and reacted by intensive mixing. After the alkylene oxide metering had ended, the crude oxyalkylation product was purified by neutralization with phosphoric acid, vacuum distillation and filtration. The cleaned oxyalkylation product had the following key figures:
OHZ = 491 mg KOH / g;
SZ = 0.09 mg KOH / g;
pH = 7.2; and
Visk ₂₅ = 2470 mPas.

Example 2

200 g of a glucose syrup (CAS No. 8829-34-4; density 1.35-1.5 g / ml at 20 ° C, viscosity 1,000 - 10,000 mPa; trade name Cerestar MS 01491 from Cerestar), mixed with hydrochloric acid or Phosphoric acid was acidified to a pH of 4.1, 3 g of aqueous 40% potassium hydroxide solution and 20 g of 1,2-propylene oxide were added at 115 ° C. under a nitrogen atmosphere. After the pretreatment, a further 580 g of 1,2-propylene oxide were added and reacted. After cleaning by neutralization with phosphoric acid, vacuum distillation and filtration, the oxyalkylation product had the following key figures:
OHZ = 496 mg KOH / g;
SZ = 0.16 mg KOH / g;
pH = 6.6; and
Visk ₂₅ = 1167 mPas.

Example 3

200 g of an acidified starch product (cationic corn starch, C * Size 05 962 from Cerestar) with a pH of 3.5 was pretreated with 100 g of aqueous 1% potassium hydroxide solution and 20 g of ethylene oxide at 112 ° C. under a nitrogen atmosphere . After the pretreatment, the water was distilled off, and after adding 20 g of glycerol, 780 g of 1,2-propylene oxide were metered in and reacted. After purification by neutralization with phosphoric acid, vacuum distillation and filtration, an oxyalkylation product was obtained with the following indicators:
OHZ = 294 mg KOH / g;
SZ = 0.1 mg KOH / g;
Water content = 0.08% by weight;
pH = 6.9; and
Visk ₂₅ = 3080 mPas.

Example 4

In this example, polyurethane foams were made using Saccharide-containing compounds from polyoxyalkylene polyols of an oligosac charids and an oxyalkylation component and their mechani measured properties. These polyurethane foams were made with a Polyurethane foam compared without the oxyalkylation component was produced.

The following polyols were used as polyol components, the amounts used being given in the table below.

• Polyol A: polyol based on sorbitol propylene glycol propylene oxide, OHZ 490 mg KOH / g; Visk ₂₅ = 16,000 mPas, SZ = 0.02 mg KOH / g.
• Polyol B: polyol based on propylene glycol propylene oxide, OHZ 180 mg KOH / g; Visk ₂₅ = 97 maas; SZ = 0.01 mg KOH / g.
• Polyol C: oxyalkylation product from Example 1
• Polyol D: oxyalkylation product from Example 2

Polyphenylmethane polyisocyanate with an NCO content of 31.5% by weight (polymer MDI Lupranat M20A from BASF) was used as the polyisocyanate component. The polyisocyanate component was mixed intensively with the polyol component in a ratio in accordance with the mixing ratio or the characteristic number given in the table, wherein

• MV means mixing ratio polyol component: isocyanate com component;
• MV 100 (as indicated in the table) means 100 parts by weight of the polyol component to the parts by weight of the polyisocyanate component specified in the table;
  

that is, KZ <100 corresponds to an excess of NCO equivalents;
KZ <100 corresponds to an excess of OH equivalents; and
KZ = 100 corresponds to an equivalent amount of NCO equivalents and OH equivalents.

Furthermore, a foam stabilizer (B 8423, Goldschmidt), Poly urethane catalyst dimethylcyclohexylamine (DMCHA), water and cyclopen tan added in the amounts specified in the table.  

The foam was prepared by mixing the polyol, the polyisocyanate component and the other additives by means of a Vollrath stirrer at a speed of 1800 min ^-1.

To foam the mold, the reacting mixture was poured into a mold with the dimensions 300 mm × 400 mm × 80 mm and heated to 45 ° C. and allowed to react there. The shaped body had a total density of 70 +/- 1 kg / m ³ . The parameters and mechanical properties given in the table were determined on this molding. The pot life or start time, the setting time, the rise time and the weight were determined according to methods known to the person skilled in the art, while the further measurements were carried out as follows:
Bolt test: measurement of the maximum impression force in the freshly foamed foam with a bolt of 20 mm in diameter and a spherical cap (radius 10 mm) as a pressure surface at 10 mm feed depending on the specified time (5 to 8 min) after mixing all components for foaming. Higher pressure forces indicate better curing.
RD _K : bulk density of the core (core density)
DF: compression set test, according to DIN 53421
DEM: Pressure modulus method, according to DIN 53457
WLZ: Thermal conductivity at 23 ° C mean temperature (Anacon device) immediately (24 h) after foaming and after 7 days of storage
WFB: heat resistance according to DIN 18164, 24 h at 160 ° C and 0.04 N / mm ²
Open cell: according to ASTM 2856, uncorrected
Hose test: Immediately after the components had been mixed, 100 g of reacting mixture were placed in an endless tube made of a plastic film with a diameter of 4.5 cm. The hose was clamped on one side and the foam length reached in cm was taken as a measure of the flowability. The higher the measured length, the better the foam flows.

The results are shown in the following table.  

table

As can be seen from the table, show that produced according to the invention polyurethane foams compared to polyurethane foams that do not contain oxycycline component, better curing (higher values for Bolt test), a lower shrinkage, a lower coefficient of thermal conductivity as well especially a much better shape stability after storage. Consequently show the moldings of the invention improved mechanical and user manure properties.

Claims (10)

1. A process for the preparation of an oligo- and / or polysaccharide-containing oxalkylation component, characterized in that

• a ₁₁₁ ) 5 to 70 wt .-% of at least one oligo- and / or polysaccharide product with a pH of 3.5 to 6 with
  a ₁₁₂ ) 20 to 94.9% by weight of at least one alkylene oxide and
  a ₁₁₃ ) 0.1 to 10% by weight of at least one alkaline agent,
  each based on the total weight of the oxalkylation component,

be implemented. 2. The method according to claim 1, characterized in that the oligo- and / or polysaccharide product a ₁₁₁ ) is glucose syrup or starch 3. The method according to claim 1 or 2, characterized in that an aqueous oligo- and / or polysaccharide product a ₁₁₁ ) is used with a pH of 3.5 to 5. 4. The method according to any one of claims 1 to 3, characterized in that 10 to 60 wt .-% oligo- and / or polysaccharide product a ₁₁₁ ), 30 to 89.7 wt .-% alkylene oxide a ₁₁₂ and 0.3 to 10 % By weight of alkaline agent a ₁₁₃ ), in each case based on the total weight of the oxyalkylation component, are reacted. 5. The method according to any one of the preceding claims, characterized in that the alkylene oxide a ₁₁₂ ) ethylene oxide, propylene oxide or butylene oxide and as the basic agent a ₁₁₃ ) sodium hydroxide solution, potassium hydroxide solution or a basic alcoholate is used. 6. Oxalkylation component, obtainable according to a process according to any of the preceding claims. 7. Process for the production of compact or cellular, oligo- and / or polysaccharide-containing polyurethanes by reacting

• a) High molecular weight compounds with at least two reactive hydrogen atoms
• b) organic and / or modified organic di- and / or poly isocyanates
  in the presence or absence of
• c) chain extenders and / or crosslinking agents,
• d) blowing agents,
• e) catalysts and
• f) aids,
  characterized in that
  the higher molecular weight compounds a)
  • a ₁ ) 1 to 100 wt .-% saccharide-containing compounds and
  • a ₂ ) 0 to 99% by weight of at least one polyol,
    each based on the total weight of a), wherein the saccharide-containing compounds a ₁ )
    • a ₁₁ ) 1 to 99% by weight of at least one oxyalkylation component and
    • a ₁₂ ) 1 to 99% by weight of at least one polyoxyalkylene polyol of an oligosaccharide and / or polysaccharide,
      each based on the total weight of a ₁ ), wherein an oxyalkylation component a ₁₁ which has been prepared according to a process according to one of Claims 1 to 5 or as defined in Claim 6 is used.

8. Oligo- and / or polysaccharide-containing polyurethane, obtainable according to a method according to claim 7. 9. Use of the polyurethane according to claim 8 for the production of Molded parts. 10. molded parts made of the polyurethane according to claim 8.