CA1150885A - Process for the production of modified polyether polyols and their use in processes for the production of polyurethane plastics - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the production of modified polyether polyols by the radical polymerization of a mixture of acrylonitrile, styrene, a salt of an .alpha.,.beta.-unsaturated monocarboxylic or polycarboxylic acid containing a primary, secondary or tertiary monoamine or polyamine and optionally copoly-merizable compounds with a polyether polyol.

Description

~15i~

_1- Mo-~075 LeA 19,528 A PROCES~ ~CR TXE PRO~UCTION OF MODIFIED
POLYETH~R POLYOLS AND THEIR USE IN PROCESSES
FOR THE PRODUCTION OF POLYU~ETHANE PLASTICS
BACKGROUND OF THE INVENTIO~
S Polyether polyols modified by polymers or copol~mers of olefinically unsaturated monomers, so-called polymer polyols, and their use for the production of polyurethane plastics, particularly foams, are known.
They are produced by the polymerization in situ of one or more vinyl monomers in standard polyether polyols. The use of acrylonitrile and mixtures thereof with styrene ha-; ac~uired the greatest commercial significance, in the presence of a radical-forming polymerization initiator. The production and use of products such as these are desc_ibed, for example, in U. S. Patents 3,3G4,273; 3,383,351; Re-28715; Re-29118; 3,523,093;
4,104,236; 4,111,865; 4,119,586; 4,125,505; 4,148,840 and 4,172,825; and in German Patents 1,222,669; 1,152,536 and 1,152,537.
Polyurethanes produced with polymer polyols of this type are distinguished by an improvement of their properties. In particular, the hardness and load bearing strength of fle~ible polyurethane foams are favorably influenced. ~herefore it is possible to obtain relatively low densities and, thus, to save on starting material for the same level of hardness and tearing strength of previous polyurethanes.
In addition, the polymer polyols provide fleY~ible foams with a greater open-cell character and, in doins so, counteract shrinkage of the fresh foams during storage. Finally, it is possible by means of the polymer polyols, provided that the starting polyether is suitably selected, to produce so-called highly elastic, col~-hardening foams~ In contrast to LeA 19,528 ..~, ~151 ~5 con~entional processes for producing foams such as these, there is no need to use ~pecial polyisocyanates with adapted reactivity;instead it is possible to use standard commercial products, particularly the tolylene diisocyanate predominantly used in the production of flexible foams.
Ideally, the polymer poly~ls are relatively low-viscosity, finely divided, non-sedimenting dispersions of the polymer, preferably an acrylonitrile or acrylonitrile/styrene graft (co) polymer, in the substantially unchanged polyether polyol. Characteristic features of the quality and processibility of the polymer polyols are 'o~ viscosity, stability in storage (resistance to sedimentation) and particle size. These properties are influenced primarily by the type of starting materials used and by the quantit~tive ratios between them.
For monomer mixtures o~ acrylonitrile and styrene, optionally together with small quantities of other co-monomers, the optLmum properties of the polymer polyol (as low a viscosity as po~sible; absence of sediment and agglomerate;small particle size), for a given molecular weight of the starting polyether~ lies within a relatively narrow range of production parameters. The monomer content of the mixture and the monomer ratio both have a particularly marked influence upon the quality of the end product~ Starting out from a polymeriz-ation mixture containing pure acrylonitrile, the viscosity, particle size and ag~lomerate content pass through a minimum with increasing styrene content of the mixture and rise sharply with increasing styrene content beyond this minimum. They also increase drastically with in-creasing monomer total, based on the starting polyether.
~owe~e-, the abovementioned ~zlues also i~creas~ wi~h decreasing molecular weight o~ the starting polyether and also with a reduction in ~he polymerization tempe-rature to below 100 C.

Le A 19 528 The polymer polyol dispersions are stabilized against sedimentation by the incorporaticn of some of the molecules of the starting polyether into the polymer formed ln situ. It may be assumed that the reaction conditions influence the grafting frequency so that it is only at the optimum Oc the parameter range that it is possible to obtain maximum grafting frequency which guarantees the stability in storage and the process-ibility of the product. If the limits of this range of parameters are exceeded, increased viscosity and coarsening of the particles in the polymer polyol to the point of agglomeration and sedimentation are the inevitable consequences. ~he use of polyethers having a short chain length, equivalent weight less than lOOO, also leads to highly viscous, coarse suspensions.
There is no technical teaching in the existing literature to show how these limitations, to which the process for producing polymer polyols is subject, can be overcome and how the properties of the end product can 2Q be improved, even in the case of mixtures which are critical in regard to viscosity and particle size.
It would be desirable for e~ample to obtain a higher solids content, irrespective of the molecular weight of the starting polyether, in order to increase further the property-improving effect of the polymer polyol and to make it possible for the processor to blend the product with other polyols adapting the requirements to the properties of his polyurethane foams.
At the same time, however, the processibility of the product should not be adversely affected. In other words neither viscosity nor particle size should be increased too areatly~
It has already beer. proposed to use standard molecular weight regulators and telogens in the in situ polymerization reaction in order to reduce the viscosity LeA 1~,~28 :~15~ 5 of polymer polyQls in cr.itical mixtures. However, this procedure has not yet been successful because these substances, for example the mercaptans normally used for polymerization purposes, compete with the polyether polyol as transfer agents with a high transfer constant and in fact reduce the grafting yield.
Although the quality of the end product can be improved to a certain extent by increasing the concentration of initiator, there are limits to this process. ~ncreased additions of peroxide involve the danger of an oxidative attack on the polyether. This promotes degradation and cross-linking reactions. At the same time, secondary products formed can give rise to core discoloration in the production of foams. A
toxic secondary product is formed from azoisobutyro-nitrile (AIBN), which has been successfully used in practice, so that in this case, too, the concentration of initiator should be kept as low as possible.
New developments in the processing technology of flexible polyurethane foams, particularly in the upholstery and automobile fields, have created a demand for flame laminatability and high frequency ("HF") weldability of flexible polyether-based foams with other materials, particularly textiles. However, commercially available fiexible polyether urethane foams cannot be subjected to high-frequency welding. There has been no shortage of attempts to make them suitable for HF-welding by the incorporation of suitable additives, primarily substances having a high dielectric constant.
In particular, it would seem to be desirable to provide the foam manufacturer with ready-formulated starting materials from wnich HF-weldable foams can be produced without any need for further additives~

LeA 1~,528 ~5~885 Numerous free radical polymerizable, ethylenically unsaturated co~pounds are described in the existing patent literature as being suitable for the production of polymer polyols. However, apart from the polyether polyols modified by the polymerization of acrylonitrile or styrene/
acrylonitrile mi~tures, no other products have as yet acquired any commercial significance. This is in spite of the fact that small quantities of other monomers may be combined with styrene and acrylonitrile without the properties of the end product being significantly altered.
In the known Patents, for example German Patent 1,222,669, reference is made to the use of a,~-unsaturated monocarboxylic and polycarboxylic acids, although products 1~ on this basis distinguished by particular properties or ~y improved processibility have not yet been described.
In particular, it is not apparent from the existing literature that the presence of ~,~-unsaturated carboxylic acids during the polymerization reaction would make it possible for the stability problems referred to above to be solved and the process limits to be extended.
The object of the present invention is to provide a process for the production of polymer polyols which may be applied more universally than those previously known. The process of the invention shows improvements in the size of the monomer content, the monomer ratio and the choice of the starting polyether and, in addition, gives products which may be converted into foams and show outstanding mechanical properties, and may also be HF-welded. The larger number of polyethers which may be converted into poly.mer polyols by the new process also ma~es it possible for new fields of application to be opened up for the class of products in ~uestion.
LeA l~r528 ^~15~885 ~E~CRIPTION OE THE INVENTION
The present invention relates to a process for the production of modified polyether polyols by the radical polymerization of S I) 1 to 60 parts by weight of a mixture of (A) 20 to 99~9% by weight of acrylonitrile, (B) 0 to 80~ by weight of styrene (C) 0.1 to 10% by weight of an ~
unsaturated monocarboxylic or polycar-boxylic acid, and (D) 0 to 20 % by weight of one or more other copolymerizable compounds, the indivi-dual quantities adding up to 100% by weight, in II) 99 to 40 parts by weight of a polyether polyol, the sum of I~ and II) adding up to 100 parts by weight~ in the presence of a free radical-forming poly-merization initiator, which is characterized in that the ~ unsaturated monocarboxylic or polycarboxylic acid (C) is used in the form of a salt with a primary, secondary or tertiary monoamine or polyamine.
The a,~-unsaturated carboxylic acids and polycarboxylic acids used for the polymerization reaction according to the invention may be any known ~,~-unsaturated carboxylic acids and polycarboxylic acids. Examples include acrylic and methacrylic acid, crotonic acid, maleic acid, fumaric acid~ itaconic acid or citraconic acid, to mention only the commercially most important.
It is also possible to use the oli~omers obtainable by Michael's addition of acrylic acid on its own which correspond to the formula O O
CH2= CH-C--O ( CH2-CH2-C-O )n H
in which n is an integer of from 1 to 5, preferably 1.
LeA 19,528 ~lCii`~85 Other suitable carboxylic acids are the semiesters and semiamides of ~,~-unsaturated dicarboxylic acids, for example monoethyl maleate or fumaric acid-n-butyl amide. The semiesters of saturated dicarboxylic acids with unsaturated alcohols, for example monoallyl succinate or phthalate are also suitable.
The choice of the amine used for salt formation is not critical and, in individual cases, might be limited solely by the poor solubility of the carboxylic acid salt formed in the monomer mixture. Thus, it is possible to use virtually any aliphatic and aromatic monoamine,a polyamine and also heterocyclic bases.
Examples of suitable amines are aliphatic open-chain or cyclic amines and hydroxy amines lS containing from 1 to 18 carbon atoms per alkyl radical, for example methyl amine, dimethyl amine, trimethyl amine, diethyl amine, triethyl amine, isopropyl amine, isobutyl amine, _-butyl amine, di-n-butyl amine, and tri-n-butyl amine. Ethanolamine, diethanolamine, tri-ethanolamine, N-methyl diethanolamine, N,N-dimethyl ethanolamine, diisopropanolamine, pyrrolidine, piperidine, piperazine, N-2-hydroxy ethyl piperazine, ~2,2,2]-diaza-bicyclo-octane, morpholine, N-methyl morpholine, ethylene diamine and N,N-dimethyl aminopropyl amine are further suitable examples.
Arcmatic amines, such an aniline, N-methyl aniline, N,N-dimethyl aniline, N,N-diethyl aniline, N,N-diethyl-p-toluidine, and phenylene diamines, are also suitable.
Heterocyclic nitrogen bases, such as for examp~ pyridine, picolines, quinoline, pyrrole, imidazole, oxazoles, thiazoles, etc., and thPir substituted derivatives may be used.

LeA 1~,528 S

The amines which are preferred in the instant invention are the tertiary amines. This is because they interfere least with the urethane-forming reaction. On the other hand it ha~ been ~ound that polymer polyols produced with di-n-butyl amine may be processed without difficulLy andthat the use of hydroxy amines, such as triethanolamine or methyl diethanolamine, does not adversely affect the processibility of the resulting products either.
However, to avoid an excessive content of foreign substances in the product, it is preferred to use mono-amines and polyamines having a molecular weight or (in the case of polyamine) equivalent weight of from 30 to 150 and preferably from 56 to lG0.
The monomers suitable for the in situ graft polymerization reaction according to the invention are, essentially, acrylonitrile and its mixtures with styrene, the acrylonitrile content of the total monomer mixture amounting to between 20 and 99.9~ by weight, preferably to between 25 and 80% by weight and the styrene content amounting to between 0 and 80% by weight and preferably to between 20 and 75% by weight~
In addition, it is possible to use small quantities of other copolymerizable comonomers, for example esters of unsaturated monocarboxylic and dicarboxylic acids.
~xamples of these are acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid, with lower alcohols containing from 1 to 8 carbon atoms, monoesters or diesters of the above-mentioned carboxylic acids with glycols, polyglycols or higher alcohols. Also suitable are vinyl acetate, vinyl c~loride, vinylidene chloride, methacrylonitrile~ acrylamide, methacrylamide, esters of the above-mentioned unsaturated carboxylic acids wi~h amino alcohol~, for example 2-N,N-dimethyl amino-ethyl methacrylate, as well a~ esters of vinyl phosphonic acid~ for example vinyl phosphonic acid dimethyl ester.
LeA lg,528 :~5~88~;

Polyether polyols which may be used as starting materials in the instant invention are the addition products known per se of cyclic ethers, such as ethylene oxide, propylene oxide, epichlorohydrin,styrene oxide, 1,2-butylene oxide and/or tetrahydrofuran, with startercompounds containing at least two Zerewitinoff-active hydrogen atoms in the molecule, as described for example in the book "Polyurethanes, Chemistry and Tech-nology", Part I, pages 32 et seq, by J. H. Saunders and K. C. Frisch. Suitable starter compounds are, for example, polyhydroxyl compounds, such as alkylene glycols, glycerol, trimethylol propane, pentaerythritol, sorbitol, glucose, glucosides, sucrose and the polyhydroxyl compounds obtainable by the condensation of formaldehyde (formose and formitol), also water, ammonia, amino alcohols, such as ethanolamine, diethanolamine or tri-ethanolamine, and finally primary and/or secondary amines or polyamines, such as ethylene diamine or aniline.
The polyether polyols used as starting materials for the production of the polymer polyols preferably have e~ui~alent weights of from lnO to 3000 and a hydroxyl functionality of from 2 to 8. The polyether chains are normally made up of propylene oxide and ethylene oxide units. The ethylene oxide units may be arranged statis--tically along the chain or in coherent blocks withinand/or at the end of the chain~ In the latter case, particularly reactive polyether polyols having a high primary hydroxyl-group content are formed, representing a particularly suita~le starting material for the 30 production of the highly elastic cold-hardening flexible foams~
The free radical polymerization reaction ~ay be initiated by th~ usual radical-forming initiators. In LeA 19,528 ~s~s - lo -this _onnection, it is desirable that their decomposition rate should be fairly hi~h~ ~e., ~hat +hP half~
life period of thermal decomposition be short enough under the polymerization conditions to ensure that an adequate supply of radicals is always available in the reaction medium. Initiators such as these are, for example, organic peroxides, such as benzoyl peroxide or lauroyl peroxide, and in particular percarboxylic acid esters, such as tert.-butyl peroctoate and tert.-butyl perpivalate, as well as aliphatic azo compounds.Azoisobutyronitrile has the greatest commercial significance and is a particularly suitable initiator for the production of polymer polyols. The initiator is preferably used in a quantity of from 0.3 to 2~ by weight, based on the monomer total. The half life period of thermal decomposition at the polyrnerization temperature should preferably be less than 5 minutes.
The instant process may be carried out either continuously or in batches. For example, a mixture containing the monomer or monomers, the initiator, the a,~-unsaturated carboxylic acid salt and, optionally, part of the polyether used, may be introduced into the polyether preheated to the polymerization temperature in a stirrer-equipped reactor. An alternative example is a mixture of all the reactants being continuously pumped into a reactor and the product commensurately removed through an overflow. Polymerization may be carried out in the presence or absence of additional solvents. In large-scale operation or in production, it is advisable, because of t~e possibility of premature initiaiion of polymeriza-tion in the monomer mixture to be added, to only introduce the initiator dissolved in a suitable organic solvent inio the monomer stream just before it enters the reaction zone, optionally via a mixing unit.

LeA 19,52~
,.

Alternatively, this solution is introduced separately into the reactor.
The temperature at which polymerization is carried out should be at least 100C and preferably be in the range of 120 to 140C. The reaction may be carried out in a system sealed against the external pressure under the pressure which is spontaneously adjusted at the temperature selected or in an open system under ambient pressure. It is necessary to displace the air p~esent from the entire apparatus by purging with an inert gas, such as nitrogen or argon, and to maintain an inert gas atmosphere in the system throughout the entire process, The product is freed from volatile fractions, particularly the residual monomers, in known manner by vacuum distillation, optionally in a thin-layer or fallin~-film evaporator.
The order in which the individual components are added during preparation of the monomer mixture is not critical, providing the suitable monomer combination has been determined and the solubility of the selected amine salt of the ~ unsaturated carboxylic acid confirmed in preliminary tests. It is more favorable to first mix the monomers, inthe selected ratio and quantity, together with the a,~-unsaturated carboxylic acid used, with the starting polyether and then to add the amine, optionally dissolved in an inert organic solvent. The polymerization initiator is best either dissolved in the monomers o~alternati~ely,it is added to the reaction mixture, for example in solution in an inert organic solvent.
The polymer polyols produced by the instant process are suitable for the production of polyurethane plastics O r al kinds, above all flexible and semirigid polyurethane foams, by known processes. They are free from coarse, filterable and sedimenting fractions and LeA lq,528 1.15~ 5 have a considerably lower viscosity than the corres-ponding products produced by conventional processes.
It is also possible by the instant process to produce readily processible, finely divided 5 dispersions of a type which previously could not be obtained free from sediment and agglomerate by known processes or which could only be obtained with such a high viscosity that they could not be processed in the usual mixing and metering units normally used in poly-urethane technology. Thus, it is possible to use newstarting polyethers or more concentrated products, opening up new fields of application for polymer polyols. One advantage of polymer polyols having higher solids content is that the mechanical properties of polyurethane foams produced therefrom, particularly compression hardness and indentation hardness, can be improved for the same unit weight. The scope available to the processor for blending with other polyethers, cross-lin~ers, plasticizers and other additives is increased without the solids content falling below a level at which no property-improving effects are observed. In addition, the production of polymer polyols having a high solids content is more economical because the production costs involved are the same as thDse of known standard products. This allows for making inexpen-sive and low-viscosity formulations upon re-dilution with pure polyether polyol~
It has surprisingly been found that the polymer polyols produced ~y the instant process may readily be high-frer~uency welded with other substrates, for example textiles, without the need for the addition of other substances having a high dielectric constant.

LeA 19,528 ~15~885 This represents a considerable advance in the processing of flexible polyether urethane foams.
The processes for producing polyurethane plastics using polyme_ polyols and the technical improvements obtainable with them are known per se.
Primary importance is attributed to the flexible, elastic and highly elastic foams and also to the semi risid foams to which the polymer polyols impart improved hardness and bearing strength coupled with a favorable hardness/unit weight relation. Other foam properties, for example the open-cell character and freedom from shrinkage of flexible foams, are also favorably affected. Freedom from agglomerates and as low a viscosity as possible are essential requirements for the machine processing of polymer polyols. Piston pump units impose a viscosity range upper limit of around 1500 to 2000 mPas.
Foaming machines equipped with different types of delivery units, for example gear pumps, are also suitable for use with the instant invention.
The instant invention also relates to a process for the production of optionally cellular polyurethane plastics by reacting A) polyisocyanates with B) polyether polyols modified by ~raft polymerization and, optionally, C) other relatively high molecular weight and/or low molecular weight compounds containing isocyan-ate reactive hydrogen atoms, optionally in the presence of D) blowing agents, catalysts and other additives known per se, which is c~aracterized in that the polymer polyols LeA 1'~,528 5~ 35 .

of the instant invention are used as component B).
The following materials are used for carrying out the process o the instant invention:
1. As starting components, aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates of the type described for example by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those corresponding to the formula Q(NCO)n in which:
n = 2 - 4, preferably 2, and Q represents an aliphatic hydrocarbon radical containing from 2 to 36 carbon atoms and preferably from 6 to 10 carbon atoms;
a cycloaliphatic hydrocarbon radical containing from 4 to 15 and preferably from 5 to 10 carbon atoms, an aromatic hydrocarbon radical containing from 6 to 15 carbon atoms and preferably from 6 to 13 carbon atoms;
or an araliphatic hydrocarbon radical containing from 8 to 15 carbon atoms and preferably from 8 to 13 carbon atoms.
Suitable examples are ethylene diisocyanate; 1,4-tetra-methylene diisocyanate; 1,6~hexamethylene diisocyanate;
1,12-dodecane diisocyanate; cyclobutane-1,3-diisocyanate;
cyclohexane-1,3- and -1,4-diisocyanate and mixtures 3Q of these isomers. Additional suitable compounds are l-isocyanato-3,3,5-trLmethyl-5-isocyanatomethyl cyclohexane (German Auslegeschrift 1,202,785, U. S.
Patent 3,401,190); 2,4- and 2,6-hexahydrotolylene diisocyanate and mixtures of these isomers; hexahydro-LeA 19,528 115~885 1,3- and/or -1,4-phenylene diisocyanate; perhydro-2,4'-and/or -4,4'-diphenyl methane diisocyanate; 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers; diphenyl methane-2,4'- and/or -4,4'-diisocyanate and naphthylene-1,5-diisocyanate.
According to the instant invention, it is also possible for example to use triphenyl methane-4,4',4"-triisocyanate, polyphenyl polymethylene polyisocyanates 10 of the type obtained by condensing aniline with formaldehyde, followed by phosgenation, and described for example in British Patents 874,430 and 848,671;
m- and p-isocyanatophenyl sulphonyl isocyanates according to U.S. Patent 3,454,606. Additional examples are 15 perchlorinated aryl polyisocyanates of the type described for example in German Auslegeschrift 1,157,601 (U.S.
Patent 3,277,138~; polyisocyanates containing carbodiimide groups of the type described in German Patent 1,092,007 (U.S. Patent 3,152,162) and in German 20 Offenlegungsschriften 2,504,400; 2,537,685, and

2,552,350; norbornane diisocyanates according to U.S.
Patent 3,492,330; polyisocyanates containing allophanate groups of the type described for example in British Patent 994,890 and Belgian Patent 761,626. Still more 25 examples of suitable compounds are for example, poly-isocyanates containing isocyanurate groups of the type described for example in U.S. Patent 3,001,973; German Patents 1,022,789; 1,222,067 and 1,027,394 and German Offenlegungsschriften 1,929,034 and 2,004,048 as well 30 as polyisocyanates containing urethane groups of the type described for example in Belgian Patent 752,261 or in U.S. Patents 3,394,164 and 3,644,457. Polyisocyanates containing acylated urea groups according to German Patent 1,230,778; polyisocyanates containing biuret groups LeA 19,528 ~A

s of the type described for example in U. S. Patents

3,1~4,605; 3,201,372 and British Patent 889,050; polyisocyanates produced by telomerization reactions of the type described for example in U. S.
Patent 3,654,106 and polyisocyanates containing ester groups of the type described for example in British Patents 965,474 and 1,072,956; U. S. Patent 3,567,763 and German Patent 1,231,688 are still more examples of suitable compounds. Reaction products of the above mentioned isocyanates with acetals according to German Patent 1,072,385 and polyisocyanates containing polymeric fatty acid esters according to U. S. Patent 3,455,883 are also suitable compounds for use as starting materials in the instant invention.
It is also possible to use the isocyanate-group-containing distillation residues obtained in the commercial production of isocyanates, optionally in solution in one or more of the above mentioned polyisocyanates. It is also possible to use any mixtures of the above mentioned polyisocyanates.
In general, it is particularly preferred to use the commercially readily available polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate, and/or any mixtures of these isomers ("TDI"). Polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation ("crude MDI") and polyisocyanates containing carbodiimide groups, urethane groups or biuret groups ("modified polyisocyanates"), particularly modified polyisocyanates of the type derived from 2,4- and/or 2,6-tolylene diisocyana~e or from 4,4'- and/or 2,4'-diphenyl methane diisocyanate are also particularly prererre~.
2. As further optional starting components:
LeA 19,528 ~115~i885 compounds con~aining at least two isocyanate-reactive hydrogen atoms an~ having a molecular weight of from 400 to 10,000. In addition to compounds containing amino groups, thiol groups or carboxyl groups, preferable compounds contain hydroxyl groups, particularly compounds containing from 2 to 8 hydroxyl groups, above all those which have molecular weights of from 400 to 7000, preferably from 1000 to 5000. Examples of these compounds are polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester amides containing at least 2, generally from 2 to 8, but preferably from 2 to

4 hydroxyl groups, of the type ~nown per se for the production of homogeneous and cellular polyurethanes.
Representatives of the above-mentioned compounds which may be used with the instant invention are described for example in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", by Saunders-Fr sch, Interscience Publishers~ New York/London, Vol. I, 1962, pages 32-42 and 44-54 and Vol. II, 1964, pages

5-6 and 198-199, and in Kunststoff-Handbuch, Vol. VII, Vieweg-~ochtlen, Carl-Hanser-Verlag, Munich, 1966, for example on pages 45 to 71. It is of course also possible to use mixtures of the above-mentioned compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of from 400 to 10,000, for example mixtures of polyethers and polyesters~
In some cases, it is particularly advantageous to combine low-melting and high~melting polyhydroxyl compounds with one another as described in German Offenlegungsschrift 2,7Q6,297.
3. Compounds containing at least two isocyanate-reactive hydrogen atoms and ~aving a molecular weight LeA 19,528 ~lX~5 of rrom 32 to 4Q0 may also be used as starting components.
These compounds also contain hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups which serve as chain extenders or cross-linkers~ These compounds generally contain from 2 to 8 and preferably from 2 to 4 isocyanate-reactive hydrogen atoms.
Here also, it is possible to use mixtures of different compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of from 32 to 400.
Examples of compounds such as these are ethylene glycol, 1,2- and 1,3-propylene glycol; 1,4- and 2,3-butylene glycol; 1~5-pentane diol; 1 r 6-hexane diol; 1,8-octane diol; neopentyl glycol; 1,4-bis-hydroxymethyl cyclohexane; 2-methyl-1,3-propane diol; and dibromobutene diol (U. S. Patent 3,723,392). Additional examples of these compounds are glycerol; trimethylol propane;
1,2,6-hexane triol; trimethylol ethane; pentaerythritol;
quinitol; mannitol and sorbitol; castor oil; diethylene glycol; triethylene glycol; tetraethylene glycol; higher polyethylene glycols having a molecular weight of up to 400, dipropylene glycol; higher polypropylene glycols having a molecular weight of up to 400; dibutylene glycol; higher polybutylene ~lycols having a molecular weight of up to 400, 4~4'~dihydroxy diphenyl propane;
dihydroxy methyl hydroquinone; ethanolamine; diethanolamine;
N-methyl diethanolamine, triethanolamine and 3-aminopropanol.
In the instant invention, suitable low molecular weight polyols are also the mixtures of hydroxyl aldehydes and hydroxy ketones ~"formose"), or the poly;
hydric alcohols obtained therefrom by reduction ("formitolN) LeA 19,528 ~15~85 which are formed in the autocondensation of formaldehyde hydrate in the presence of metal compounds as catalysts and compounds capable of enediol formation as cocatalysts (German Offenlegungsschriften 2,639,084; 2,714,084;
2,714,104; 2,721,186; 2,738,154 and 3,738,512).
In order to obtain plastics with improved flame resistance, these formoses are advantageously used in combination with aminoplast formers and/or phosphites IGerman Offenlegungsschriften 2,738,513 and 2,738,532). Solutions Of polyisocyanate polyaddition products, particularly solutions of polyurethane ureas containing ionic groups and/or solutions of polyhydrazodicarbonamides, in low molecular weight polyhydric alcohols may also be used as the polyol component in the present invention (German Offenlegungsschrift 2,638,759).
Aliphatic diamines suitable for use in the instant invention are, for example~ ethylene diamine, 1,4-tetramethylene diamine, l~ll-undecamethylene diamine, 1,12-dodecamethylene diamine and mixtures thereof.
Additional examples are l-amino-3,3,5-trimethyl-5-amino-methyl cyclohexane (nisophorone diamine"), 2,4- and 2,6-hexahydrotolylene diamine and mixtures thereof~ Perhydro-2,4'- and -4,4'-diaminodiphenyl methane; ~-xylylene diamine; bis-(3-aminopropyl)-methyl-amine; diaminoperhydro anthracenes (German Offenlegungsschrift 2,638,731) and cycloaliphatic triamines according to German Offenlegungs-schrift 2,614,244 are still further examples of suitable aliphatic diamines~ It is also possible in the present inYention to use hydrazine and substituted hydrazines, for example methyl hydrazine, N,N'-dimethyl hydrazine and their homologs. Acid dihydrazides~ for example carbodihydrazide; oxalic acid dihydrazide; the dihydra-zides of malonic acid; succinic acid; slutaric acidt adipic acid; ~-methyl adipic acid; sebacic acid; hydracrylic LeA 1~,528 ~1S~885 acid and terephtAalic acid; semicarbazido propion-c acid hydrazide (German Offenlegungsschrift 1,770,591) are also suita~le. Semicarbazido alkylene carbazinic esters such as, for example, 2-semicarbazido ethyl carbazinic ester (German Offenlegungsschrift 1,918,504) or even amino-semicarbazide compounds such as, for example, ~-aminoethyl semicarbazido carbonate (German Offenlegungs-schrift 1,902,931) may also be used in the present inven-tion. To control their reactivity, the amino groups may be completely or partly blocked by aldimine or ketimine groups (U. S~ Patent 3,734,894; German Offenlegungsschri'ft 2,637,115).
Examples of aromatic diamines are bis-anthranilic acid esters according to German Offenlegungsschriften 2,040,644 and 2,160,590; 3,5- and 2,4-diaminobenzoic acid esters according to German Offenlegungsschrift 2,025,900; the diamines containing ester groups described in German Offenlegungsschriften 1,803,635 (U. S. Patents 3,681,290 and 3~736,350); 2,040,650 and 2,160,589. The diamines containing ether groups according to German Offenlegungsschriften 1,770,525 and 1,809,172 (U. S. Patents 3,654,364 and 3,736,295);
2-halogen-1,3-phenylene diamines which may be substituted in the 5-position (.German Offenlegungsschriften 2,0al,772; 2,025,896, and 2,065,869); 3,3'-dichloro-4,4'-diaminodiphenyl methane; tolylene diamine; 4,4'-diamino-diphenyl methane; 4,4'-diaminodiphenyl disulfides (.German Offenlegungsschrift 2,404,976) are further examples of suita~le aromatic diamines. Diaminodiphenyl dithioethers (German Offenlegungsschrift 2~50.9,4041;
aromatic diamines su~stituted by alkyl thio groups (.German O~fenlegungsschrift 2~638,760~; diaminobenzene phosphonic acid esters ~German Offenlegungsschrift 2,459,491); aromatic diamines containing sulfonate or car~oxylate groups (German Offenlegungsschrift 2,720,1661 ~eA 19,528 ~5~885 and the high-melting diamines described in German Offenlegungsschrift 2,635,400 are further examples.
Examples of aliphatic-aromatic diamines are the amino-alkyl thioanilines according to German Offenlegungsschrift 2,734,574.
In the instant invention, other suitable chain extenders are such compounds as l-mercapto-3-amino-propane, amino acids which may be substituted for example glycine, alanine, valine, serine and lysine and dicarboxylic acids which may be substituted for example succinic acid, adipic acid, phthalic acid, 4-hydroxy phthalic acid and 4-aminophthalic acid.
In addition, isocyanate-monofunctional compounds may be used as so-called chain terminators in proportions Of from 0.01 to 10% by weight, based on polyurethane solids. Monofunctional compounds such as these are, for example, monoamines, such as butyl and dibutylamine, octylamine, stearylamine, N-methyl stearylamine, pyrrolidine, piperidine and cyclohexylamine and monoalco-hols such as butanol, 2-ethyl hexanol, octanol, dodecanol, the various amyl alcohols~ cyclohexanol, ethylene glycol monoethyl ether.
4. As optional additives and auxiliaries:
Water and/or readily volatile inorganic or organic substances as blowing agents. Organic blowing agents include for example, acetone, ethylacetate, halogen-substituted alkanes, such as methylene chloride, ch~oro-form, ethylidene chloride, vinylidene chloride, monofluoro-trichloromethane, chlorodifluoromethane~ dichloro-difluoromethane, also butane, hexane, heptane ordiethyl ether. Inorganic blowing agents include for example, air, CO2 or N2O. A blowing effect may also be obtaine~ by adding compounds which decompose at temper-atures above room temperature giving off gases, such as ~eA 19,528 -~2-nitrogen, for exa~.ple azo compounds such as azo-dicarbonamide or azoisobutyronitrile. Other examples of blowing agents and information on the use of blowing agents can be found in Kunststoff-Handbuch, Vol. VII, by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example on pages 108 and 109, 453 to 455 and 507 to 510.
Catalysts known per se, for example tertiary amines may also be used. Examples of such tertiary amines are triethylamine, tributylamine, N-methyl morpholine, N-ethyl morpholine, N,N,N'N'-tetramethyl ethylene diamine, pentamethyl diethylene triamine and higher homologs (German Offenlegungsschriften 2,624,527 and 2,624,528); 1,4-diazabicyclo-(2,2,2)-octane; and N-methyl-N'-dimethylaminoethyl piperazine. Bis-(dimethyl-aminoalkyl)-piperazines (German Offenlegungs-schrift 2,636,787); N,N-dimethyl benzylaminej N,N-dimethyl cyclohexylamine; N,N-diethyl benzylamine; bis-(N,N~-diethyl-aminoethyl)-adipate; N,N,N'NI-tetramethyl-1,3-butane diamine; N,N-dimethyl-~-phenyl ethylamine;
1,2-dimethyl imidazole; 2-methyl imidazole; monocyclic and bicyclic amidines ~German Offenlegungsschrift 1,720,633) arestill further examples of suitable compounds.
Bis-(dialkylamino)-alkyl ethers (U. S. Patent 3,330,782, German Auslegeschrift 1,030,558 and German Offenlegungs-schriften 1,~04,361 and 2,618,280) and tertiary amines containing amide groups (preferably formamide groups) according to German Offenlegungsschriften 2,523,633 and 2,732,292 are further examples of suitable compounds.
Other suitable catalysts are the Mannich bases known per se of secondary amines, such as dimethylamine, and alde-hydes, preferably formaldehyde, or ketones, such as acetone, methylethyl ketone or cyclohexanone, and phenols, such as phenol, nonyl phenol or bisphenol.
LeA 19,528 -~3_ Tertiary amines containing isocyanate-reactive hydrogen atoms suitable for use as catalysts are, for example, triethanolamine, triisopropanolamine, N-methyl diethanolamine, N-ethyl diethanolamine, N,N-dimethyl ethanolamine and their reaction productswith alkylene oxides, such as propylene oxide and/or ethylene oxide. Also suitable as catalysts are secondary-tertiary amines according to German Offenlegungsschrift 2,732,292.
Other suitable catalysts are sila-amines containing carbon-silicon bonds, of the type described for example in German Patent 1,229,290 (corresponding to U. S. Patent 3~620,984), for example 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl tetramethyl disiloxane.
Other suitable catalystsare nitrogen-containing bases, such as tetraalkyl ammonium hydroxides, also alkali hydroxides such as sodium hydroxide, alkali phenolates, such as sodium phenolate, or alkali alcoholates, such as sodium methylate. Hexahydrotriazines may also be used as catalysts as described in German Offenlegungs-schrift 1,769,043.
~ he reaction between ~CO-groups and Zerewitinoff-active hydrogen atoms is also greatly accelerated by lactams and azalactams, an associate between the lactam and the compound containing acid hydrogen initially being formed. Associates such as these and their catalytic effect are described in German Offenlegungsschriften 2,062,288; 2,062,289; 2,117,576 (U. S. Patent 3,758,444);
2,129,198; 2,330,175 and 2,330,211).
It i5 also possible to use organometallic compounds, particularly organo tin compounds, as catalysts.
In addition to sulfur-containing compounds, such as di-_-octyl tin mercapti~e as described in German Auslegeschrift LeA 19,528 ~15~`885 1,769,367 and U. S. Patent 3,645,927, preferred organo tin compounds are tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin(II) laurate, and tin (IV) compounds, for example dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate.
All the above mentioned catalysts may of course be used in the form of mixtures~ In this respect, combinations of organometallic compounds and amidines, aminopyridines or hydrazino pyridines as described in German Offenlegungsschriften 2,343,185; 2,601,082 and 2,603,834 are of particular interest.
Further examples of catalysts suitable for use in the instant invention and information on the way in which they work can be found in Kunststoff-Handbuch by Vieweg and Hochtlen, Vol. VII, Carl-Hanser~Verlag, Munich 1966, for example on pages 96 to 102.
The catalysts are generally used in a quantity of from about 0.001 to 10~ by weight, based on the total quantity of compounds containing at least two isocyanate-reactive hydrogen atoms.
Surface-active additives, such as emulsif-ers and foam stabilizers may also be used with the instant invention. Suitable emulsifiers are for example the sodium salts of castor oil sulfonates or salts of fatty acids with amines, such as diethylamine oleate or diethanolamine stearate. Alkali or ammonium salts of sulfonic acids, 3~ such as for example dodecyl benzene sulfonic acid or dinaphthyl methane disulfonic acid, or of fatty acids, such as ricinoleic acid, or of polymeric fatty acids may also be used as surface-ac-ive additives~

LeA 19,528 :~S~885 Sultable roam stabilizers are, above all, polyether siloxanes, particularly water soluble types.
The structure of these comDounds is generally such that a copolymer of ethylene oxide and propylene oxide is attached to a polydimethyl siloxane residue. Foam stabilizers such as these are described for example in U. S. Patents 2,834,748; 2,917,480 and 3,629,308.
In many cases, polysiloxane-polyoxyalkylene copolymers branched through allophanate groups according to German Offenlegungsschrift 2,558,523 are of particular interest.
Reaction retarders, for example acid-reacting substances such as hydrochloric acid or organic acid halides are suitable for use with the instant invention.
Cell regulators known per se, such as paraffins or fatty alcohols or dimethyl polysiloxanes and also pigments or dyes and flameproofing agents known per se, for example tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate are also suitable.
Stabilizers against the effects of aging and weatner, plasticizers and fungistatic and bacteriostatic substances as well as fillers such as barium sulfate, kiesel~uhr, carbon black or whiting are examples of other additives which may be used with the instant invention.
Purther examples of surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flameproofins agents, plasticizers, dyes, fillers, fungistatic and bacteriostatic substances which may be used in the instant invention and information on the way in which these additives are used and on their respective modes of action can be found in Kunststoff-~andbuch by Vieweg and Hochtlen, Vol. VII, Carl-Hanser-Verlag, Munich 1~66, for example on pages 1~3 to 113.
The proc~ss of the instant invention is carried out as descrihed below LeA 19,5~8 i85 mhe reaction components are reacted by the one-shot process known per se, by the prepolymer process or by the semi-prepolymer process, in many cases using machines, for example of the type described in U. S~ Patent 2,764,565. Particulars of processing machines which may also be used can be found in Kunststoff-Handbuch by Vieweg and Hochtlen, Vol. VII, Carl-Hanser-Verlag, Munich, 1966, for example on pages 121 to 205.
In the production of foams, it is also possible to carry out foaming in closed molds. The reaction mixture is introduced into a mold. Suitable mold materials are metals, for example aluminum, or plastics, for example epoxide resin. The foamable reaction mixture foams in the mold and forms the molding.
In-mold foaming may be carried out in such a way that the molding has a cellular structure at its surface, although it may also be carried out in such a way that the molding has a compact skin and a cellular core.
It is possible to introduce foamable reaction mixture into the mold in such a quantity that the foam formed just fills the mold. It is also possible to introduce into the mold more foamable reaction mixture th~n is required for filling the interior of the mold with foam. This particular technique is known as overcharging and is known for example from U, S. Patents 3,178,490 and 3,182,104.
In many cases~ "external release agents"
known per se, such as silicone oils, are used for in-mold foaming. It is also possible to use so-called "internal release agents", which may be used in admixture with external release agents, of the type known for exam~le from German Offenlegungsschriften 2,121,670 and 2,307,589.
LeA 19,528 .

~15~ 35 It is also possible to produce cold-hzrdening foams (cf. British Patent 1,162,517 and German Offenlegungsschrift 2,153,086).
It is of course also possible to produce foams by block foaming or by the laminator process known per se.
The instant process is illustrated, but in no way restricted, by the following Examples in which the quantities quoted represent parts by weight or percentages by weight, unless otherwise stated.
The following abbreviations and designations are used in the following Examples:
AIBN: Azoisobutyronitrile (radical polymerization initiator) 15 AS: Acrylic acid DAS: Dimeric acrylic acid CH2=CH-CO-O ~H2~OOH
MAS: Methacrylic acid MSA: Maleic acid anhydride ITS: Itaconic acid 20 TEA: Triethyl amine DBA: Di-n-butyl amine TELA: Triethanolamine MDELA; Methyl diethanolamine DMA: N,N-dimethyl aniline5 Polyol A: A trimethylol-propane-started polypropylene oxide polyether containing terminal poly-oxyethylene blocks and ha~ing an ethylene oxide content of 17% and a molecular weight of approximately 4800.0 Polyol B: A trimethylol-propane-started polypropylene oxide having a molecular weight of approx-imately 3000.
Polyol C: A glycerol-started polypropylene oxide polyether containing terminal polyoxyethylene LeA 19,528 ~15(~88S

blocks (5%) and having a molecular weight of approximately 3000.

Polyol D: A polypropylene glycol having a molecular weight of approximately 2000.
Polyol E: A polypropylene glycol containing 5% of terminal polyoxyethylene blocks and having a molecular weight of approximately 2000.
Polyol F: A polypropylene glycol having a molecular weight of approximately 1000.
Polyol G: A propoxylated trimethylol propane having a molecular weight of approximately 300.
Polyol H: A trimethylol-propane-started polypropylene oxide polyether containing 13% of terminally incorporated polyoxyethylene blocks and having a molecular weight of approximately 6000.
The viscosities were determined at room temperature (22-23C) using a Haake-Viskotester* (VT 02; No. spindle).
In order to determine the non-filterable component, the product was filtered through a metal sieve (mesh width 100 ~m), the sieve residue was washed with methanol, dried and weighed out; the quantities observed are based on the total solids.
EXAMPLES

100 g of polyol A were heated to 120C in a reaction vessel equipped with a blade stirrer, reflux condenser, thermometer, gas inlet pipe and dropping funnel and heated by an oil bath. A mixture of 500 g of polyol A, 140 g of styrene, 240 g of acrylonitrile, 20 g of DAS, 20.7 g of TELA and 4 g of AIBN (1~, based on the total amount of monomer) was introduced through the dropping funnel over a period of two hours. On completion 35 of the addition, the mixture was heated with stirring for 4 hours and, finally, the volatile fraction was distilled * Trademark LeA 19,528 5~`s885 off in vacuo, leaving a pale yellowish, finely divided dispersion free from agglomerate particles and sediment and havina a viscosity of 4100 mPas at 22C. The hydroxyl number amounted to 31.9, the acid number to 2.1 and the quantity of distilla~e to 32 g. According to a gas chromatogram, the distillate consisted of acrylonitrile and styrene and contained traces of TELA. The analytical data show a monomer conversion of 92% and a solids content of the dispersion of 38%.
For comparison, the test was repeated using DAS itself rather than its amine salt as comonomer. For otherwise the same procedure, a highly viscous, gritty paste was formed. It had a viscosity of 55,000 mPas at 22C and was unsuitable for further processing into polyurethane plastics~

Under the same conditions as in Example 1, a mixture of 3000g of polyol A, 1125 g of styrene ! 1800 g of acrylonitrile, 75 g of AS, 134 g of DBA and 30 g of AIBN was added dropwise over a period of 5 hours at 120C to 1500 g of polyol A, after which the reaction mixture was stirred for 3 hours at 120C. Vacuum distillation gave 249 g of distillate, the product was a white, yellow-tinged homogeneously finely divided dispersion having a viscosity of 4600 mPas/23C, a hydroxyl number of 22.2, an acid number of 1.6 and a solids content of 3~.1%
The test was repeated in a 100 liter stainless steel autoclave using a batch increased by a factor of 10, 3000 g of toluene being added to the mixture introduced in order to reduce its viscosity. The product had a solids content of 39~2%, a viscosity of 4700 mPas, a hydroxyl number of 19.3 and an acid number of 2 4.
The test could be carried out without difficulty on an even larger scale.
LeA 19,528 ~15~S
- 29 a -A trial run was carried out in a 500 1 stainless steel steam heated kettle,427 kg of a polymer polyol havinga n OH number of 2008, an acid number of 104, and a viscosity of 5200 m PaOs at 20 C are obtained, which was free from sedimenting particles and passed through a 100 um sieve without leaving a residue.

Le A 19,528 The procedure was as in Example 1. The following mixture was added dropwise over a period of 2 hours at 120C to 100 g of polyol A:
Polyol A5Q0 g Styrene15Q g Acrylonitrile 240 g M~S 12 g TE~A 2Q.7 g AIBN 4 g Distillate32 g Solids content 38.1 Monomer conversion 92 ~
Viscosity 4200 mPas/23C
OH number 33.9 Acid number 2.1 This batch was increased by a factor of 67.5 and the test repeated in a 100 liter fine-steel autoclave in the same way as in Example 2. The product was a finely divided, stable dispersion having a solids content of 39.5%, a hydroxyl number of 37.2, an acid number of 2.4 and a viscosity of 6000 mPas. The test was repeated in a 500 1 stirred reactor yielding a dispersion with an OH-number of 42.3, an acid number of 0.85, and a viscosity of 7800 mPas/20C. It passed through a 100 ~m sieve without leaving a residue.

300 g of polyol A were heated to 120C and the following mixture added over a period of 2 hours:
Polyol A1800 g Styrene360 g Acrylonitrile 530 g DAS 10 g TELA 10 g AIBN 9 g A total of 55.5 g of volatile fractions was distilled _ vacuo. This corresponds to a conversion of LeA 19,528 `~

S~

94% of the monomers used and to a solids content of 28.7%.
A very finely divided dispersion having a viscosity of 3700 mPas/22C was formed.

This Example shows that the effect of the reduction in viscosity occurs even with only partial salt formation of the ~,~-unsaturated carboxylic acid. In one test, the carboxylic acid used was not neutralized at all; in another test, it was only 50~ neutralized with the amine. The procedure was as in Example 1.
Test I II
Product initially introduced: Polyol 100 g 100 g A (heated under nitrogen to 120C) ~S;xture introduced:
Poly~l A 500 g 500 g Styrene 156 g 156 g Acrylonitrile240 g 140 g AS g TELA - 4~1 g Toluene 200 g 200 g A13N 4 g 4 g Mbnomer conversion: 95.5 % 98.8 %
Solids content; 38.9 % 39.7 ~
Viscosity at 23C; 18,000 mæas 3900 mPas Appearance I~ generally finely d:~ided dispersion permeated by co~rse agglomerate particles II) finely divided, agglomerate-free and sediment-free dispersion EX~MPLES 6 to 19 The following tests were carried out in a two LeA 19,528 S`85 -3~-liter capacity alass apparatus of the type described in Example 1. The quantities by weight are given in g.
The reaction temperature was 120C in every case.
Exam~le No. 6 7 8 9 10 11 12 13 Product init;~lly mtroduced (in ~m~) Polyol A 200200 200 200 200 100 100 100 Toluene 25 25 25 25 25 25 25 25 Mixture introduced:
Poly~l A 400400 400400 400 400 400 300 10 T~luene 50 50 5050 50 50 50 50 A~ryloni-trile 240240 240200 200 375 300 360 Styrene 150150 155190 185 100 190 220 15 DAS _ _ _10 - 25 M~;A -- 10 DBA - - - - 23 - -30.7 TEIA - - - 10.3 -20 MDEIA - 12.1 -DMA 16.8 AI~N 4 4 4 4 4 5 5 6 LeA 19,528 O O~ InO~ ~ ~ ~ ~ ~ O
~` CO~ ~ oo ~ o In ~~ ul ~

u~ I~ ~ r-- cr~ ~ o o _I
I o j~ r-- _I~ cn r~ ~ o o I ~ I o I~r ~1 ~~ 1~ ~ a~o O ~ a~ u~I LO~
. . . - , $ ~
b ~ `J co ~ o o a~
er ~D n o ~ ~ o . , . . . . .~ o ~i r~ I` oo co ~D ~00t~l O
a~ O

In U'~ r o ~ o . . . . . . . I o C) ;~
~D Il Ct> C~ ~ ~ OC~ ~1 0 _I
o~ Q
__ ~ .
.~
~ ~ ~ ~ oO
a _l O s~ o ,1 a~ n~ u~

l ~ ~

I~ 19,528 `~15i`~35 Example N~.14 15 16 17 18 19 -- _ Product ~nitially introduced (in grams) P~ly~l B 200200 200 200 200 200 T~luene 25 25 50 50 50 50 Mixture introduced:
Polyol B 400400 400 400 300 200 T~luene 50 50 100 100 100 100 ~crylonitrile 240 240 240 200 300 360 Styrene 150145 155 190 190 215 M~S - 15 - - 10 T~ 14 - 7.8 DB~ - 22.5 - - - 44.8 DM~ - - - 16.8 _ _ 17.7 LeA 19,528 ~s~s Example No. 14 15 16 17 18 19 ~r oonversion (~)93.7 94.5 93.1 95.1 97.8 95.2 Acrylonitrile bcun~l) 58.2 58.9 58.0 48.4 59.7 59.0 Styrene boundl)39.1 37.1 40.7 49.0 38.3 36.6 GC-analysis of the distillate:
% Acrylonitrile22,0 17.4 24.3 16.1 8.2 22.9 % Styrene 3.4 4~8 3~7 3.6 2.9 6.0 Solids oontent (%) 38.4 38.6 38.3 38.8 49.4 58.8 OH-numker 34.3 34~5 34.7 33.9 38.9 23.5 Nbn-filterable ccmponent (%, based on solids); 100 ~m mesh sieve- ~ O,1 - - - <O,1 Visoosity (mPas) 3300 2900 2900 4300 4600 490Q
1) %, based on the solids oontent LeA 19,528 :~15~35 EX~NPIES 20 bo 27 The following Examples were carried out under the same conditions as EXamples 6-19.

Example Nb.20 21 22 23 24 25 26 27 Product initially ~troduced (in grams):
Polyol C 200200 200 100 100 PD1Y~1 E - - - - - 100100 100 P~1YD1 F - - - - - 100100 100 Tbluene 50 50 50 50 50 50 50 50 Mixture intra~uced (in grams):
PDlyol C 400400 400 400 300 PD1Y~1 F - - - - - 300250 250 Acrylonitrile 240 240 240 300360160 240 240 Styrene 150145 155 190 215 30 50 50 M~S - 15 - 10 - - - -TEL~ - - - 17.7 - - -2a.7 DBA - 22~5 - - 44.8 - -TE~ 14 - 7.8 - - 14 14 l~luene 100lQ0 lOQ lQ0 100100100 lQQ

LeA 1~528 t~ I O ~ O O ~ er ~D g . I`O 1` O~_i ~ er O
o~o~ ~ ~ ~ I~ _I
ou~ $
~D~ U~ ~~7 ~ O~ CO
C~
~nlo~ u~ ~ o ~ o~ o .. . . , . . o . .. . , . . o u~

~ ¦.. . ~ . . g " ~ D O

co r~ ~ ~ O
O~In ~_I ~ ~ ~
~ r OD OU~1` 8 U) O1`~DO o : o~

R ~ ~ v R
, @ ~ 8 IR~ 19,528 ;~ ~5~i85 E~LE 28 The following polymer polyol dispersion was produced usi~g the procedure described in Exam~le 1:
400 g of polyol D were heated under nitrogen to 125C~ A mixture of 93G g of acrylonitrile, 240 g of styrene, 18 g of AIBN, 1400 g of polyol D, 400 g of toluene, 30 g of AS and 42 g of TEA, produced by mixing the individual components in this order, was added over a period of ~ hours, the temperature being kept constant lQ at 125C after an initial rise to 132C. After stirring for 2 hours at the same tempe~ature, the toluene was distilled off together with the residual monomers in a water jet vacuum at 130C. The distillate collected in a dry ice trap weighed 438.4 g and, according to analysis by gas chromatoaraphy, contained 1.27% of styrene, corresponding to 5.6 ~, and 7.7~ of acrylonitrile, corresponding to 33.7. This gives a monomer conversion of 96.7% and a solids content of 39.2~. The solid contained 77.2% of bound acrylonitrile and 20.2% of bound styrene. The hydroxyl number amounted to 34.6, the acid number to 1.3 and the viscosity at room temper-ature to 2850 mPas. The product was a yellowish, uniformly finely divided dispersion free from nonfilterable components.
50 parts of this dispersion were diluted with 50 parts polyol D and the resulting mixture reacted with pure 2,4-diisocyanatotoluene to form a pre-polymer having an NCO content of 3.15~. Hardening was carried out with diethyl tolylene diamine at an NC~/NH2-index of 110. A
similar product was prepared with pure polyol D as sole hydroxyl component. ~he following mechanical properties were dete~mined on test specimens of the two elastomers which had been tempered for 24 hours at 110C:

LeA 19,528 ~15i3~85 Comparison Polymer poly-test ol according Polyol to the _ D invention Tensile strength ~DIN 53 504) 9.1 Mpa 25.1 Mpa Elongation at break (DIN 53 504) 400 % 445 %
Tear propagation resistance (DIN 53 515) 16.9 KN/m 38.5 KN/m Hardness, Shore A (DIN 53 505) 77 87 Elasticity (DIN 53 512) 55 % 52 %

LeA 19,528 ,8~5 ~X~LES 28-33 The follo~ing tests were carried out by the method described in Example 1. The quantities of the materials used are given in grams. The reaction temperature was 125C.
Example No. 28 29 30 31 32 33 Produc~ initially introduced:
Polyol A 70 70 60 60 50 50 Polyol G 105 105 90 90 75 75 Toluene 25 25 25 25 25 25 Mixture introduced:
Polyol A 210 210 180 180 150 150 Polyol G 315 315 270 270 225 225 Toluene 50 50 50 50 50 50 Acrylonitrile140 150 190 200 235 250 Styrene 150 150 200 200 250 250 ~lethacrylic acid 10 - 10 - 15 Triethyl amine 12 - 12 - 18 Monomer Conversion(%)96.2 96.9 97.1 95.9 95.5 96.8 Acrylonitrile bound45.5 49.247.0 48.9 45.7 48.9 Styrene boundl)51.0 50.8 50.5 51.1 51.0 51.1 Acrylonitrile (distillate) (~)12.9 13.6 11.8 14.7 12.0 13.3 Styrene (distillate) (%)4.3 4.2 6.1 4.7 4.25 2.7 Polymer content (%)29.2 29.339.3 39.C 48.85 ag.2 Hydroxyl nu~er245.8 244 207.5 208.9 176 175 Non-filterable componer,t (based on solids) - lOO,um mesh 2 (0) - 14 ) ~o.~-) n.d. ~o.i2) n-d-Viscosity (mPas) 3900 7000 7100 - 11800 )based on the polymer content 2! after 1:1 dilution ~ith toluene n.d. = not determined ~ he products of Examples 2S, 30 and 32 were finely divided and completely or substantially free from relatively coarse agglomerate particles. This was also confirmed by the running of a sample down a clean pla.e of glass, resulting in the formation of a thin, uniformly translucent, film. Example 29 produced a preparation heavily permeated by agglom-erates whilst Examples 31 and 33 produced viscous sritty compositions whose viscosity was estimated at more than 100,000 mPa.s and was not measured.
The products of Examples 28, 30 and 32 were processed in a standard formulation for integral skin rigid foam using com~ercial diphenyl methane diisocyanate to form mouldings increasing in thick-ness in steps. No surface voids occurredi the resulting mouldings had a smooth, streak-free surface and were distinguished by improved thermal stability under load and an increased E-modulus.
EXA~IPLES 34-38 The following testSwere carried out in accordance with Example 1. The reaction temperature was 130C in each case.
Example ~lo. 3~ 35 _ 36 37 38 Product initially introduced:
Polyol D 200 200 200 100 100 Mixture introduced:
Polyol D 400 400 400 400 300 Toluene 125 125 125 125 125 Acr~lonitrile 240 240 160 300 360 Styrene 150 145 220 190 215 ~AS - 15 ~SA - - 20 10 _ _ 49.4 i~5`~85 ~xa~ le No. 34 35 36 37 38 -T~ 14 TETA - - - 30.4 DBA - 22.5 - - 44.8 AIB'.~ 4 4 6 5 9 Monomer conversion (%) 94.9 96.3 97.0 95.8 96.8 Acrylonitrile boun21) 58.5 59.2 38.8 59.2 59.4 Styrene bound ) 38.8 36.9 56.0 38.7 26.3 Acrylonitrile in the distillate (%) 20.3 16.8 14.6 11.3 18.2 Styrene in the distillate (~) 2.9 4.1 3.8 3.1 5.2 Polymer content (~)39.6 40.2 41.8 50.4 60.4 Hydroxyl number 33.6 33.6 32.8 46.9 22.7 t~Gn-filterable component based on solids - lOOl~m mesh - (~) after 1:1 dilution with toluene ~ 0.1 ~ 0.11.2 ~ 0.1 0.8 EX~IPLE 39 10,000 g of polyol H were initially introduced into a reac'ion vessel equipped with a stirrer, reflux condenser, gas inlet pipe, temperature sensor and metering unit, after which the air was displaced by nitrogen and the contents of the vessel were heated with stirrins under nitrogen to a tem?erature of 125C. .~ mixture of 30,000 g of polyol H, 24,000 g of acrylonitrile, 15,200 g of styrene, 800 g of acrvlic acid, 1120 g of triethyl amine, 400 g of AIBN and 4000 g of toluene was then introducea over a period of 7 hours by means of a membrane pump (metering rate approximately 200 ml/minute). On completion of the addition, the mixture was stirred for 4 hours at 125C and then stripped at the same temperature under a vacuum of 2 mbar. The distillate was collectec in a receiver cooled with dry ice/acetone followed by a ccld trap. After 11 hours, strippina 115~85 was terminated and the product - a pale yellow finely divided dispersion - was drained off still hot through a 100 ~m mesh sieve. In order to characterize the product, the following data were determined or calculated from measured values:
Quantity of distillate 5115 g including acrylonitrile 18.6%
styrene 3.2%
acrylic acid 0.1%
triethylamine traces Monomer conversion 97.2%
Acrylonitrile bound ) 57.6%
Styrene bound 1) 37.6 Solids content 50.0%
Sieve residue 1) 0.03%
Hydroxyl number/acid number 14.3/1.7 Viscosity at 24C 11,800 mPa.s 1) based on total solids content " ~
The following formulations were foamed in a Hennecke* type UBT 78 high-pressure foaming machine.
Polyol I is a polyether triol of polyoxypropylene and terminal polyoxyethylene sequences, started with trime~hylol propane, which contains 13% of ethylene oxide and has a molecular weight of 4800 and a hydroxyl number of 35. The two polymer polyols used were produced semi-continuously in a 400-litre-capacity stirrer-equipped vessel in accordance with Examples 4 and 5 and corresponds in all their analytical data to the products obtained in those Examples. The quantities are quoted in parts by weight.
* Trademark LeA 19,528 ~' ~ 44 ~

r ~ple ~o. 40 41 ~2 ~3 Pol~er polyol of Example 2 100 50 - -Polymer poly~l of ~xample 3 - - 100 50 Polvol I ~ 50 - 50 Water 4.0 ~.0 4.0 4.0 Polysiloxane stabiliser 1.2 1.2 1.2 1.2 Triet-ylene diamine 0.050.05 0.05 0.05 Dimethyl ethanolamine 0.2 0.2 0.2 0.2 Tin dioctoate 0.3 0.3 0.3 0.3 Tolylene diisocyanate containing 80~ by weight of the 2,4-isomer 24.5 24.2 22.8 23.4 Tolylene diisocyanate containing 65~ by weight of the 2,4-isomer 24.5 2g.2 22.8 23.4 NCO/OH index 105 105 105 105 Polyol input (kg./min.) 26 28 26 28 Rise time (sec.) 60 60 55 65 Gel time (sec.) 200 155 180 105 Testing of the mechanical properties produced the follo~ing values:
Example ~o 40 41 42 43 Unit weight (kg/~

Tensile strength (kPa) Breaking elongation (%) Compression hardness at 40% deformation (kPa)-DIN 53 577 7.1 4.4 11.0 5.8 The approximately 2 m long and 1 m wide foam blocks were free from faults such as, for example, base bubbles, cracks or voids. During ageing in the absence of heat and moisture, no above-average deterioration in properties was observed. All the foams readily lend themselves to high-frequency welding to polyamide fabric.

~,,YA1`5~LE 4 q ~ hishly elastic foam was produced ir accordance with the following formulation in the foarming machine mentioned in the preceding Examples:
Polymer polyol o~ Example 4 50 parts by weight Polvol I 50 Water 4-0 Triethylene diamine 0.2 Tin dioctoate 0.4 "
Silicone stabiliser 0.8 "
Diethanolamine 1.5 Tris-2-chloroethyl phosphate 2.0 "
Tolylene diisocyanate containing 30%
by weight of the 2,4-isomer50.6 NCO/OH index 105 Input of polyol 28 kg./min.
Rise time 49 secs.
The fo'.lowing mechanical properties were determined on the foam:
Unit weight 26 kg/m3 Tensile strength 115 kPa Breaking elongation 115 Compression hardness at 40~ deformation 4.1 kPa This foam could also be effectively high-frequency welded to polyamide fabric.

Mouldings of integral rigid foam were produced in a Hennecke type HK 100 high-pressure foaming machine using a plate mould measuring 900 m~ long x 450 mm wide x 10 mm thick. The following formulations were foamed (quantitie~ in parts by weight):
A ~ C
Polymer polyol of Ex~mple 13 60 60 Commercial polyo - - 60 ~solids content 20~) ~ 5 A B C
Polyol I 3 3 3 Ethylene glycol 25 25 25 Ethylene diamine/propylene oxide adduct 1.5 1.5 1.5 Fatty-acid-based surfactant 7 7 7 Silicone stabiliser Organometallic activator 0.1 0.1 0.1 Phosphorus-containir.g flameproofing preparation 20 30 20 Trichloromonofluoromethane 8 8 8 The isocyanate component was a diphenylmethane-diisocyanate containing polymeric fractions which had been obtained by distilling off part of the binuclear co~ponent from 'he crude phosgenation product of an aniline-formaldehyde condensate. It was used in quantities corresponding to an NCO/OH
index of 110. A11 of the formulations could be foamed satisfactorily and without difficulty. The mouldings had a smooth, bubble-free surface, free from eddies and flow marks, ar.d a fault-free foamed core. The following mechanical values were determined:
A B C
Gross density (g/cc) 596 616 623 E-modulus in flexure (mPa) 1049 1012 435 Tensile strength (mPa) 14.3 13.1 11.7 Brea~ing elongation (%) 86.6 17.4 E-modulus in elongation (mPa) 634607 372 Heat distortion te~.perature (C) 96 83 71 These data illustr2'e the advantages of using polymer polyols having high polymer contents such as can be produce~ in accordance with the present invention.

~S~;S8S

EX~'~LEa 46 to 55:
The following formulations were foamed in a laboratory mould (aluminium, capacity 4 litres, dimensions 20 x 20 x 10 cm). To carry this out, the components of the formulation, other than the isocyanate, ~ere stirred to~ether in a cardboard container using a high-speed blade stirrer (2000 r.p.m.). After 60 seconds, the isocyanate was added and, after stirring for another 10 seconds, the mixture was poured into the mould the cover of which was held down by clips. After a residence time in the mould of 3 to 5 minutes, the mouldings were removed and compressed once to open the cells.
The quantities quoted in the Table represent parts 15 by weisht.
Example No. 46 47 48 49 Polymer of polyol of Example 2 25 - 25 Polyol H 75 50 75 50 Commercial polymer polyol (solids content 20%) - 50 - 50 Polymer content of the polyol ccmponent 10 10 10 10 Water 2.9 2.9 3.6 3.6 Commercial amine activator 0.72 0.72 0.82 0.82 Commercial organometallic catalyst 0.02 0.02 0.02 0.02 Commercial polysiloxane stabiliser 1.1 1.1 0.9 0.9 Polyisocyanate of Example 45 35.6 35.6 44.8 44.8 NCO/OH-index 100 100 100 100 ~15~

Exam~le No. 50 51 i2 53 .
Pol~mer polyol of Example 2 37.5 - 37.5 Polyol ~ 62.5 25 62.5 25 Commercial Pol~er polyol (solids content 20%) - 75 - 75 Polymer content of the pol~ol component 15 15 15 15 Water 2.9 2.9 3.6 3.6 Commercial amine activator 0. 72 0. 72 0. 82 0. 82 Commercial organometallic 0~ 02 0 . 02 0.02 0.02 catalyst Commercial polysiloxane1.1 1.1 0.9 0.9 stabiliser Polyisocyanate of Example 45 35.6 35.6 44. 7 44.7 NCO/OH-index 100 100 100 100 Example No. 54 55 Polymer polyol of Example 2 50 Polyol H 50 Commercial polymer polyol - 100 (solids content 20%) Polymer content of the 20 20 polyol component Water 2.9 2. 9 Commercial amine activator 0. 72 0. 72 Commercial organometallic 0. 02 0. 02 catalyst Commercial polysiloxane1.1 1.1 stabiliser Polyisocyanate of Example 45 35.3 35.3 ~CO/OH-index 100 100 S

~ he physical values set out in the follo~in~
Ta~le were determined for the foam mouldings. The different gross densities for the same water contents in the formulation are attributable to different inputs of the foam mixture. In these cases, compression hardness may be compared by standardisation to a single unit weight. The corresponding values are also shown in the Table.
Comparison of the polymer polyol of Example 2 with the commercial polymer olyol for the same amount of polymer in the formulation shows that the former is slightly to distinctly superior in its mechanical properties. So far as the optical ~uality of the mouldin~s (homogeneity, freedom from edge and internal cracks, cell structure and skin formation) is concerned, no differences were observed.
Example No. 46 47 48 49 50 3 _ Gross density (kg/m ) DIN 53 420 44 42 37.532 44 -Tensile strength (KPa) Breaking elongation (%) 170 155 150 140 160 Compression hardness at 40% deformation (KPa) DIN 53 577 4.8 4.3 5.43.6 5.6 Compression set (%) at 90~ compression 7.6 - 9.8 - 9.4 at 50~ compression - 4.9 - 8.2 Compression nardness comparison by standardisation to a sin~le unit weight: 3 unit weight (~.g~m ) 44 44 37.5 37.5 44 compression hardness (KPa) 4.8 4.7 5.4 4.7 5.6 t~ 5 ExamPle No. 51 52 53 54 55 Gross density (kg/m ) Tensile strength (KPa) Breaking elongation (%)150 145 125 145 135 Compression hardness at 40~ deforr,lation (XPa) DIN 53 577 4.2 6.5 4.7 6.3 4.8 Compression set (~0) at 90% compression - 13 - 3.7 at 50. co~.pression 6~0 - 6.3 - 7.3 Co~.pression nardness comparison by standardisation to a single unit weight: 3 unit weight (kg/m ) 44 38 38 43 43 compression hardness (KPa) 5.0 6.5 5.9 6.3 5.4 E~LES 56 to 59 The polymer polyol of Example 3, formulated with polyol H to a solids content of 10%, was also compared with the similarly adjusted commercial polymer polyol. The components of the fGrmulation not specified correspond to those in Examples 46 to 55. The quantities are again quoted in parts by weight.
Example No. 56 57 53 59 Polymer polyol Gf Example 3 25 - 25 Polyol H 75 50 75 50 Commercial polymer polyol - 50 - 50 Water 2.9 2.9 3.6 3.6 Polyisocyanate 36.4 36.4 45.645.6 NCO/OH index 100 100 100 100 Gross density (kg/m3) 45 42 35.5 32 Tensile stren~th (KPa) 205 155 175 155 Brea~in~ elongation (%)160 155 140 140 Compression hardness at 40O compression (KPa) 5.0 4.2 5.5 3.6 Compression hardness for standard unit weighl 3 Unit weisht (kg/m )45 45 35.535.5 compression hardness (~Pa) ~ n ~ R

In tnis test series, too, equally good mouldings were obtained from the polymer polyol according to the invention and the co~mercial polymer polyol without any foaming problems in either case. Once asain, the polymer polyol according to the invention is slishtly superior in its mechanical properties.
EXAMPLES 60 to 63 ~eat-setting moulded foams were produced in a 4-litre mould in the same way as in the preceding Examples. The following formulations were used (quantities in parts by weight):
Example No. 60 61 62 63 Polymer polyol of Example 20 25 Polymer polyol of Example 21 - 25 - -Polymer polyol of Example 24 - - 17 Polyol C 75 75 93 100 Polymer content of polyol (O) iO 10 10 10 ~,~iater 3-4 3 4 3 4 3 4 Commercial amine activator0.20.2 0.2 0.2 Tin dioctoate 0.1 0.1 0.1 0.1 Silicone stabiliser 1.0 1.0 1.0 1.0 Tolylene diisocyanate containing 80% of the 2,4-isomer Index 102 102 102 102 Mechanical testing produced the following values:
Example No. 60 61 62 63 ... _ ~ __ Unit weight (kg/mJ) 30 30 30 30 Tensile strength (KPa) 130 125 120 110 Breaking elongation (%) 180 165 125 180 Compression hardness at 40%
compression (KPa) 4.4 4.7 5.3 3.7 Compression set 90% compression (~) 4.7 5.3 6.2 3.5 All the mouldings had open cells and ~!ere free from internal cracks, voids and skin faults.

Claims (11)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the production of modified polyether polyols by the free radical polymerization of I. 1 to 60 parts by weight of a mixture of:
A) 20 to 99.9% by weight of acrylonitrile, B) 0 to 80% by weight of styrene, C) 0.1 to 10% by weight of an .alpha.,.beta.-unsaturated monocarboxylic or poly-carboxylic acid and D) 0 to 20% by weight of one or more other copolymerizable, olefinically unsaturated compounds;
II. 99 to 40 parts by weight of a polyetherpolyol, in the presence of a free-radical forming polymerization initiator characterized in that the .alpha.,.beta.-unsaturated monocarboxylic or polycarboxylic acid is used in the form of a salt with a primary, secondary or tertiary monoamine or polyamine.

2. A process as claimed in Claim 1, wherein said amines used are selected from the group consisting of aliphatic amines, cycloaliphatic amines, amino alcohols, aromatic amines and heterocyclic nitrogen bases having a molecular weight or an equivalent weight of from 30 to 150.

3. A process as claimed in Claim 1, characterized in that the .alpha.,.beta.-unsaturated carboxylic acid (C) used is a compound selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, oligomers of acrylic acid corresponding to the formula in which n is an integer of from 1 to 5, LeA 19,528 maleic acid, fumaric acid, itaconic acid, citraconic acid, semiesters or semiamides of .alpha.,.beta.-unsaturated polycarboxylic acids and semiesters or semiamides of saturated polycarboxylic acids with unsaturated, poly-merizable alcohols or amines.

4. A process as claimed in Claim 1, wherein said copolymerizable monomers (D) used are selected from the group consisting of esters of .alpha.,.beta.-unsaturated monocarboxylic or polycarboxylic acids with monohydric or polyhydric alcohols, vinyl esters, vinyl halides, .alpha.,.beta.-unsaturated nitriles, .alpha.,.beta.-unsaturated amides, aminoalkyl esters of .alpha.,.beta.-unsaturated monocarboxylic or polycarboxylic acids, esters of vinyl phosphonic acid or vinyl aromatic hydrocarbons and mixtures thereof.

5. A process as claimed in Claim 1, wherein said radical-forming polymerization initiators used have half life periods of thermal decomposition, at the polymerization temperature, of less than 5 minutes.

6. A process as claimed in Claim 1 wherein organic peroxides or aliphatic azo compounds are used as said polymerization initiators.

7. A process as claimed in Claim 1, characterized in that azo-bis-isobutyronitrile is used as the poly-merization initiator.

8. A process as claimed in Claim 1, wherein said polymerization reaction is carried out in the presence of toluene.

9. A process as claimed in Claim 1, wherein said polymerization reaction is carried out at temperatures in the range from 100°C to 140°C.

10. A process for the production of optionally cellular polyurethane plastics by reacting A) polyisocuanates with LeA 19,528 B) polyether polyols modified by graft polymerization and, optionally C) other relatively high molecular weight and/or low molecular weight compounds containing isocyanate-reactive hydrogen atoms, optionally in the presence of D) blowing agents, catalysts and other additives known per se, characterized in that component (B) comprises a polyether produced by the free radical polymerization of:
I. 1 to 60 parts by weight of a mixture of;
A) 20 to 99.9% by weight of acrylonitrile, B) 0 to 80% by weight of styrene, C) 0.1 to 10% by weight of an .alpha.,.beta.-unsaturated monocarboxylic or polycarboxylic acid and D) 0 to 20% by weight of one or more other copolymerizable, olefinically unsaturated compounds;
II. 99 to 40 parts by weight of a polyether polyol; in the presence of a free-radical forming polymerization initiator, wherein the .alpha.,.beta.-unsaturated monocarboxylic or polycarboxylic acid is used in the form of a salt with a primary, secondary or tertiary monoamine or polyamine.

11. A process as claimed in Claim 1, wherein said polymerization reaction is carried out in the presence of an inert organic solvent.

LeA 19,528