United States Patent (19) 11 Patent Number: 4,500,656 Rasshofer et al. (45) Date of Patent: Feb. 19, 1985

54 PROCESS FOR THE PREPARATION OF A Saunders and Frisch, Interscience Publishers, pp. CELLULAR POLYURETHANE 228-239 (1964). 75 Inventors: Werner Rasshofer, Cologne; A. Smola, Mitteilungen des Chemischen Forschungsin Ernst-Christoph Prolingheuer, Herne, tituts der Wirtschaft Osterreichs 2, 38-40 and 43-45 both of Fed. Rep. of Germany (1948). Chemical Abstracts 43 (1949), 6157h. 73 Assignee: Bayer Aktiengesellschaft, Primary Examiner-Herbert S. Cockeram Leverkusen, Fed. Rep. of Germany Attorney, Agent, or Firm-Gene Harsh; Joseph C. Gil; (21) Appl. No. 594,054 Thomas W. Roy 22 Filed: Mar. 28, 1984 57 ABSTRACT 30 Foreign Application Priority Data The present invention relates to a process for the prepa ration of a cellular polyurethane by the reaction of Apr. 5, 1983 DE Fed. Rep. of Germany ...... 3.32215 (A) a polyisocyanate with 51 Int. Cl...... C08G 18/14; C08G 18/32 (B) an isocyanate reactive component containing 52 U.S. Cl...... 521/164; 521/904 (1) at least one component having a molecular weight 58) Field of Search ...... 521/164,904 of about 60-2000 and a functionality of 2 to 8, containing isocyanate reactive groups, (56) References Cited (2) optionally at least one component having a molec U.S. PATENT DOCUMENTS ular weight of about 2000 to 12,000 and a function 2.343,808 3/1944 Schlack ...... 528/85 ality of 2 to 8 containing isocyanate reactive 3,261,813 7/1966 Ramos ...... 528/63 groupS. 3,391,091 7/1968 Considine et al...... 528/58 (3) about 0.1 to 30 parts, based on 100 parts of 3,425,964 2/1969 Stanley ...... 260/775 AM (B1)+(B2), of a liquid adduct of an amine and 3.5l 1,814 5/1970 Ogura et al...... 260/50.2

carbon dioxide, and 4,077,920 3/1978 Yukuta et al. ... 521/17 (4) optionally water, blowing agents, foam stabilizers, 4,136.241 1/1979 Ammann ...... 521/63 catalysts and other auxiliary agents and additives, FOREIGN PATENT DOCUMENTS characterized in that the liquid adduct of amine and 1570571 7/1969 Fed. Rep. of Germany . carbon dioxide is liquid at 20 C., optionally contains 2200480 7/1972 Fed. Rep. of Germany . water, and is an adduct of carbon dioxide and an amine 103506 2/1968 United Kingdom . having at least one amino group and containing at least one primary, secondary or tertiary hydroxyl group, OTHER PUBLICATIONS which amine may be solid or liquid at 20° C. Smola, Chem. Abs. 43 (1949) 6157h. "Polyurethane-Chemistry and Technology", Part II, 12 Claims, No Drawings 4,500,656 1. 2 having a functionality of 22 and a molecular weight of PROCESS FOR THE PREPARATION OF A from about 60 to 200. CELLULAR POLYURETHANE In particular, it has also surprisingly been found that not only carbamates, which are ammonium salts of alkyl BACKGROUND OF THE INVENTION 5 carbamic acids, but also salts of carbonic acid with these 1. Field of the Invention polyamines containing hydroxyl groups, which salts are This invention relates to a process for the preparation obtained by carrying out the reaction of the amines with of cellular polyurethanes, using liquid adducts of mono carbon dioxide in the presence of water, and the mix or polyamines containing one or more hydroxyl groups tures of salts of the carbamic acids and carbonic acid, and carbon dioxide, in particular with the addition of 10 are liquid. The differences between carbamates as salts liquid carbonic acid salts of such hydroxyl group-con of carbamic acid and carbonates or bicarbonates as salts taining mono- or polyamines. of carbonic acid are well known to the man of the art 2. Description of the Invention and have been described, for example, in A. Smola, The use of carbon dioxide addition products of hy Mitteilungen.des Chemischen Forschungsinstituts der droxyl group containing amines (hereinafter called: 15 Wirtschaft Österreichs 2, 38-40 and 43–45 (1948) hydroxylic amines) for the preparation of polyurethanes (Chemical Abstracts 43 (1949), 6157 h). is known perse and the use of ethanolamine carbamate The fact that liquid carbonic acid salts of amines in a process for the production of a cellular polyure containing hydroxyl groups are now available also thane elastomer is mentioned in DE-OS 2200 480, but this prior publication does not disclose whether the 20 makes it possible to overcome the disadvantages of the ethanolamine carbamate is in the solid or liquid state. carbanates of such hydroxyl group-containing amino DE-PS 2 621 582, however, reveals that carbamates compounds known in the art. Thus it is mentioned in which are reaction products of primary or secondary DE-PS2 621 582 that amino carbamates of the aforesaid amines containing one or two hydroxyl groups and "amines are generally hygroscopic' and that "the carbon dioxide are solid and are obtained in the solid 25 aminocarbamate which has been synthesized separately, state if they are prepared by introducing carbon dioxide isolated and purified is difficult to store in the form of a in an alcohol or other solvent, and cannot form a homo fine powder' and that there is "insufficient dispersion in geneous, monophasic mixture with a polyol. The last the polyol'. mentioned prior publication does not disclose that the DE-OS 2200 480 teaches that the aminocarbamates carbon dioxide addition products in question are liquid are generally no longer heat stable at temperatures from at room temperature or that they can be obtained as about 35 C. and decompose at such temperatures. A liquids. similar teaching is given in DE-OS 1570.571, according It is known from DE-OS 1570 571 that liquid carba to which conversion of the amines into carbamates by mates of compounds containing amino groups do exist. reaction with CO2 can only be carried out at tempera The amines mentioned in the said prior publication are, 35 tures of from -40° C. to 40° C., preferably from O C. however, limited to diamines or polyamines containing to 20 C. The carbamates prepared by way of example ether groups, wherein from 0.1 to 50% of the amino in this prior publication for the most part already de groups may be replaced by hydroxyl groups. In this compose at room temperature or at 30° C. reference it is preferred, however, to use high molecu The liquid carbon dioxide adducts according to the lar weight or relatively high molecular weight amines 40 present invention, on the other hand, are surprisingly generally having only a low basic nitrogen content and stable. They are prepared at temperatures of up to with the amino groups frequently attached to secondary 80°-90° C. or even higher and vigorous uptake of car carbon atoms, so that the amount of carbon dioxide bon dioxide in some cases only begins at this tempera taken up is low. ture. The hygroscopic character mentioned in the prior The use of products according to DE-OS 2200 480 45 publication as a disadvantage of the crystalline carba and DE-PS 2 621 582 for the production of polyure thane foams is also known. mates of the hydroxyl-containing amines is now of no The state of the art therefore does not provide the importance since the (hydrogen) carbonates which are man of the art with the possibility of using liquid, low assumed to be formed from the carbamates by uptake of viscosity carbon dioxide adducts of hydroxyl group 50 water are in any case liquid and suitable for the prepara containing mono- or polyamines with a high amine and tion of cellular polyurethanes. Moreover, the liquid carbon dioxide content for the production of polyure carbamates according to this invention were not ob thane foams, and in particular, no homogeneous, opti served to have any pronounced tendency to absorb cally clear, monophasic, stable mixtures of such carbon water. The carbamates and (hydrogen) carbonates ac dioxide adducts and polyols containing at least two 55 cording to the invention could also be subjected to isocyanate reactive hydrogen atoms are known. prolonged heating to temperatures up to 100° C., e.g. It has now surprisingly been found that carbon diox 50 C., and could be subjected to a vacuum at room ide adducts of mono- or polyamines containing one or temperature, e.g. of 20 mbar, without any evolution of more hydroxyl groups, in which the amino groups may carbon dioxide or loss of water being observed. be primary and/or secondary and possibly also tertiary 60 Liquid carbamates and (hydrogen) carbonates of and may be substituents on or chain members in acyclic hydroxyl group-containing amines, in particular (hy. or cyclic aliphatic compounds are obtained in a liquid drogen) carbonates having such properties could not be form and remain liquid without crystallization if they inferred from the published state of the art, nor could are prepared by addition of the hydroxyl-containing their use in a process for the production of foamed amines to carbon dioxide and optionally water, and that 65 polyurethane and/or polyurea resins, in which, by vir the adducts prepared by this method are homoge tue of their stability, solubility and liquid aggregate neously soluble in the polyols conventionally used for state, they are more easily worked up than the carba the preparation of polyurethanes, in particular polyols mates and carbonates known in the art. 4,500,656 3 4. N,N-di- and N,N,N-tri-(3-hydroxyalkyl)amines and SUMMARY OF THE INVENTION of N-mono-, N,N'-di- and N,N',N'-tri-((3-hydroxyalk The present invention relates to a process for the yl)ethylenediamine are preferred, in particular those preparation of a cellular polyurethane by the reaction of of ethanolamine, diethanolamine, propanolamine, (A) a polyisocyanate with 5 isopropanolamine, diisopropanolamine and N (B) an isocyanate reactive component containing hydroxyethyl ethylenediamine. (1) at least one component having a molecular weight The following are compounds having at least one of about 60-2000 and a functionality of 2 to 8, primary, secondary or tertiary hydroxyl group and at containing isocyanate reactive groups, least one primary, secondary and optionally tertiary (2) optionally at least one component having a molec 10 amino group which may be used for the preparation of ular weight of about 2000 to 12,000 and a function the carbon dioxide adducts (B3); ality of 2 to 8 containing isocyanate reactive Monoamino-nono- or -dihydroxy compounds (having groups, primary or secondary amino groups), e.g. 2-aminoe (3) about 0.1 to 30 parts, based on 100 parts of thanol, 2-methyl-2-aminoethanol, 2-ethyl-2-aminoe (B1) -- (B2), of a liquid adduct of an amine and 15 thanol, 6-hydroxyhexylamine; bis-hydroxyalkyl de carbon dioxide, and rivatives of primary amines, e.g. bis-(3-hydroxye (4) optionally water, blowing agents, foam stabilizers, thylamine, bis-(3-hydroxypropyl)-amine, and catalysts and other auxiliary agents and additives, N,N,N'-tris-(3-hydroxypropyl)-ethylene dianine; characterized in that the liquid adduct of amine and also compounds such as 3-aminomethyl-3,5,5-trime carbon dioxide is liquid at 20 C., optionally contains thylcyclohexanol, 2-amino-2-hydroxymethyl-1,3- water, and is an adduct of carbon dioxide and an amine propanediol, 2-amino-2-methyl-1,3-propanediol or having at least one amino group and containing at least 2-amino-2-methyl-propanol. one primary, secondary or tertiary hydroxyl group, Also monoalkoxylated diamines derived from ali which amine may be solid or liquid at 20 C. phatic straight chained or branch chained diamines, 25 preferably having 2 to 12 carbon atoms, or cycloali DETAILED DESCRIPTION OF THE phatic diamines of the cyclohexane, dicyclohexyl, dicy INVENTION clohexylmethane, dicyclohexyl-2,2-propane or dicy In a preferred process according to the invention, the clohexyl-1,1-cyclohexane series optionally substituted liquid adduct of amine and carbon dioxide has been with alkyl groups, and alkylene oxides such as ethylene obtained by the action of carbon dioxide on the amine, 30 oxide, propylene oxide, butylene-2,3-oxide as well as optionally in the presence of water but in the absence of styrene oxide. Monoalkoxylated aliphatic diamines hav solvents of the type of aliphatic (halogenated) hydro ing 2 to 6 carbon atoms and in some cases also cycloali carbons, optionally nitrated or halogenated aromatic phatic diamines which have been alkoxylated with eth hydrocarbons optionally carrying alkyl groups, lower ylene oxide or propylene oxide are preferred. The fol aliphatic alcohols, acid amides, lactams and aprotic 35 lowing are examples: N-(3-hydroxyethyl)-ethylenedia polar solvents (e.g. ketones, ethers, nitriles, N-sub mine, N-(AG-hydroxyethyl)-propylenedianine-(1,2), N stituted acid amides or N-substituted lactams), at tem (3-hydroxyethyl)-propanediamine-(1,3), N-(g-hydrox peratures of from about -25 C. to 160° C., preferably yethyl)-hexanediamine-(1,6), N-((3-hydroxyethyl)- from 0 C. to 130° C., most preferably from 15° C. to dodecanedianine-(1,12), N-(6-hydroxypropyl)- 100 C. On the other hand, polyols with an OH number 40 ethylenediamine, N-(3-hydroxypropyl)-propylenedia above 112 containing 2-8 hydroxyl groups may be used mine-(1,2), N-(A-hydroxypropyl)-propanediamine-(1,3), as solvents but it is most particularly preferred not to N-(3-hydroxypropyl)-butanediamine-(1,4), N-(3- use solvents. hydroxybutyl)-ethylenediamine, N-(R-hydroxybutyl)- In another process which is preferred according to hexanediamine-(1,6), N-(3-hydroxyethyl)-xylylenedia the invention, the liquid adduct of amine and carbon 45 mine-(1,3), N-((3-hydroxyethyl)-cyclohexanediamine dioxide has (1,3) or -(1,4), N-((3-hydroxyethyl)-2,2,4-trimethylhex (a) a basic nitrogen content of about 19 to about 3.5% ane diamine-(1,6), 1-methyl-2-amino-4-N-(2-hydroxye by weight, thyl)-aminol-cyclohexane, N-((3-hydroxyethyl)-isopho (b) a hydroxyl group content of about 27.5 to about rone diamine, N-(3-hydroxyethyl)-4-aza-4-methyl-hep 8.5% by weight, 50 tanediamine-(1,7). Bis-(hydroxyalkyl)-diamines which (c) a carbon dioxide content of about 42 to 1.0% by have been obtained from the corresponding straight weight and chained or branched chained aliphatic or cycloaliphatic (d) a water content from 0 to about 15% by weight. diamines by alkoxylation with alkylene oxides are also Another preferred process according to the invention suitable, particularly those obtained by alkoxylation is characterized in that the liquid adduct of amine and 55 with ethylene oxide and/or propylene oxide. The fol carbon dioxide is a carbonate and/or bicarbonate, lowing are examples: N,N'-bis-(3-hydroxyethyl)- which is liquid at 20° C., of an amine having at least one ethylenediamine, N,N'-bis-(3-hydroxypropyl)- primary, secondary or tertiary amino group and con ethylenediamine, N,N'-bis-(g-hydroxyethyl)-propylene taining at least one primary, secondary or tertiary hy diamine-(1,2), N,N'-bis-(6-hydroxypropyl)-propanedia droxyl group, which amine may be solid or liquid at 20 60 mine-(1,3), N,N'-bis-(g-hydroxyethyl)-1-methyl-2,4- C., and in that it has and -2,6-diaminocyclohexane, N,N'-bis-(3-hydroxy (a) a basic nitrogen content of about 17 to about 3.5% propyl)-1-methyl-2,6- and -2,4-diaminocyclohexane, (b) a hydroxyl group content of about 20.5 to about N,N'-bis-((3-hydroxyethyl)-isophoronediamine, N,N'- 8.5%, bis-(3-hydroxypropyl)-p-xylylene diamine, and N-((3- (c) a carbon dioxide content of about 36% to about 65 hydroxyethyl)-N'-((3-hydroxypropyl)-ethylenediamine. 2.5% by weight, and Alkoxylated triamines and polyamines may also be (d) a water content of about 3 to about 15% by weight. used, e.g. tris-((3-hydroxyethyl)-1,6, 11-triaminoundec Liquid carbonates and/or bicarbonates of N-mono-, ane. Mixtures of compounds in various stages of alkoxy 4,500,656 5 6 lation may also be used, e.g. mixtures of mono-, bis- and ried out by introducing a vigorous stream of carbon tris-hydroxyethyl-ethylenediamine or mixtures of dioxide into the amine which has been previously intro mono- and diethanolamine. duced into a suitable stirrer vessel, optionally with a Compounds such as 1,3-diamino-propanol-2; 1,6- suitable quantity of water, without cooling or external diamino-hexanol-2; 1,5-diaminopentanol-3; 3,4-diamino 5 heating. The reaction, which in most cases sets in imme 2,2-dimethyl-butanol-1; diaminocyclohexanols and diately with vigorous evolution of heat, rapidly raises 1,1-diaminoundecanol-6 may also be used. the temperature of the mixture to about 40°-130' C. Other suitable compounds include 6-hydroxyethyl A marked fall in temperature occurs towards the end hydrazine and g-hydroxypropylhydrazine. of the reaction. If the reaction temperature rises rapidly Also suitable for the preparation of carbonic acid 10 due to the exothermic reaction, e.g. to 100° C., external adducts (but not for the preparation of the carbamates) cooling is preferably applied to prevent the side reac are compounds containing at least one but preferably tions (e.g. ring formation) and discolorations which Several hydroxyl groups and at least one tertiary amino occur if the temperatures are too high. group. These include, for example, triethanolamine, If desired, the amine or mixture of amine and water tris-(3-hydroxypropyl)-amine, 6-methyl-3-oxa-6- 15 azaheptanol, tetra-(3-hydroxyethyl)-ethylenediamine, may from the start be heated to an elevated temperature tetra-((3-hydroxypropyl)-ethylenediamine, tetra-(6- before the CO2 is introduced. No advantages are ob hydroxyethyl)-isophoronediamine, bis-(3-hydroxye tained by maintaining the reaction temperatures within thyl)-methylamine, bis-(3-hydroxyethyl)-butylamine, the range of from -40° C. to 40° C. although this is bis-(g-hydroxypropyl)-ethylamine, bis-(3-hydroxy 20 possible, as described in DE-OS 1570 571. In many propyl)-methylamine, bis-(3-hydroxypropyl)-hexyla cases, it is even advisable to employ elevated tempera mine and bis-(3-hydroxyethyl)-oleylamine. tures in order to make the mixture more easily stirrable. Preferred for the preparation of the carbon dioxide What has been said above concerning the heat of adducts are those amine compounds which may be reaction produced and the limits of reaction tempera thought of as being obtained by the reaction of 1 to 2 25 ture to be maintained applies both to the preparation of mols of ethylene oxide and/or propylene oxide with the carbamates and to the preparation of the carbonic ammonia or the reaction of 1 to 3 mols of ethylene oxide acid salts, but in the case of the latter it should be re and/or propylene oxide with ethylenediamine. membered that the bringing together of amine and These amines containing hydroxyl groups are con water is in itself sufficient to release a considerable verted into carbon dioxide adducts by a reaction with quantity of heat. The temperatures occurring with the carbon dioxide. If no water is used in the reaction, so introduction of carbon dioxide are on average below called carbamates are formed, which constitute ammo those produced in the preparation of the carbamates. nium salts of alkylcarbamic acids. If water is used in The carbon dioxide adducts are clear, low viscosity stoichiometric or even larger quantities (based on the liquids, generally light in color, and they are stable and amine), carbonic acid salts of the corresponding amino 35 show no tendency to crystallization. They are generally compounds are obtained. If a quantity of water less than Soluble in polar media such as methanol, ethanol, di that required for complete formation of the carbonic methylformamide, acetonitrile, dimethylsulphoxide, acid Salt is used, the corresponding mixtures of carba sulpholan, etc. and in low molecular weight polyols, mates and (hydrogen) carbonates are obtained. Water e.g. with OH numbers from about 200 to 1800, such as may, of course, also be used in a larger than the stoichio 40 are obtained, for example, by the addition of ethylene metric quantity required for formation of the carbonic oxide to glycerol or trimethylolpropane. In quantities of acid salt. The reaction is carried out at temperatures in up to about 50% by weight, however, they are also the range of from about -25° C. to 160° C., preferably stable in storage in polyol mixtures of the kind used, for from about 0°C. to 130° C., most preferably from about example, for the preparation of rigid polyurethane 15 C. to 100° C., without any solvents of the type of 45 foam, and form monophasic, clear solutions therein. aliphatic (halogenated) hydrocarbons, optionally ni When used for the preparation of cellular polyurethanes trated or halogenated aromatic hydrocarbons option according to the invention, they act as blowing agents, ally containing alkyl groups, lower aliphatic alcohols, cross-linking agents and catalysts. aprotic polar solvents, acid amides or lactams. Polyols The following components are used for carrying out with an OH number above 112 containing 2 to 8 hy SO the process according to the invention. droxyl groups may, however, be used as solvents al As starting component (A): aliphatic, cycloaliphatic, though it is preferred to carry out the reaction without araliphatic, aromatic and heterocyclic polyisocyanates solvents. such as those described, for example, by W. Siefken in The adducts (B3) are put into the process in a quan Justus Liebigs Annalen der Chemie, 562, pages 75 to tity of from about 0.1 to 30 parts, preferably from about 55 136, for example those corresponding to the formula 0.15 to 15 parts, most preferably from about 0.2 to 2.99 parts, based on 100 parts of (B1)+(B2). Q(NCO) Preparation of the adducts may be carried out with any form of carbon dioxide, preferably with unpurified wherein carbon dioxide from steel cylinders, and it may be car 60 n = 2-4, preferably 2, and ried out at subatmospheric or excess pressure but pref Q denotes an aliphatic hydrocarbon group having erably at normal pressure. The temperatures at which 4-18, preferably 6-10, carbon atoms, the preparation is carried out generally range from a cycloaliphatic hydrocarbon group having 4-15, about -25 C. to the boiling point of the amine used if preferably 5-10, carbon atoms, this is below 200° C. at normal pressure, otherwise to 65 an aromatic hydrocarbon group having 6-15, prefera about 160° C. A narrower, preferred range is from bly 6-13, carbon atoms, about O' C. to 130 C, and from about 15° C. to 100° C. or an araliphatic hydrocarbon group having 8-15, is particularly preferred. The process is preferably car preferably 8-13, carbon atoms. 4,500,656 7 8 Examples include 1,4-tetramethylene, diisocyanate, As starting component B(1): compounds containing 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocy at least two isocyanate reactive hydrogen atoms and anate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- generally having a molecular weight of from about 60 and -1,4-diisocyanate and any mixtures of these isomers, to 2000. These include compounds containing amino 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl groups, thiol groups or carboxyl groups or preferably cyclohexane (German Auslegeschrift No. 1 202 785, hydroxyl groups, in particular from 2 to 8 hydroxyl U.S. Pat. No. 3,401,190), 2,4- and 2,6-hexahydrotoly groups, especially those with molecular weights of from lene diisocyanate and any mixtures of these isomers, about 200 to 1000, preferably from about 300 to 800, e.g. hexahydro-2,4'- and/or -4,4'-diphenylmethane diisocya polyesters, polyethers, polythioethers, polyacetals, nate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6- 10 polycarbonates and polyester amides having at least 2, tolylene diisocyanate and any mixtures of these isomers, generally 2 to 8, preferably 2 to 6 hydroxyl groups, such diphenylmethane-2,4'- and/or 4,4'-diisocyanate, and as the known compounds used for the preparation of naphthylene-1,5-diisocyanate. both homogeneous and cellular polyurethanes. Poly The following, for example, may also be used accord ether polyols are particularly preferred. ing to the invention: triphenylmethane-4,4',4'-triisocya 15 (a) Suitable polyesters containing hydroxyl groups nate; polyphenyl-polymethylene polyisocyanates which include, for example, the reaction products of polyhyd may be obtained by aniline-formaldehyde condensation ric, preferably dihydric alcohols with the optional addi followed by phosgenation and have been described, for tion of trihydric alcohols and polybasic, preferably example, in British Pat. Nos. 874 430 and 848 671; m dibasic carboxylic acids. Instead of using free polycar and p-isocyanatophenylsulphonyl isocyanates accord 20 boxylic acids, the corresponding polycarboxylic acid ing to U.S. Pat. No. 3,454,606; (perchloroinated aryl anhydrides or polycarboxylic acid esters of lower alco polyisocyanates as described, for example, in German hols or mixtures thereof may be used for the preparation Auslegeschrift No. 1 157 601 (U.S. Pat. No. 3,277,138); of the polyesters. The polycarboxylic acids may be polyisocyanates containing carbodiimide groups as de aliphatic, cycloaliphatic, aromatic and/or heterocyclic scribed in German Pat. No. 1 092 007 (U.S. Pat. No. 25 and may be substituted, e.g. with halogen atoms, and/or 3, 152,167) and in German Offen legungsschriften Nos. 2 unsaturated. 504 400, 2537 685 and 2552 350; norbornane diisocya The following are examples of such carboxylic acids nates according to U.S. Pat. No. 3,492,350; polyisocya and their derivatives: nates containing allophanate groups as described e.g. in succinic acid, adipic acid, suberic acid, azelaic acid, British Pat. No. 994 890, Belgian Pat. No. 761. 626 and 30 sebacic acid, phthalic acid, isophthalic acid, trimellitic Netherlands Patent Application No. 7 102524; polyiso acid, phthalic acid anhydride, tetrahydrophthalic acid cyanates containing isocyanurate groups as described anhydride, hexahydrophthalic acid anhydride, tetra e.g. in U.S. Pat. No. 3,001,973, German Pat. Nos. 1022 chlorophthalic acid anhydride, endomethylene tetrahy 789, 1 222 067 and 1 027 394 and in German Offen drophthalic acid anhydride, glutaric acid anhydride, legungsschriften Nos. 1929 034 and 2004 048; polyiso 35 maleic acid, maleic acid anhydride, fumaric acid and cyanates containing urethane groups as described e.g. in dimerized and trimerized unsaturated fatty acids option Belgian Pat. No. 752 261 or in U.S. Pat. Nos. 3,394, 164 ally mixed with monomeric unsaturated fatty acids such and 3,664,457; polyisocyanates containing acylated urea as oleic acid, dimethylterephthalate and terephthalic groups according to German Pat. No. 1 230 778; poly acid-bis-glycol esters. Suitable polyhydric alcohols in isocyanates containing biuret groups as described e.g. in 40 clude e.g. ethylene glycol, propylene glycol-(1,2) and U.S. Pat. Nos. 3, 124,605, 3,201,372 and in British Pat. -(1,3), butylene glycol-(1,4), -(1,3) and -(2,3), hexanedi No. 889 050; polyisocyanates prepared by telomeriza ol-(1,6), octanediol-(1,8), neopentyl glycol, 1,4-bis tion reactions as described in e.g. in U.S. Pat. No. hydroxymethylcyclohexane, 2-methyl-propane-1,3- 3,654,106; polyisocyanates containing ester groups as diol, glycerol, trimethylolpropane, hexanetriol-(1,2,6), mentioned, for example, in British Pat. Nos. 965 474 and 45 butanetriol-(1,2,4), trimethylolethane, pentaerythritol, 1 072956, U.S. Pat. No. 3,567,763 and German Pat. No. - quinitol, mannitol and sorbitol, formitol, methyl glyco 1 231 688; reaction products of the above mentioned side, diethylene glycol, triethylene glycol, tetraethylene isocyanates with acetals according to German Pat. No. glycol and higher polyethylene glycols, dipropylene 072 385; and polyisocyanates containing polymeric glycol, and higher propylene glycols and dibutylene fatty acid esters according to U.S. Pat. No. 3,455,883. 50 glycol and higher polybutylene glycols. The polyesters The distillation residues containing isocyanate groups may contain a proportion of carboxyl end groups. Poly from the commercial production of isocyanates may esters of lactones such as e-caprolactone or of hydrox also be used, optionally dissolved in one or more of the ycarboxylic acids such as a)-hydroxycaproic acid may above mentioned polyisocyanates. Any mixtures of the also be used. above mentioned polyisocyanates may also be used. 55 (b) The hydroxypolyethers containing at least 2, gen Aromatic polyisocyanates are preferably used and as erally 2 to 8, preferably 2 to 6 hydroxyl groups, which a rule it is particularly preferred to use industrially may also be used according to the invention and are in readily available polyisocyanates such as 2,4- and 2,6- fact preferred, are known perse and may be prepared, tolylene diisocyanate and any mixtures of these isomers for example, by the polymerization of epoxides such as: ("TDI'), polyphenyl-polymethylene polyisocyanates 60 ethylene oxide, propylene oxide, butylene oxide, tetra such as may be prepared by anilineformaldehyde con hydrofuran, styrene oxide or epichlorohydrin either on densation followed by phosgenation ("crude MDI") their own, e.g. in the presence of Lewis catalysts such as and polyisocyanates containing carbodiimide groups, BF3 or by their chemical addition, preferably the addi urethane groups, allophanate groups, isocyanurate tion of ethylene oxide and propylene oxide, optionally groups, urea groups or biuret groups ("modified poly 65 as mixtures or successively, to starting components isocyanates"), in particular the modified polyisocya containing reactive hydrogen atoms, such as water, nates derived from 2,4- and/or 2,6-tolylene diisocya alcohols, ammonia or amines, for example the follow late. ing: ethylene glycol, propylene glycol-(1,3) and -(1,2), 4,500,656 9 10 trimethylolpropane, glycerol, sorbitol, mannitol, quini tainable by the autocondensation of formaldehyde hy tol, trimethylolethane, pentaerythritol, hexanetriol drate and of compounds capable of enediol formation as (1,2,6), 4,4'-dihydroxy-diphenylpropane, aniline, etha co-catalysts (German Offenlegungsschriften Nos. 2639 nolamine or ethylene diamine. Sucrose polyethers such 084, 2 714084, 2714 104, 2721 186, 2738 154 and 2 738 as those described, for example, in German Ausleges 512). chriften Nos. 1 176 358 and 1 064 938 and polyethers (f) Low molecular weight polyols with molecular started on formitol or formose (German Offendegungss weights of up to 400 suitable for the purpose of the chriften Nos. 2 639 083 and 2737951) may also be used invention also include ester diols corresponding to the according to the invention. It is frequently preferred to general formulae use polyethers containing predominantly primary OH O groups (up to about 90% by weight thereof, based on all HO-(CH2)-CO-O-(CH2)-OH and of the OH groups in the polyether). (c) Polyester amides and polyamides, hydroxyl poly HO-(CH2)-O-CO-R-CO-O-(CH2). carbonates, polyacetals, polythioethers and polybutadi --OH enes of known type containing OH, NH and/or SH 15 in which groups may also be used in the process according to the R represents an alkylene group having 1-10, prefera invention. bly 2 to 6 carbon atoms or a cycloalkylene or aryl (d) Polyhydroxyl compounds already containing ene group having 6 to 10 carbon atoms, urethane or urea groups and modified or unmodified X=2 to 6 and natural polyols such as castor oil or carbohydrates, e.g. 20 y = 3 to 5, starches, may also be used. Products of addition of e.g. 8-hydroxybutyl-ehydroxycaproic acid ester, co alkylene oxides to phenol formaldehyde resins or to hydroxyhexyl-y-hydroxybutyric acid ester, adipic acid urea formaldehyde resins may also be used according to bis-(g-hydroxyethyl)-ester and terephthalic acid-bis-(g- the invention. hydroxyethyl)-ester; (e) The starting components may also include com 25 pounds with molecular weights of from about 32 to 400 diolurethanes corresponding to the general formula containing at least two isocyanate reactive hydrogen atoms. These are also compounds containing hydroxyl groups and/or amino groups and/or thiol groups and /or carboxyl groups, preferably hydroxyl groups and wherein /or amino groups, and may be used as chain lengthening R" represents an alkylene group having 2-15, prefera agents or cross-linking agents. These compounds gener bly 2-6, carbon atoms or a cycloalkylene or aryl ally contain from 2 to 8, preferably 2 to 4, isocyanate ene group having 6-15 carbon atoms and reactive hydrogen atoms. x represents a number from 2 to 6, These compounds with molecular weights of from 35 e.g. 1,6-hexamethylene-bis-(3-hydroxyethylurethane) about 32 to 400 containing at least two isocyanate reac O 4,4'-diphenylmethane-bis-(3-hydroxybutyl-ure tive hydrogen atoms may also be used as mixtures of thane); and diol ureas corresponding to the general such compounds. The following are examples of such formula compounds: ethylene glycol, propylene glycol-(1,2), and -(1,3), bu 40 tylene glycol-(1,4), -(1,3) and -(2,3), pentanediol-(1,5), hexanediol-(1,6), octanediol-(1,8), neopenty glycol, kn kn 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3- propanediol, dibronobutenediol (U.S. Pat. No. wherein 3,723,392), glycerol, trimethylolpropane, hexanetriol 45 R' represents an alkylene group having 2-15, prefer (1,2,6), trimethylolethane, pentaerythritol, quinitol, ably 2-9, carbon atoms or a cycloalkylene or aryl mannitol and sorbitol, castor oil, diethylene glycol, ene group having 6-15 carbon atoms, triethylene glycol, tetraethylene glycol, higher polyeth R" represents hydrogen or a methyl group and ylene glycols with molecular weights of up to 400, X represents 2 or 3, dipropylene glycol, higher polypropylene glycols with SO e.g. 4,4'-diphenylmethane-bis-(3-hydroxyethylurea) or molecular weights of up to 400, dibutylene glycol, the compound CH3 CH3 HO-CH2-CH-NH-CO-NH

CH3 CH-NH-CO-NH-CH2-CH-OH higher polybutylene glycols with molecular weights of up to 400, 4,4'-dihydroxydiphenylpropane, dihydrox ymethyl-hydroquinone, dihydroxyethyl-hydroquinone For some purposes, it is advantageous to use polyols and dihydroxyethylresorcinol. containing sulphonate and/or phosphonate groups Low molecular weight polyols with molecular (German Offenlegungsschrift No. 2719.372), preferably weights below 2000 used according to the invention 65 the adduct of bisulphite and butane-1,4-diol or its al may also be mixtures of hydroxyaldehydes and hydrox koxylation products. yketones ("formoses") and the polyhydric alcohols The polyhydroxyl compounds mentioned above may obtained from them by reduction (“formitol'), as ob be modified in various ways before they are put into the 4,500,656 11 12 polyisocyanate polyaddition process. Thus according to been modified according to German Offenlegungss German Offenlegungsschriften Nos. 2 210 839 (U.S. chriften Nos. 2 442 101, 2 644. 922 and 2 646 141 and Pat. No. 3,849,515) and 2544 195, a mixture of various graft polymerization with vinyl phosphonic acid esters polyhydroxyl compounds (e.g. a polyether polyol and a and optionally (meth)acrylonitrile, (meth)acrylamide or polyesterpolyol) may be condensed by etherification in 5 OH functional (meth)acrylic acid esters. Polyhydroxyl the presence of a strong acid to form a relatively high compounds into which carboxyl groups have been in molecular weight polyol consisting of various segments troduced by radical graft polymerization with unsatu connected by ether bridges. rated carboxylic acids and optionally other olefinically Amide groups may also be introduced into the poly unsaturated monomers (German Offenlegungsschriften hydroxyl compounds, for example, according to Ger 10 Nos. 2714291, 2 739 620 and 2 654746) are particularly man Offenlegungsschrift No. 2 559 372, or triazine advantageously used in combination with mineral fill groups may be introduced by a reaction with polyfunc eS. tional cyanic acid esters according to German Offen When modified polyhydroxyl compounds of the type legungsschrift No. 2 620487. Polyhydroxyl compounds mentioned above are used as starting components in the containing guanidine, phosphonoformamide or acylu 15 polyisocyanate polyaddition process, the polyurethane rea groups are obtained by the reaction of a polyol with products obtained in many cases have substantially a less than equivalent quantity of a diisocyanato-car improved mechanical properties. bodiimide followed by reaction of the carbodiimide Representatives of the above mentioned compounds group with an amine, amide, phosphite or carboxylic to be used according to the invention have been de acid (German Offenlegungsschriften Nos. 2714 289, 2 20 scribed, for example, in High Polymers, Volume XVI, 714. 292 and 2 714293). It is in some cases of particular "Polyurethanes, Chemistry and Technology' by Saun interest to convert the relatively high molecular weight ders-Frisch, Interscience Publishers, New York, Lon polyhydroxyl compounds completely or partly into the don, Volume I, 1962, pages 32-42 and pages 44-54 and corresponding anthranilic acid esters by a reaction with Volume II, 1964, pages 5-6 and 198-199 and in Kunstst isatoic acid anhydride, as described in German Offen 25 off-Handbuch, Volume VII, Vieweg-Höchtlen, pub legungsschriften Nos. 2019 432 and 2 619 840 and in lishers Carl-Hanser-Verlag, Munich, 1966, e.g. on pages U.S. Pat. Nos. 3,808,250, 3,975,428 and 4,016, 143. Rela 45-7. tively high molecular weight compounds containing Mixtures of the above mentioned compounds con aromatic amino end groups are thus obtained. taining at least two isocyanate reactive hydrogen atoms To produce polymer products with improved flame 30 and having molecular weights of from about 2000 to resistance, these formoses are advantageously used in 12,000 may, of course, also be used, e.g. mixtures of combination with aminoplast formers and/or phos polyethers and polyesters. phites (German Offenlegungsschriften Nos. 2738 513 It is then in some cases particularly advantageous to and 2 738 532). Solutions of polyisocyanate polyaddi use a combination of low melting and high melting tion products, in particular of polyurethane ureas con 35 polyhydroxyl compounds (German Offenlegungss taining ionic groups and/or polyhydrazodicarbona chrift No. 2706297). mides, in low molecular weight, polyhydric alcohols (g) Aliphatic polyamines suitable for the purpose of may also be used as polyol components according to the the invention, belonging to components B(l) or compo invention (German Offenlegungsschrift No. 2 638759). nent B(2), depending upon their molecular weight, in Polyhydroxyl compounds containing high molecular 40 clude, for example, ethylene diamine, 1,4-tetramethy weight polyadducts or polycondensates or polymers in lene diamine, 1, 1 1-undecamethylene diamine, 1, 12 a finely dispersed or dissolved form may also be used dodecamethylene diamine and mixtures of these com according to the invention. Such polyhydroxyl com pounds, 1-amino-3,3,5-trimethyl-5-aminomethylcy pounds are obtained, for example, when polyaddition clohexane ("isophorone diamine'), 2,4- and 2,6-hexahy reactions (e.g. reactions between polyisocyanates and 45 drotolylene diamine and mixtures thereof, perhydro aminofunctional compounds) or polycondensation reac 2,4'- and -4,4'-diaminodiphenylmethane, p-xylylene di tions (e.g. between formaldehyde and phenols and/or anine, bis-(3-amino-propyl)-methylamine, diaminoper amines) are carried out in situ in the above mentioned hydroanthracenes (German Offen legungsschrift No. 2 hydroxyl compounds. Such processes have been de 638 731) and cycloaliphatic triamines according to Ger scribed, for example, in German Auslegeschriften Nos. 50 man Offenlegungsschrift No. 2 614 244. Hydrazine and 1 168 075 and 1 260 142 and in German Offendegungss substituted hydrazines, e.g. methyl hydrazine, N,N'- chriften Nos. 2324 134, 2423984, 2612 385, 2513 815, dimethylhydrazine and their honologues and acid dihy 2550 796, 2550 797, 2550 833, 2550 862, 2633 293 and drazides may also be used according to the invention, 2 639 253. Alternatively, according to U.S. Pat. No. e.g. carbodihydrazide, oxalic acid dihydrazide, the di 3,869,413 or German Offenlegungsschrift No. 2550 860 55 hydrazides of malonic acid, succinic acid, glutaric acid, a previously prepared aqueous polymer dispersion may adipic acid, 6-methyladipic acid, sebacic acid, hydra be mixed with a polyhydroxyl compound and the water crylic acid and terephthalic acid, semicarbazido-alky may then be removed from the mixture. lene hydrazides such as 6-semicarbazido-propionic acid Polyhydroxyl compounds modified with vinyl poly hydrazide (German Offenlegungsschrift No. 1 770591), mers, e.g. the compounds obtained by the polymeriza 60 semicarbazido alkylene carbazic esters such as 2 tion of styrene and acrylonitrile in the presence of poly semicarbazido ethyl carbazic ester (German Offen ethers (U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093 legungsschrift No. 1 918 504) or aminosemicarbazide and 3,1 10,695 and German Auslegeschrift No. 1 152 compounds such as (3-aminoethyl-semicarbazido car 536) or in the presence of polycarbonate polyols (Ger bonate (German Offenlegungsschrift No. 1 902 391). man Patent No. 1 769 795, U.S. Pat. No. 3,637,909) are 65 The amino groups may be partly or completely blocked also suitable for the process according to the invention. by aldimine or ketimine groups to control their reactiv Polymer products with exceptional flame resistance are ity (U.S. Pat. No. 3,734,894, German Offenlegungss obtained when using polyether polyols which have chrift No. 2 637 115). 4,500,656 13 14 According to German Offendegungsschrift No. 2546 German Offenlegungsschrift No. No. 2 734 574 are 536 and U.S. Pat. No. 3,865,791, relatively high molecu examples of aliphatic-aromatic diamines. lar weight compounds containing amino end groups are The chain lengthening agents used according to the obtained by a reaction of isocyanate prepolymers with invention may also be compounds such as 1-mercapto hydroxyl-containing enamines, aldimines or ketimines 5 3-aminopropane, substituted or unsubstituted amino followed by hydrolysis. Other methods of preparation acids such as glycine, alanine, valine, serine and lysine, of relatively high molecular weight compounds having and Substituted or unsubstituted dicarboxylic acids such amino groups or hydrazine groups in end positions are as Succinic acid, adipic acid, phthalic acid, 4-hydrox described in German Offenlegungsschrift No. 1694 152 yphthalic acid and 4-aminophthalic acid. (U.S. Pat. No. 3,625,871). O Compounds which are monofunctional in their reac In these compounds, the groups in end positions car tion with isocyanates may also be included as so-called rying the amino groups may also be attached to the chain breakers in proportions of from about 0.01 to 10% polyether chain by urethane or ester groups. Prepara by weight, based on the polyurethane solids content. tion of these "aminopolyethers' is carried out in known Examples of such monofunctional compounds include manner. For example, amination of polyhydroxy poly 15 monoamines such as butylamine and dibutylamine, oc ethers such as polypropylene glycol ethers may be car tylamine, stearylamine, N-methylstearylamine, pyrroli ried out by a reaction with ammonia in the presence of dine, piperidine and cyclohexylamine, monohydric al Raney nickel and hydrogen (Belgian Pat. No. 634741). cohols such as butanol, 2-ethylhexanol, octanol, U.S. Pat. No. 3,654,370 describes the preparation of dodecanol, Various amyl alcohols, cyclohexanol and polyoxyalkylene polyamines by a reaction of the corre 20 ethylene glycol monoethylethers. sponding polyol with ammonia and hydrogen in the Compounds belonging to component B(2) include (a) presence of a nickel, copper or chromium catalyst. The hydroxyl polyesters obtained from the same carboxylic preparation of cyanoethylated polyoxypropylene ethers acids and polyols as those mentioned above provided is described in German Pat. No. 1 193 671. Other meth they have molecular weights above 2000, (b) polyether ods for the preparation of polyoxyalkylene (polyether) 25 polyols obtained from the units described above, pro amines are described in U.S. Pat. Nos. 3,155,728 and vided they have molecular weights above 2000, (c) 3,236,895 and French Pat. No. 1551 605. The prepara polybutadienes, polythioethers, polyacetals, polycar tion of polyethers containing secondary amino end bonates, polyester amides and polyamides of known groups, for example, is described in French Pat. No. 1 type containing OH, NH and/or SH groups, provided 30 they have molecular weights above 2000, and the types 466 708. of compounds mentioned under B(1)(d), B(1)(e), Relatively high molecular weight polyhydroxyl B(1)(f), and B(1)(g), provided they have molecular polyethers may be converted into the corresponding weights above 2000. anthranilic acid esters suitable as component (B) ac The following are optionally used as auxiliary agents cording to the invention by a reaction with isatoic acid 35 and additives B(4): anhydride, as described, for example, in German Offen (a) Water and/or readily volatile inorganic or organic legungsschriften Nos. 2019 432 and 2619 840 and U.S. substances as blowing agents. Examples of organic Pat. Nos. 3,808,250, 3,975,428 and 4,016,143. The poly blowing agents include acetone, ethyl acetate, halogen ethers obtained by this reaction contain aromatic amino substituted alkanes such as methylene chloride, chloro end groups. 40 form, ethylidene chloride, vinylidene chloride, mono Other aminopolyethers within the above mentioned fluorotrichloromethane, chlorodifluoromethane and molecular weight range, for example those obtainable dichlorodifluoromethane, butane, hexane, heptane and according to DE-OS 2948 419, DE-OS 3.039 600 or EP diethylethers; suitable inorganic blowing agents include 71 834 may also be used. e.g. air, CO2 and N2O. The effect of a blowing agent 45 may also be obtained by the addition of compounds Examples of aromatic diamines include bis which decompose at temperatures above room temper anthranilic acid esters according to German Offen ature with the release of gases (e.g. nitrogen), e.g. azo legungsschriften Nos. 2040 644 and 2 160 590, 3,5- and compounds such as azo dicarbonamide or azo isobu 2,4-diamino-benzoic acid esters according to German tyric acid nitrile. Offenlegungsschrift No. 2 025 900, the diamines with 50 Further examples of blowing agents and details con ester groups described in German Offenlegungss cerning the use of blowing agents may be found in chriften Nos. 1803 635 (U.S. Pat. Nos. 3,681,290 and Kunststoff-Handbuch, Volume VII, published by Vie 3,736,350), 2 040 650 and 2 160 589, the diamines con weg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, taining ether groups according to German Offen e.g. on pages 108 and 109, 453 to 455 and 507 to 510. legungsschriften Nos. 1770.525 and 1809 172 (U.S. Pat. 55 (b) Known types of catalysts, e.g. tertiary amines Nos. 3,654,364 and 3,736,295), 2-halogen-1,3- such as triethylamine, tributylamine, N-methylmorpho phenylenediamine optionally substituted in the 5-posi line, N-ethylmorpholine, N,N,N',N'-tetramethyle tion (German Offenlegungsschriften Nos. 2001 772, 2 thylenediamine, pentamethyl-diethylene triamine and 025 896 and 2 065 869), 3,3'-dichloro-4,4'-diaminodi higher homologues (German Offenlegungsschrift No. 2 phenylmethane, tolylene diamine, 4,4'-diaminodi 60 624 527 and 2 624 528), 1,4-diaza-bicyclo-(2,2,2)-octane, phenylmethane, 4,4'-diamino-diphenyldisulphides (Ger N-methyl-N'-dimethylaminoethylpiperazine, bis-(dime man Offenlegungsschrift No. 2 404 976), diaminodi thylcyclohexylamine, N,N-diethylbenzylamine, N,N- phenyl dithioethers (German Offenlegungsschrift No. 2 dimethylcyclohexylamine, N,N-diethylbenzylamine, 509 404), aromatic diamines substituted by alkylthio bis-(N,N-diethylaminoethyl)-adipate, N,N,N',N'-tet groups (German Offenlegungsschrift No. 2 638 760), 65 ramethyl-1,3-butanediamine, N,N-dimethyl-6-phenyle diaminobenzene phosphoric acid esters (German Offen thylamine, 1,2-dimethylimidazole, 2-methylimidazole, legungsschrift No. 2 720 166) and the high melting monocyclic and bicyclic amidines (German Offen diamines mentioned in German Offenlegungsschrift No. legungsschrift No. 1 720 633), bis-(dialkylamino)-alkyl 2 635 400. The aminoalkyl thioanilines according to ethers (U.S. Pat. No. 3,330,782, German Auslegeschrift 4,500,656 15 16 No. 1 030 558, German Offenlegungsschriften Nos. 1 fatty acids with amines, such as oleic acid diethylamine 804 361 and 2 618 280) and tertiary amines containing or stearic acid diethanolamine. Alkali metal or ammo amide groups (preferably formamide groups) according nium salts of sulphonic acids such as dodecylbenzene to German Offenlegungsschriften Nos. 2523 633 and 2 sulphonic acid or dinaphthylmethane disulphonic acid, 732 292. The known Mannich bases of secondary 5 or of fatty acids such as ricinoleic acid or of polymeric amines such as dimethylamine and aldehydes, prefera fatty acids may also be used as surface active additives. bly formaldehyde, or ketones such as acetone, methyl The main foam stabilizers used are polyether silox ethyl ketone or cyclohexanone and phenols such as anes, especially those which are water-soluble. These phenol, nonlylphenol or bisphenol may also be used as compounds generally consist of a copolymer of ethyl catalysts. O Examples of tertiary amines with isocyanate reactive ene oxide and propylene oxide linked to a polydimethyl hydrogen atoms used as catalysts include triethanol siloxane group. Foam stabilizers of this kind have been amine, triisopropanolamine, N-methyl-diethanolamine, described, for example, in U.S. Pat. Nos. 2,834,748, N-ethyldiethanolamine, N,N-dimethyl-ethanolamine 2,917,480 and 3,629,308. Polysiloxanepolyoxyalkylene and their reaction products with alkylene oxides such as 15 copolymers branched at allophanate groups according propylene oxide and/or ethylene oxide as well as se to German Offenlegungsschrift No. 2 558 523 are in condary-tertiary amines according to German Offen many cases of particular interest. legungsschrift No. 2732 292. (d) Reaction retarders, e.g. compounds which are Silaamines with carbon-silicon bonds may also be acid in reaction, such as hydrochloric acid or organic used as catalysts, e.g. the compounds described in Ger- 20 acid halides; known cell regulators such as paraffins or man Pat. No. 1 229 290 (corresponding to U.S. Pat. No. fatty alcohols or dimethylpolysiloxanes, pigments, dyes 3,620,984), e.g. 2,2,4-trimethyl-2-silamorpholine and and flame-retarders of known type such as trischloroe 1,3-diethylaminomethyl-tetramethyldisiloxane. thylphosphate, tricresylphosphate and ammonium Basic nitrogen compounds such as tetraalkylam phosphate and polyphosphate, stabilizers against aging nonium hydroxides, alkali metal hydroxides such as 25 and weathering, plasticizers and fungistatic and bacte sodium hydroxide, alkali metal phenolates such as so riostatic substances and fillers such as barium sulphate, dium phenolate and alkali metal alcoholates such as silica gel, carbon black or whiting may also be used. sodium methylate may also be used as catalysts. Hex Further examples of surface active additives and ahydrotriazines are also suitable catalysts (German Of foam stabilizers optionally used according to the inven fenlegungsschrift No. 1 769 043). 30 tion as well as cell regulators, reaction retarders, stabi The reaction between isocyanate groups and Zerewi lizers, flame retarding substances, plasticizers, dyes, tinoff active hydrogen atoms is powerfully accelerated fillers and fungistatic and bacteriostatic substances and by lactams and aza lactams, an associate being first details concerning the use and action of these additives formed between the lactam and the compound contain are described in Kunststoff-Handbuch, Volume VII, ing acidic hydrogen. Such associates and their catalytic 35 published by Vieweg and Höchtlen, Carl-Hanser-Ver action are described in German Offenlegungsschriften lag, Munich 1966, e.g. on pages 103 to 113. Nos. 2 062 288, 2062 289, 2 117 576 (U.S. Pat. No. Method of carrying out the process according to the 3,758,444), 2 129 198, 2330 175 and 2330 211. invention: Organic metal compounds may also be used as cata The components are reacted together according to the lysts according to the invention, in particular organic 40 invention by the known one-shot process, prepolymer tin compounds. Suitable organic tin compounds include process or semiprepolymer process, in many cases using compounds containing sulphur, such as di-n-octyl-tin mechanical devices such as those described in U.S. Pat. mercaptide (German Auslegeschrift No. 1 769367, U.S. No. 2,764,565, for example. Details concerning process Pat. No. 3,645,927), but the tin compounds used are preferably tin(II)-salts of carboxylic acids, such as tin- 45 ing apparatus suitable for the purpose of the invention (II)-acetate, tin(II)-octoate, tin(II)-ethylhexoate and may be found in Kunststoff-Handbuch, Volume VII, tin(II)-laurate and tin(IV)-compounds such as dibutyl published by Vieweg and Höchtlen, Carl-Hanser-Ver tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, lag, Munich 1966, e.g. on pages 121 to 205. dibutyl tin dilaurate, dibutyl tin maleate and dioctyl tin Cold setting foams may also be produced by the pro diacetate. 50 cess according to the invention (see British Pat. No. 1 All the catalysts mentioned above may, of course, be 162 517, German Offenlegungsschrift No. 2 153 086). used as mixtures. Combinations of organic metal com Foams may, of course, also be produced by block pounds and amidines, aminopyridines and hydrazino foaming or by the known laminator process. pyridines are of particular interest (German Offen For the purpose of the invention, it is preferred to legungsschriften Nos. 2 434 185, 2 601 082 and 2 603 55 produce the foams by the frothing process (see e.g. 834). Kunststoff-Handbuch Volume VII, published by Vie Other representatives of catalysts to be used accord weg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, ing to the invention and details concerning the action of pages 455, 456, 509 and 534). these catalysts are described in Kunststoff-Handbuch, The polyurethane foams obtainable by the process Volume VII, published by Vieweg and Höchtlen, Carl- 60 according to the invention may be flexible, semi-rigid or Hanser-Verlag, Munich 1966, e.g. on pages 96 to 102. rigid, the rigid foams being preferred. They may be The catalysts are generally used in a quantity of from used, for example, for insulating refrigerators, for the about 0.001 to 10% by weight, based on the total quan production of spray insulations and coatings and as tity of compounds containing at least two isocyanate one-component foams. reactive hydrogen atoms. 65 The invention is further illustrated, but is not in (c) Surface active additives such as emulsifiers and tended to be limited by the following examples in which foam stabilizers. The emulsifiers used may be, for exam all parts and percentages are by weight unless otherwise ple, sodium salts of castor oil sulphonates or salts of specified. 4,500,656 17 18 was maintained at 80 C., first by cooling and towards EXAMPLES the end of the reaction by heating. Example 1 4.3 122 g of ethanolamine (2 mol) at a temperature of Comparison examples to DE-OS 2200 480, Example 20 C. was gassed with carbon dioxide until satura 5 (page 17) 5 tion was reached. During this process, the tempera In this example, carbon dioxide was passed through a ture rose to 120° C. without cooling. 20% weight per volume solution of ethanolamine in 4.4 122 g of ethanolamine (2 mol) were heated to 140 carbon tetrachloride. C. and gassed with CO2. The bath heated to 140 C. When attempts were made to reproduce this experi was not removed until saturation was reached. The ment, it was found that at temperatures from 20 to 35 10 temperature of the reaction mixture rose to 160° C. in C., ethanolamine would not dissolve in carbon tetra the course of the reaction. The product had a distinct chloride in amounts of 20% by weight nor 10% by yellow color, in contrast to the polar products ob weight nor 5% by weight (20, 10 and 5 parts of ethanol tained in 4.1 to 4.3. amine, respectively, and 80, 90 and 95 parts of tetra Clear, non-crystallizing liquids of medium viscosity chloromethane). This experiment was therefore not 15 were obtained from all four reaction mixtures. reproducible. The quantities of gas measured were virtually identi Example 2 cal: Comparison example to DE-PS2 621 582, Example 4 (page 10) 20 Vol. 1 (i) Vol. 2 (1) In this example, it was asserted that a white, pulveru 4.1. 19.8 21.3 4.2. 2.4 23 lent diethanolamine carbamate was obtained by the 4.3. 18.9 20.4 introduction of carbon dioxide into a solution of dieth 4.4. 17.8 20.0 anolamine in benzene. g 19.51 a 21.11 When attempts were made to reproduce this experi 25 ment, it was found that diethanolamine was immiscible with benzene (and also with toluene) over a wide range Volume 1 was the quantity of nitrogen obtained when of concentrations. When carbon dioxide was neverthe taking an average of the quantities of CO2 recorded on less introduced into such a diphasic mixture, no carba a gas meter and the quantities of CO2 calculated from mate precipitated, nor any other solid substance and the 30 weighing the reaction mixture after it had been gassed components therefore remained in the form of a dipha with CO2. Volume 2 was the quantity of gas determined sic system. When, for example, carbon dioxide was volumetrically after the addition of excess dilute hydro introduced into a diphasic system of 100 ml of diethan chloric acid to the product. olamine and 500 ml of benzene until saturation point It will be seen that the absorption of carbon dioxide was reached, and the resulting mixture was then decom- 35 was substantially independent of the reaction tempera posed with excess, dilute hydrochloric acid, 11.5 l of ture; the quantity of CO2 absorbed was always the same CO2 were liberated, corresponding to an almost exactly within the limits of error (approximately 1 mol of CO2 equivalent ratio of amino groups to carbon dioxide of to 2 mols of aminoalcohol). 2:1. 4.5 3183 l (approximately 6.35 kg) of carbon dioxide 40 were introduced into 21.6 kg of ethanolamine in the Example 3 course of 7 hours with the reaction temperature rising Comparison example to GB 1 103 506, Example 9 from 20° C. to 85 C. The reaction mixture was (pages 5 and 6) cooled to prevent the reaction temperature from In this example, a salt was precipitated by the intro rising above 85 C. The pale, liquid material did not duction of carbon dioxide into a solution of hydroxy 45 crystallize even after one year. ethyl hydrazine in DMF. When this experiment was repeated without solvent, Example 5 i.e. carbon dioxide was introduced into hydrazinoe This example investigates the storage stabilities of thanol, and external cooling was applied to ensure that carbamates and carbonic acid adducts of ethanolamine. the reaction temperature did not exceed 80° C., 9.2 1 of 50 5.1 The carbamates prepared in Example 4 and two CO2 (0.41 mol) were absorbed for every 100 g of hy carbonic acid salts prepared analogously to 4.1 and drazinoethanol. Contrary to the previous description, 4.2. (122 g of ethanolamine and 36 g of water) were the pale, clear product was liquid and did not crystallize heated to 80° C. for 2 hours. No evolution of gas even after prolonged storage. could be ascertained either gravimetrically or volu The carbonic acid salt prepared with the addition of 55 metrically. water was also liquid and did not crystallize (Example 5.2 The carbamates prepared in Example 4 and two 6, 4). carbonic acid salts prepared analogously to 4.1. and 4.2.from 122 g of ethanolamine (2 mol) and 36 g of Example 4 water (2 mol) of CO2 until saturation were heated to This example demonstrates the influence of the reac- 60 60° C. for 30 minutes at 20 mbar pressure and any loss tion temperature on the formation of the carbon dioxide of gas was ascertained by weighing and by acidolytic adduct. decomposition accompanied by CO2 measurement. 4.1 CO2 was introduced into 122 g of ethanolamine (2 No loss of gas could be ascertained in any of the 6 mol). The reaction temperature was maintained at 20 samples. C. by external cooling and regulation of the speed at 65 which CO2 was introduced. Example 6 4.2 122 g of ethanolamine (2 mol) were heated to 80 C. Various other liquid carbon dioxide adducts were and CO2 was introduced. The reaction temperature prepared in Example 6. 4,500,656 19 6.1 Ethanolamine-carbonic acid salt Carbon dioxide was introduced until saturation into a 800 g of a 98% ethanolamine (12.8 mol) and 120g of mixture of isopropanolamine (500 g = 6.7 mol) and water (16.67 mol) were combined and 1381 of CO2 120 g of water (6.67 mol). 99.2 1 of CO2 (4.4 mol) (6.16 mol) were introduced into the mixture in the were absorbed. course of one hour. The temperature of the mixture 5 6.6. N-methyldiethanolamine carbonic acid salt rose to 85 C. during the exothermic reaction. Carbon dioxide was introduced into a mixture of Cooling was provided to prevent the temperature 305.5 g of N-methyldiethanolamine (2.28 mol) and from rising above this level. 47 g of water (1.68 mol) while the mixture was In another experiment using the same quantity of cooled with ice. 33.7 g of CO2 (0.74 mol) had been reaction mixture, 144 l of CO2 (6.43 mol) were ab 10 absorbed at this temperature after 3 days. Sorbed. The clear liquid product was stable for at least three The product obtained is a clear liquid from which no years, did not crystallize and did not release any gas. carbon dioxide was released. It was stable for at least Examples of practical application one year. 6.2 Diethanolamine-carbon dioxide adducts 15 Polyols used in the process 6.2.1. Diethanolamine carbonic acid salt Polyol (A): Polyether polyol with OH number about Carbon dioxide was introduced into a mixture of 380, functionality 5.8 and viscosity 12,000 mPas at 25 diethanolamine (900 g=8.57 mol) and 80 g of C., obtained by propoxylation of a mixture of cane water (4.44 mol) until saturation. In the course of sugar (87.4% of OH equivalents), water (6.2%) and 75 minutes, 73 l of CO2 (3.26 mol) were introduced propylene glycol (6.4%). into one sample and 72 1 (3.21 mol) into another Polyol (B): Polyether polyol with OH number about sample. The reaction temperature rose to 63 C. 380, functionality 3 and viscosity 600 mPas at 25 C. without cooling. obtained by propoxylation of a mixture of cane sugar 6.2.2. Diethanolamine carbamate (45%), water (2%) and propylene glycol (53%). 25 Polyol (C): Polyether polyol with OH number about 78 of CO2 (3.48 mol) (saturation) were introduced 470, functionality 2 and viscosity 85 mPas at 25 C., into 1000 g of diethanolamine (9.52 mol), the reac obtained by ethoxylation of ethyl diethanolamine. tion temperature rising from 25 C. to 70° C. Polyol (D): Polyether polyol with OH number about The clear liquid product had no tendency to crystal 470, functionality 5.3 and viscosity about 34,000 mPas lize or evolve gas and was stable for at least one 30 at 25 C. obtained by propoxylation of a mixture of year. cane sugar (82.8%), water (3.1%) and propylene 6.3. N-hydroxyethylethylenediamine carbonic acid salt glycol (14.1%). 6.3.1. 238 l of carbon dioxide (10.63 mol) (saturation Polyol (E): Polyether polyol with OH number about limit) were introduced in the course of 150 minutes 380, functionality 3 and viscosity 1500 nPas at 25 C. into a mixture of 1400 g of N-g-hydroxyethylethy 35 obtained by propoxylation of a mixture of cane sugar lene diamine and 242 g of water (13.46 mol each). The (45%) and propylene glycol (55%). reaction temperature rose to 80 C. Polyol (F): Polyether polyol with OH number about 6.3.2. CO2 was introduced to saturation point into a 455, functionality 3 and viscosity 400 mPas at 25 C., mixture of 400 g of N-6-hydroxyethylethylene di obtained by propoxylation of glycerol. amine (3.85 mol) and 88 ml of water (4.89 mol) while 40 Polyol (G): Polyether glycol with OH number about the mixture was cooled with ice to prevent the reac 650, functionality 4 and viscosity about 20,000 mPas tion temperature rising above 25 C. 1301 of CO2 (5.8 at 25 C., obtained by propoxylation of ethylene di mol) were absorbed. amine. 6.3.3. N-hydroxyethylethylenediamine-carbamate Polyol (H): Polyether polyol with OH number 35 and Carbon dioxide was introduced until saturation into 45 functionality 3 obtained by blockwise addition of 1000 g of N-hydroxyethylethylenediamine, and the propylene oxide to trimethylol propane. reaction temperature rose from 25 C. to 70° C. 119 Polyol (I): Polyether polyol with OH number about 500 1 of CO2 (5.3 mol) were absorbed. The clear liquid and functionality 3, obtained by propoxylation of products had no tendency to crystallize or evolve triethanolamine. gas and were stable for at least one year. 50 6.4. Hydrazinoethanol carbonic acid salt Example 7 Carbon dioxide was introduced until saturation into a Use of the carbon dioxide adducts in rigid foam mixture of 500 g of hydrazinoethanol (6.58 mol) 7.1 Use of carbamate compounds and 59 g of water (3.29 mol). 49.5 l of carbon diox Formulation: ide (2.2 mol) were absorbed while the temperature 55 60 parts of polyol D rose to 83 C. 23.6 parts of polyol B The clear liquid product had no tendency to crystal 16.4 parts of polyol E lize or evolve gas and was stable for at least one 2.1 parts of water year. 1.9 parts of cell stabilizer (80% solution of a poly 6.5. Isopropanolamine-carbon dioxide adducts 60 ether siloxane in a polypropylene glycol having 6.5.1. Isopropanolamine carbamate an OH number of 500) 55 l of carbon dioxide (2.46 mol) were introduced in 3.3 parts of amine catalyst 1 (Desmorapid catalyst: the course of 2 hours into 500 g of isopropanola Sample PU 3144 of BAYERAG) mine. The temperature rose to 62 C. x parts of carbamate compound The clear, rather more viscous product had no ten 65 X parts of amine catalyst 2 (Desmorapid catalyst: 726 dency to crystallize or evolve gas and was stable b of BAYERAG) for at least one year. Various quantities of different carbamates were 6.5.2. Isopropanolamine carbonic acid adduct added to 100 parts of the polyol formation (OH number 4,500,656 21 about 430) and the formulation was reacted using vari ous quantities of amine catalyst 2. -continued Parts of Parts of amine Crean time Gel time carbamate catalyst 2 (sec.) (sec.) Carbamate Parts of amine Cream time Gel time 5 Parts (from Example) catalyst 2 (sec.) (sec.) 5 0.7 2 82 O 23 O4 4.S. 1. 5 04 2 4.5. 0.9 7 107 Formulations containing more than 2 parts of etha 3 4.5. 0.9 4 105 nolamine carbamate were difficult to work up in the 4 4.5. 0.8 3 OO O laboratory because of the foaming effect. When polyol 3 6.2.2. 0.5 l 06 mixtures containing 3 or more parts of ethanolamine 3 6.3.3. 1.8 8 05 carbamate were foamed up in a high pressure machine 3 6.5. . 4. O4 (HK 100 of Maschinenfabriken Hennecke, St. Augustin, Federal Republic of Germany, using a needle nozzle The polyol mixtures containing carbamates and cata 15 mixing head), the reaction mixture was already foamed lysts were mixed with 40 parts of trichlorofluorometh up as it left the outlet tube and formed a froth of the ane with vigorous stirring. An isocyanate index of 105 kind which is otherwise only observed when about 5 to was maintained while the mixture was foamed up with 8 parts of dichlorodifluoromethane or similar low boil 150 parts of an isocyanate consisting of a crude phos ing substances are added. genation product of an aniline-formaldehyde conden 8.2. Use of ethanolamine carbonic acid salt sate from which diisocyanatodiphenylmethane was When another batch of formulation 8.1. was prepared distilled off in the quantity required to leave a residue for use with ethanolamine carbonic acid salt (from Ex having a viscosity of 200 mPas at 25 C., a dinuclear ample 4.5.) and the quantitative proportions were var content of 44.3%, a trinuclear content of 23.5% and a ied in the same manner, no difference was found be higher nuclear content of polyisocyanates of 32.2%. 25 tween the ethanolamine carbamate and the carbonate. The NCO content was about 31% by weight. This is equally true whether or not the water content of 7.2 Use of carbonic acid compounds: the carbonic acid salt has been considered in the formu When another batch of reaction mixture 7.1. was lation. prepared but the carbamates from Examples 4.5, 6.3.3., Example 9 6.5. and 6.2.2. were replaced by the corresponding car 30 bonic acid compounds from Examples 6.1., 6.2.1., 6.5.2. Another example of using carbon dioxide salts in and 6.3.2., the foaming characteristics were found to be rigid foam the same as those obtained with the carbamates. This is 9.1. Use of carbamates true whether or not the water content of the carbonic Formulation: acid salts was considered in the formulation. There was 35 60 parts of polyol D found to be no difference between carbamates and car 30 parts of polyol F bonic acid salts as regards the kinetic foaming data and 10 parts of polyol G 2 parts of water the appearance, behavior, etc. of the foam. 2 parts of a siloxane polyether copolymer with Example 8 40 viscosity m700 mPas at 25 C. Ethanolamine-carbon dioxide adducts in rigid foam 0.5 parts of amine catalyst 3, (Desmorapid PV of 8.1. Use of ethanolamine carbamate BAYERAG) Formulation: 100 parts of polyol formulation were mixed with 3 80 parts of polyol A 45 parts of ethanolamine carbamate (from 4.5.), diethanol 12 parts of polyol B amine carbamate (from 6.2.1.) and isopropanolamine 8 parts of polyol C carbamate (from 6.5.2.) and activated with amine cata 0.5 parts of dimethylethanolamine lyst 2. After addition of 35 parts of trichlorofluorometh ane, the mixture was reacted with 148 parts of the poly 2.1 parts of water isocyanate from Example 7.1. 1.5 parts of stabilizer (as in 7.1.) 50 Various quantities of ethanolamine carbamate (from 4.5.) were added to 100 parts of the polyol formulation Parts of (OH number about 380) and the reaction mixture was amine Cream Gel reacted using amine catalyst 2 as in Example 7. After Catalyst time time 55 2 (sec.) (sec.) the addition of 38 parts of trichloromonofluorometh 3 parts of ethanolamine 3. 4. 76 ane, the mixture was reacted with 130 parts of the isocy carbanate (from 4.5.) anate from Example 7.1. 3 parts of diethanolamine 3 7 76 All mixing was carried out with a laboratory stirrer at carbarnate (from 6.2.2.) 1000 revS/min. 3 parts of isopropanolamine 3 4. 82 60 carbamate (from 6.5.1.) O 2 75 Parts of Parts of annine Cream time Gei time 9.2. Use of carbonic acid salt carbanate catalyst 2 (sec.) (sec.) When another batch of formulation 9.1. was prepared O 5 16 85 65 1 .2 O 84 and the carbamates from Examples 4.5., 6.2.2, and 2 1.0 5 83 6.5.1. were replaced by the corresponding carbonates 3 0.8 4. 87 from Examples 6.1., 6.2.1., and 6.5.2., the foaming char 4. 0.7 3 88 acteristics were found to be the same as those obtained 4,500,656 23 24 with the carbamates, regardless of whether or not the product of an aniline/formaldehyde condensate from water content of the carbonic acid salts in the formula which diisocyanatodiphenylmethane had been distilled tion has been considered. No difference can be found off in the quantity required to produce a distillation between carbamates and carbonates (carbonic acid salts) as regards the kinetic foaming data, appearance, residue having a viscosity of 100 mPas at 25 C., a dinu behavior, properties, etc. of the foam. clear content of 59.7%, a trinuclear content of 21.3% Examples 7.1.-9.2. demonstrate that carbamates and and a higher nuclear polyisocyanate content of 19.0%, (bi)carbonates show the same behavior when foaming is using a polypropylene glycol with OH number about carried out within the given concentration ratio. Both 507. types of compounds, when added to the formulations, 10 12.2. (according to the invention) give rise to the formation of a froth of the kind normally Formulation: observed only when a substance such as dichlorodifluo 101 parts of polyol H romethane, for example, is used. Moreover, the foams 5 parts of ethylene glycol obtained are found to have much fewer bubbles and 0.4 parts of triethylene diamine (Dabco catalyst) signs of roll-back than systems processed with dichloro 15 14 parts of trichlorofluoromethane difluoromethane. 0.1 parts of foam stabilizer according to Example Example 10 12.1. 5 parts of carbonate composition A Investigation of storage stability 100 parts of this polyol component were foamed up 100 parts of the polyol system from Example 8.1. 20 with 47 parts of the isocyanate from 12.1. were mixed with 3 parts of ethanolamine carbamate (from Example 4.5.) and stored at 25 C. Carbonate composition A Carbon dioxide was introduced into a mixture of 500 Foaming after parts of ethanolamine, 500 parts of polyol I and 75 parts instantly 7 d 14 d 35 d 70 d 105 d 0.5 year 25 of water at a reaction temperature which rose from 20 Cream 4 4. 4 4 4. 4 4 C. to 68 C. 88.5 l of CO2 were taken up. The pale time yellowish, clear product was a stable monophasic sub (sec.) Stance. Ge. 78 77 77 76 78 78 80 time 12.3. (according to the invention) (sec.) 30 Formulation: 101 parts of polyol H No change in the reaction times, frothing effect and 5 parts of ethylene glycol quality of the foam could be observed even after 6 0.4 parts of triethylene diamine (Dabco catalyst) months' storage. 14 parts of trichlorofluoromethane 35 0.1 part of foam stabilizer according to Example Example 11 12.1. Investigations into storage stability 5 parts of carbonate composition B 100 parts of the polyol system from Example 8.1. 100 parts of this polyol component were foamed up were mixed with 3 parts of ethanolamine carbamate with 41 parts of the isocyanate from 12.1. (from Example 4.5.) and 1.3 parts of amine catalyst 2 40 from Example 7 and stored at 60° C. Carbonate composition B Carbon dioxide was introduced to saturation into a Foaming after mixture of 500 parts of diethanolamine, 500 parts of instantly 4 d 7 di 14 d 28 d 45 polyol I and 40 parts of water at 60° C. 321 of CO2 were Crean time 4 4 4 4 4. taken up. The yellowish product was a clear, monopha (sec.) sic liquid and was stable in this form. Gel time 83 83 83 83 83 (sec.) 50 Comparison of 12.l., 12.2. and 12.3. (free foams) Cream Rise Gel No change in reaction times, frothing or quality of time time time Unit weight the foam could be observed after one month's storage. Example (sec.) (sec.) (sec.) (kg/m) Example 12 12.1. 20 48 50 146.5 12.2. 18 65 70 118 Formulation for semi-rigid polyurethane foam 55 12.3. 4. 70 80 23 12.1 Comparison 101 parts of polyol H 9 parts of ethylene glycol The carbonate products accelerated the starting 0.4 parts of triethylene diamine phase to creaming and increased the viscosity of the 0.1 parts of water 60 reaction mixture during this phase. The carbonate prod 0.1 parts of a foam stabilizer based on a polyether ticts of this example also had a cell opening effect. polysiloxane copolymer (DC 193 of Dow-Corning) Although the invention has been described in detail in 14 parts of trichlorofluoromethane the foregoing for the purpose of illustration, it is to be 100 parts of this polyol component were reacted with understood that such detail is solely for that purpose 45 parts of a polyisocyanate having an isocyanate con 65 and that variations can be made therein by those skilled tent of 27 to 29% by weight and a viscosity of 130-30 in the art without departing from the spirit and scope of mPas at 25 C., which polyisocyanate had been ob the invention except as it may be limited by the claims. tained by partial urethanization of a crude phosgenation What is claimed is: 4,500,656 25 26 1. A process for the preparation of a cellular polyure having at least one primary, secondary or tertiary amino thane which comprises reacting group and containing at least one primary, secondary or (A) a polyisocyanate with tertiary hydroxyl group, which amine is solid or liquid (B) an isocyanate-reactive component containing at 20° C., and in that it has (1) at least one component in the molecular weight 5 (a) a basic nitrogen content of about 17 to about 3.5%, range of from about 60 to 2000 containing (b) a hydroxyl group content of about 20.5 to about isocyanate-reactive groups and having a func 8.5%, tionality of 2 to 8, (c) a carbon dioxide content of about 36% to about (2) optionally at least one component in the molec 2.5% by weight and ular weight range of from about 2000 to 12000 10 (d) a water content of about 3 to about 15% by containing isocyanate-reactive groups and hav weight. ing a functionality of 2 to 8, 5. The process according to claim 4, characterized in (3) about 0.1-30 parts, based on 100 parts of that said liquid amine-carbon dioxide adducts are car B(1) --B(2), of a liquid adduct of an amine and bonates or bicarbonates of N-mono-, N,N-di- and carbon dioxide, and 5 N,N,N-tri-((3-hydroxyalkyl)-amines and N-mono-, (4) optionally water, blowing agents, foam stabiliz N,N'-di- and N,N',N'-tri-(3-hydroxyalkyl)-ethylenedia ers, catalysts and other auxiliary agents and addi mine. tives, 6. The process according to claim 5, characterized in wherein the liquid amine-carbon dioxide adduct is a that said liquid amine-carbon dioxide adducts are car liquid adduct at 20 C., optionally containing water, 20 bonates or bicarbonates of ethanolamine, diethanol based on carbon dioxide and an amine which has at least amine, propanolamine, isopropanolamine, diisopropa one amino group and contains at least one primary, nolamine and N-hydroxyethylethylenediamine. secondary or tertiary hydroxyl group, which amine is 7. The process according to claim 1, characterized in solid or liquid at 20 C. that the polyisocyanates used are optionally modified 2. The process according to claim 1, characterized in 25 tolylene diisocyanates or phosgenation products of that the liquid amine-carbon dioxide adduct is obtained aniline/formaldehyde condensates. by the action of carbon dioxide on the amine, optionally 8. The process according to claim 6, characterized in in the presence of water and/or polyols with an OH that the polyisocyanates used are optionally modified number above 1 12 having 2 to 8 hydroxyl groups, in the tolylene diisocyanates or phosgenation products of absence of solvents of the type of aliphatic halogenated 30 aniline/formaldehyde condensates. hydrocarbons, optionally nitrated or halogenated, op 9. The process according to claim 1, characterized in tionally alkyl group-containing aromatic hydrocarbons, that polyethers with a molecular weight of from 200 to lower aliphatic alcohols, acid amides, lactams and 1000 containing 3-6 hydroxyl groups are used as com aprotic solvents, at temperatures of from about -25 C. ponent B(1). to 160 C. 35 10. The process according to claim 6, characterized 3. Process according to claim 1, characterized in that in that polyethers with a molecular weight of from 200 the liquid amine-carbon dioxide adduct has to 1000 containing 3-6 hydroxyl groups are used as (a) a basic nitrogen content of about 19 to about 3.5% component B(1). by weight, 11. The process according to claim 7, characterized (b) a hydroxyl group content of about 27.5 to about 40 in that polyethers with a molecular weight of from 200 8.5% by weight, to 1000 containing 3-6 hydroxyl groups are used as (c) a carbon dioxide content of about 42 to about component B(1). 1.0% by weight and 12. The process according to claim 8, characterized (d) a water content from 0 to about 15% by weight. in that polyethers with a molecular weight of from 200 4. The process according to claim 1, characterized in 45 to 1000 containing 3-6 hydroxyl groups are used as that the liquid amine-carbon dioxide adduct is a carbon component B(1). ate and/or bicarbonate, liquid at 20° C., of an amine sk xk k k -k

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