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CA2052048A1 - Urethanes, a process for their preparation and their use as catalysts for isocyanate polyaddition processes - Google Patents

Urethanes, a process for their preparation and their use as catalysts for isocyanate polyaddition processes

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Publication number
CA2052048A1
CA2052048A1 CA002052048A CA2052048A CA2052048A1 CA 2052048 A1 CA2052048 A1 CA 2052048A1 CA 002052048 A CA002052048 A CA 002052048A CA 2052048 A CA2052048 A CA 2052048A CA 2052048 A1 CA2052048 A1 CA 2052048A1
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Canada
Prior art keywords
isocyanate
compounds
german published
acid
catalysts
Prior art date
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Abandoned
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CA002052048A
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French (fr)
Inventor
Stephan Kirchmeyer
Gerhard Heilig
Hanns-Peter Muller
Rolf Wiedermann
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Bayer AG
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Individual
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Publication of CA2052048A1 publication Critical patent/CA2052048A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1841—Catalysts containing secondary or tertiary amines or salts thereof having carbonyl groups which may be linked to one or more nitrogen or oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Building Environments (AREA)

Abstract

Mo-3632 LeA 27,919 NEW URETHANES, A PROCESS FOR THEIR PREPARATION AND THEIR
USE AS CATALYSTS FOR THE ISOCYANATE POLYADDITION PROCESSES
ABSTRACT OF THE DISCLOSURE
New urethanes of the general formulae (I) and/or (II) in which R1 represents H or CH3;
R2 and R3 are identical or different and each represent a C1-C10-alkyl radical or together represent a C2-C1O-alkylene radical which can be interrupted by hetero atoms such as 0 or NR4 (R4 = C1-C6-alkyl), and A is an optionally branched C1-C10-alkylene radical or a C5-C10-cycloalkylene radical, excluding the compounds where R1 = H, R2 and R3 = CH3 and A =
-(CH2)3-, and mixtures thereof have been found to be useful as catalysts for the isocyanate polyaddition process.

Mo3632

Description

~2~

Mo-3632 LeA 27,919 NEW URETHANES, A PROCESS FOR THEIR PREPARATION AND THEIR
USE_AS CATALYSTS FOR ISOCYANATE POLYADDITION PROCESSES
The present invention relates to new urethanes and mixtures thereof, a process for their preparation and their use as catalysts for the diisocyanate polyaddition process.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide new urethane compounds.
It is also an object of the present invention to provide a process for the production of these urethane compounds.
It is another object of the present invention to provide new catalysts for the isocyanate addition reaction.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting (a) ethylene carbonate and/or propylene carbonate with an amine represented by the formula \R

in which A, R2 and R3 each represent a specified group at a temperature of from O to 160C.
DETAILED DESCRIPTION OF THE INVENTION
New compounds of the general formulae (I) and (II) IRl 9 /R2 HO-CH-CH2-0-C-NH-A-N \ \ (I) "R3_~
and/or 25HO-CH2-CH-O-l-NH-A-N / ~ (II) T~ ~7 Sl9 ~. q~ c3 2 ~
in which Rl represents H Ol CH3;
R2 and R3 are identical or different and each represents a Cl-C10-alkyl radical or together represent a C2-ClO-alkylene radical which may be interrupted by hetero atoms such as 0 or NR4 (R4 = Cl-C6-alkyl), and A is an optionally branched CI-ClO-al~ylene radical or a C5-CIO-cycloalkylene radical, excluding the compounds where Rl = H, R2 and R3 = CH3 orR2 andR3=
-CH2 -CH3 or R2 ~d R3 = - CH2 - CH2 - O -CH2 - CH2 - and A -(CH2)3, and mixtures of compounds represented by these formulae, in weight ratios of 1:99 to 99:1, preferably 80:20 to 20:80 have been found.
These compounds are produced by reacting ethylene carbonate and/or propylene carbonate and an amine of the general formula ~R2--`
H2N-A-N \ I (III) in which R2, R3 and A have the above-mentioned meanings at a temperature of from 0 to 160C. The urethanes represented by formulae (I) and (II) and mixtures thereof are particularly suitable as catalysts for the isocyanate addition process, in particular for the preparation of optionally cellular - polyurethanes.
It has been found, surprisingly, that compounds of the general formulae (I) and (II) and mixtures thereof can be prepared in a form which is virtually free from byproducts by reacting ethylene carbonate and/or propylene carbonate with an amine of the general formula (III). This is surprising because it would have been expected that in the reaction of ethylene Mo3632 7' - - - - - - ... . .. .

2 ~ ~ ~

carbonate and/or propylene carbonate with the amine of formula (III), free amine would react with already formed urethane to form urea derivatives as by-products. This is not the case.
Pure products which can be used without the need for further processing steps such as purificat;on are obtained.
The process for producing the compounds of the present invention may be carried out in the presence of a solvent but is preferably be carried out as a solvent free process. When a solvent is used, suitable solvents include polar solvents, such as acetonitrile, dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylacetamide and chloroform. Suitable reaction temperatures are in the range of from 0 to 160aC, preferably from 20 to 100C.
Ethylene carbonate and/or propylene carbonate and the amine of the formula (III) are preferably brought together without applying heat externally, so that the heat formed by the spontaneous reaction does not heat the reaction mixture above 60C. The reaction is brought to complete conversion at 100C. The process in which the amine of the formula (III) is added to ethylene carbonate and/or propylene carbonate is particularly preferred. If a solvent is used, each of the two reaction components ~i.e., the amine and the carbonate) components are preferably dissolved in the solvent and the amine represented by formula (III) is slowly added to the ethylene carbonate and/or propylene carbonate at 0 to 25C.
The reaction is tnen brought to complete conversion by heating ~reflux of the solvent).
Working under normal pressure is preferred, but the reaction can also be carried out under increased pressure. The process otherwise requires no special process features. The same applies to the working up. After the low-boiling constituents have been removed (for example by distillation or thin-film methods~, the product is obtained as a water-clear or slightly yellowish liquid having a purity of greater than 95 per cent which can be used without further treatment.
Mo3632 2~S2~

The resulting isomer mixtures can be separated by techniques known to tho~.e skilled in the art, for example, by fractionation over a column.
As is known to the expert, the isocyanate polyaddition process can be used to prepare polyadducts, in particular, polyurethanes, polyureas and polyamides, with diverse physical properties. These polyadducts are formed by reacting a diisocyanate or a polyisocyanate with a compound containing several isocyanate-reactive groups such as hydroxyl, amine and/or carboxyl groups. If appropriate, water and/or other blowing agents, catalysts, emulsifiers and other additives may be included in the reaction mixture. (See, for example, "Methoden der Organischen Chemie (Methods of Organic Chemistry): (Houben-Weyl), Volume E20; publisher H. Bartl, J.
Falbe; George Thieme Verlag, Stuttgart, New York 1987, pages 1561-1710 and "Kunststoff-Handbuch, Neuausgabe ~Plastics Ha~ndbook, New Edition) Volume 7: Polyurethane (Polyurethanes), publisher G. Becker, D. Braun, Hanser Verlag, Munich 1983).
Additional crosslinking reactions can also take place, to form allophanate, biuret and isocyanurate structures.
Depending upon the isocyanate and isocyanate-reactive components chosen, the polyaddition product may be homogeneous or cellular, flexible, elastic or rigid.
The starting components useful in producing isocyanate addition products in accordance with the present invention are described in detail below. These components include a polyisocyanate component, a component having at least two hydrogen atoms which are reactive towards isocyanate groups and if appropriate, other additives and auxiliaries. Blowing agents, catalysts, surface-active additives, reaction retarders, age;ng agents, plasticizers, flameproofing agents and fillers are among the appropriate additives and auxiliaries.

Mo3632 2 ~ 3 The urethanes of the formulae (I) and (,I) and mixtures thereof are useful as catalysts in the isocyanate addition process of the present invention.
Suitable isocyanates for the isocyanate polyaddition process using compounds of the formulae (I~ and (II) and mixtures thereof include: aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates. Such polyisocyanates are described, for example, in "Methoden der Organischen Chemie (Methods of Organic Chemistry)"
(Houben-Weyl), Volume E20; editors H. Bartl, J. Falbe; George Thieme Verlag, Stuttgart, New York 1987, pages 1588-1594.
Examples of appropriate isocyanates include those represented by the formula Q(NCO)n in which n represents a number from 2 to 4, preferably 2, and Q represents an aliphatic hydrocarbon radical having from 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical having from 4 to 14 (preferably 5 to 10) carbon atoms, an aromatic hydrocarbon radical having from 6 to 15 (preferably 6 to 13) carbon atoms, or an araliphatic hydrocarbon radical having from 8 to 15 (preferably 8 to 13) carbon atoms.
Specific examples of such isocyanates are: ethylene diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate, dodecane 1,12-diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, hexahydro-toluylene 2,4- and 2,6-diisocyanate and any desired mixtures of these isomers, hexahydrophenylene 1,3- and/or 1,4-di-isocyanate, perhydrodiphenylmethane 2,4'- and/or 4,4'-Mo3632 2 ~3 2 ~ ~ ~

diisocyanate, phenylene 1,3- and 1,4-diisocyanate, toluylene 2,4- and 2,6-diisocyanate and any desired mixturPs of these isomers and diphenylmethane 2,4'- and/or 4,4'-diisocyanate.
Other examples of possible polyisocyanate components for the isocyanate polyaddition process in which the compounds represented by formulae (I) and (II) and mixtures thereof are employed include: triphenylmethane 4,4',4"-triisocyanate, polyphenyl-polymethylene polyisocyanates such as are obtained by aniline-formaldehyde condensation and subsequent phosgenation (see, for example, British Patent Specifications 874,430 and 848,671), m- and p-isocyanatophenyl sulphonyl isocyanates (see, for example, U.S. Patent 3,454,606), perchlorinated aryl polyisocyanates (see, for example, U.S.
Patent 3,277,138), polyisocyanates containing carbodiimide (see, for example, German Patent Specification 1,092,007, U.S.
Patent 3,152,162, DE-OS (German Published Specification) 2,504,400, DE-OS (German Published Specification) 2,537,685 and DE-OS (German Published Specification) 2,552,350), norbornane diisocyanates (see, for example, U.S. Patent 3,492,330), polyisocyanates containing an allophanate group (see, for example, British Patent Specification 994,890, Belgian Patent Specification 761,626 and Dutch Patent Specification 7,102,542), polyisocyanates containing isocyanurate groups (see, for example, U.S. Patent 3,001,973, German Patent Specifications 1,022,789, 1,222,067 and 1,027,394 and DE-OS
- (German Published Specifications) 1,929,034 and 2,004,048), polyisocyanates containing a urethane group (see, for example, Belgian Patent Specification 752,261 and U.S. Patents 3,394,164 and 3,664,457), polyisocyanates containing acylated urea groups ~see, for example, German Patent Specification 1,230,778), polyisocyanates containing biuret groups (see, for example, U.S. Patents 3,124,605 and 3,201,372 and British Patent Specification 889,050~, polyisocyanates prepared by telomerization reactions (see, for example, U.S. Patent 3,654,106), polyisocyanates containing ester groups (see, for Mo3632 2 ~ ;~ 2 ~ ~ 8 example, British Patent Specifications 965,474 and 1,072,956, U.S. Patent 3~567,763 and German Patent Specification 1,231,688), reaction products of the above-mentioned isocyanates with acetals (see, for example, German Patent Specification 1,072,385) and polyisocyanates containing polymeric fatty acid esters (see, for example, U.S. Patent 3,455,883), as well as the distillation residues which are obtained during the industrial preparation of such isocyanates.
It is also possible to use mixtures of a polyisocyanate component and an epoxide component which have been stabil ked, if appropriate, by heat treatment in the presence of an alkylating agent, that is to say so-called isocyanate/epoxide combination resins, as the polyisocyanate component. (See, for example, DE-AS (German Published Specification) 1,115,932, German Patent Specification 2,655,367, DE-AS (German Published Specification) 2,359,386, DE-OS (German Published Specification) 2,430, European Patent Specification 223,087, DE-OS (German Published Specification) 2,432,952, U.S. Patents 3,020,262 and 4,728,676 and ~uropean Patent Specification 272,563).
Reaction components having at least two hydrogen atoms which are reactive towards isocyanates which are suitable for the isocyanate polyaddition process include compounds having a molecular weight of from about 400 to about 10,000. In addition to compounds containing amino groups, thiol groups or carboxyl groups, compounds containing hydroxyl groups specifically those having from two to eight hydroxyl groups and molecular weight of from about 1000 to about 8000, preferably those having a molecular weight of from about 1500 to about 4000 may be used. Specific examples of such isocyanate-reactive compounds include: polyesters, polyethers, polythioethers, polycarbonates and polyester-amides containing at least two, generally from 2 to 8, and preferably from 2 to 4 hydroxyl groups. Specific compounds which are useful for the Mo3632 ~2~

preparation of homogeneous and cellular polyurethanes are known to those skilled in the art.
Suitable polyesters containing hydroxyl groups include, for example, reaction products of polyhydric, preferably dihydric and if appropriate addit;onally trihydr;c, alcohols with polyoasic, preferably dibasic, carboxylic acids.
Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for the preparation of the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and/or heterocyclic in nature, and may bP substituted, for example by halogen atoms, and/or unsaturated.
Specific examples of such carboxylic acids and derivatives thereof are: succinic acid, adipic acid, suberic acid, azeleic acid, sebacic acid, phthalic acid, isophthalic acid, tr~imellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated fatty acids, if appropriatP as a mixture with monomeric unsaturated fatty acids, dimethyl terephthalate and terephthalic acid bisglycol esters.
Suitable polyhydric alcohols are, for example, ethylene glycol, propylene 1,2- and 1,3-glycol, butylene 1,4- and 2,3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 1,4-bis(hydroxymethyl)cyclohexane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, formitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyethylene glycols, dipropylene glycols and higher polypropylene glycols as well as dibutylene glycols and higher polybutylene glycols.
Mo3632 I~J ~ ~ 2 ~ ~ ~

The polyesters may contain a proportion of terminal carboxyl groups. Polyesters of lactones, for example ~-caprolactam, or of hydroxycarboxylic acids, for example ~-hydroxycaproic acid, may also be employed.
Suitable polyethers containing at least two, generally from 2 to 8, preferably two to three, hydroxyl groups are known to those skilled in the art. These polyethers may be prepared, for example, by self-polymerization of epoxides, such as ethylene`oxide, propylene oxide, butylene ox;de, styrene oxide or epichlorohydrin, or of tetrahydrofuran. The self-polymerization may be carried out, for example, in the presence of a Lewis catalyst such as BF3. The polyethers may also be formed by addition of an epoxide, preferably of ethylene oxide and propylene oxide (either as a mixture or in succession) onto starting components containing reactive hydrogen atoms, such as water, alcohols, ammonia or amines. Specific examples of starting components having reactive hydrogen atoms are:
ethylene glycol, propylene 1,3- or 1,2-glycol, glycerol, sorbitol, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine and ethylenediamine. Sucrose polyethers (see, for example, DE-OS (German Published Specifications) 1,176,358 and 1,064,938), and polyethers started on formitol or formose (DE-OS (German Published Specification) 2,639,083 and 2,737,951) may also be used. Polybutadienes containing hydroxyl groups are also suitable.
Suitable polythioethers for the isocyanate addition process include: condensation products of thioglycol with itself and/or other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols. Depending upon the co-components, the products may be mixed polythioethers, polythioetheresters or polythioether-ester-amides.
Suitable polyacetals can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-di(hydroxyethoxy) diphenyldimethyl-methane, hexanediol and formaldehyde.
3~ Suitable polyacetates can also be prepared by polymerization of Mo3632 2~2~

cyclic acetals such as trioxane (DE-OS (German Published Specification) 1,694,128).
Useful polycarbonates containing hydroxyl groups are known. These polycarbonates may be prepared, for example, by reaction of a diol such as propane-1,3-diol, butane-1,4-diol and/or hexane-1,6-diol, diethylene glycol, triethylene glycol, tetraethylene glycol or thiodiglycol with a diaryl carbonate (for example, diphenyl carbonate) or phosgene (DE-OS (German Published Specifications) 1,694,080 and 2,221,751).
Polyester-amides and polyamides which may be used in the isocyanate addition reaction include, for example, the predominantly linear condensates obtained from polybasic saturated or unsaturated carboxylic acids or anhydrides thereof and polyfunctional saturated or unsaturated aminoalcohols, diamines, polyamines and mixtures thereof.
Polyhydroxyl compounds which already contain urethane or urea groups~ optionally modified naturally occurring polyols (such as castor oil) or carbohydrates (for example, starch) may also be used. Addition products of alkylene oxides on phenol-formaldehyde resins can also be used.
The polyhydroxyl compounds mentioned above can also be modified in various ways. For example, DE-OS (German Published Specification) 2,210,839, (U.S. Patent 3,849,515) and DE-OS
(German Published Specification) 2,544,195, each discloses a process in which a mixture of different types of polyhydroxyl compounds (for example of a polyether and a polyester-polyol) can be subjected to a condensation reaction by etherification in the presence of a strong acid to give a higher molecular weight polyol which is built up from different segments bonded via ether bridges. It is also possible to introduce amide groups into the polyhydroxy compound (see, for example, DE-OS
(German Published Specification) 2,559,372), or for triazine groups to be introduced by reaction with polyfunctional cyanic acid esters (DE-OS (German Published Specification) 2,620,487).
Guanidine and phosphonoformamidine compounds are obtained by Mo3632 ~ ~'3 ~ g reacting a polyol with less than the equivalent amount of diisocyanatocarbodiimide and subsequent reaction of the carbodiimide group with an amine, amide, phosphite or a carboxylic acid (DE-OS (German Published Specifications) 2,714,289, 2,714,292 and 2,714,293).
Po1yhydroxyl compounds containing high molecular weight polyadducts or polycondensates or polymers in finely dispersed, dissolved or grafted form are also suitable. Such modified polyhydroxy compounds may be obtained when polyaddition reactions (for example, reactions between polyisocyanates and compounds containing amino functional groups) or polycondensation reactions (for example, reactions between formaldehyde and phenols and/or amines) are allowed to proceed in situ in the compounds containing hydroxyl groups. Such processes are described, for example, in DE-AS (German Published Specifications) 1,168,075 and 1,126,142, as well as DE OS (German Published Specifications) 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,220,796, 2,55~,797, 2,550,833, 2,550,862, 2,633,293 and 2,639,254. It is also possible, in accordance with U.S. Patent 3,869,413 and DE-OS (German Published Specification) 2,550,860, to mix a finished aqueous polymer dispersion with a polyhydroxy compound and for water subsequently to be removed from the mixture.
Polyhydroxyl compounds modified by vinyl polymerization, such as those obtained by polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. Patents 3,383,351, 3,323,093 and 3,110,695 and DE-AS (German Published Specification) 1,152,536) or polycarbonate-polyols (German Patent Specification 1,769,795 and U.S. Patent 3,637,909) are also suitable.
If polyether polyols which have been modified in accordance with DE-OS (German Published Specifications) 2,442,101, 2,644,922 and 2,646,141 by graft polymerization with vinylphosphonic acid esters and if appropriate (meth)-Mo3632 ~J ~

acrylonitrile, (meth)acrylamide, or (meth)acrylic acid esters containing OH functional groups are used, plastics having a good flame retardancy are obtained.
Representative isocyanate-reactive compounds which can be used for the diisocyanate polyaddition process in which urethanes of the formulae (I) and (II) and mixtures thereof are used as the catalyst are described, for example, in High Polymers, Volume XVI "Polyurethanes, Chemistry and Technology", by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32, 42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199, and in Kunststoff-Handbuch (Plastics Handbook) Volume YII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munich, 1966, for example on pages 45 to 71. It is, of course, possible to employ mixtures of the above-mentioned compounds having at least two hydrogen atoms which are reactive towards isocyanate groups and a molecular we~ight of 400 to 10,000, for example mixtures of polyethers and polyesters.
Polyetherpolyamines containing terminal aromatic primary 20 amino groups such as those described in European Patent Specification A-79,536, DE-OS (German Published Specification) 2,948,419, DE-OS (German Published Specification) 2,019,432, DE-OS (German Published Specification) 2,619,840 and U.S.
Patents 3,808,250, 3,975,426 or 4,016,143 may also be used in 25 the polyaddition process.
In some cases, it is of particular advantage to combine low-melting and high-melting polyhydroxy compounds with one another (DE-OS (German Published Specification) 2,706,297).
Compounds having a molecular weight of 32 to 399 may be used, where appropriate, as components having at least two reactive hydrogen atoms. These compounds which may rontain hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably hydroxyl groups and/or amino groups serve as chain lengthening agents. These compounds generally Mo3632 2~2~

have from 2 to 8, preferably from 2 to 4, hydrogen atoms which are reactive towards isocyanate groups.
It is also possible to use mixtures of various chain lengthening compounds having at least two hydrogen atoms which are reactive towards isocyanates and a molecular weight of 32 to 399.
Examples of suitable chain lengthening compounds are:
ethylene glycol, propylene 1,2- and 1,3-glycol, butylene 1,4-and 2,3-glycol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 1,4-bis(hydroxymethyl)-cyclohexane, 2-methyl-1,3-propanediol, dibromobutanediol (U.S. Patent 3,723,392), glycerol, trimethylolpropane, hexane-1,2,6-triol, trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, castor oil, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyethylene glycols having a molecular weight of up to 399, dipropylene glycol and higher polypropylene glycols having a molecular weight of up to 399, and dibutylene glycol and higher polybutylene glycols having a molecular weight of up to 399, 4,4'-dihydroxydiphenylpropane, di(hydroxymethyl)hydroquinone, ethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine and 3-aminopropanol.
Other low molecular weight polyhydroxy compounds which may be employed include: mixtures of hydroxyaldehydes and hydroxyketones ("formose") and the polyhydric alcohols obtained therefrom by reduction ("formitol"). Such compounds are formed during the self-condensation of formaldehyde hydrate in the presence of a metal catalyst and of a compound capable of enediol formation as the co-catalyst (DE-OS (German Published Specification) 2,639,084, 2,714,084, 2,721,186, 2,738,154 and 2,738,512).
Examples of suitable diamines are ethylenediamine, 1,4-tetramethylenediamine, hexamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine and mixtures thereof, 1-amino-3,3,5-trimethyl-5-amino-Mo3632 ~32~ ~

methylcyclohexane ("isophoronediamine"), 2,4- and 2,6-hexahydrotoluylenediamine and mixtures thereof, perhydro-2,4'-and 4,4'-diaminodiphenylmethane, p-xylylenediamine, bis(3-aminopropyl)methylamine, diaminoperhydroanthracenes (DE-OS (German Published Specification) 2,638,731) and cycloaliphatic triarnines according to DE-OS (German Published Specification) 2,614,244; hydrazine and substituted hydrazines such as methylhydrazine, N,N'dimethylhydrazine and homologues thereof; acid dihydrazides such as carbodihydrazide, oxalic acid dihydrazide and the dihydrazides of malonic acid, succinic acid, glutaric acid, adipic acid, ~-methyladipic acid, sebacic acid, hydracrylic acid and terephthalic acidi and semicarbazido-alkylene hydrazides such as ~-semicarbazido-propionic acid hydrazide (DE-OS (German Published Specification) 1,770,591); semicarbazidoalkylene-carbazic esters such as 2-semicarbazidoethylcarbazic ester (DE-OS
(German Published Specification) 1,918,504); and aminosemi-carbazide compounds such as ~-aminoethylsemicarbazido-carbonate (DE-OS (German `Published Specification) 1,902,931).
Examples of appropriate aromatic diamines are bisanthranilic acid esters (DE-OS ~German Published Specifications) 2,040,644 and 2,160,590); 3,5-and 2,4-diaminobenzoic acid esters (DE-OS (German Published Specification) 2,025,900); diamines containing ester groups (described in DE-OS (German Published Specification) 1,803,635, (U.S. Patent 3,681,290) t DE-OS (German Published Specifications) 2,040,650 and 2,160,589); diamines containing ether groups (DE-OS (German Published Specifications) 1,770,525 and 1,809,172 (U.S. Patents 3,654,364 and 3,736,295);
2-halo-1,3-phenylenediamines optionally substituted in the 5-position (DE-OS (German Published Specifications) 2,001,772, 2,025,896 and 2,065,869);
3,3'-dichloro-4,4'-diaminodiphenylmethane; tolylenediamine;
4,4'-diaminodiphenylmethane; 4,4'-diaminodiphenyl disulphide (DE-OS (German Published Specification) 2,404,976);
Mo3632 ~'J ~.3 diaminodiphenyl dithioethers tDE-OS (German Published Specification) 2,509,404); aromatic diamines substituted by alkylthio groups (DE-OS tGerman Published Specification) 2,638,760); diaminobenzenephosphonic acid esters (DE-OS (German Published Specification) 2,459,491); aromatic diamines containing sulphonate or carboxylate groups (DE-OS (German Published Specification) 2,720,166); and the high-melting diamines listed in DE-OS (German Published Specification) 2,635,400. Examples of suitable aliphatic-aromatic diamines 10 include the aminoalkylthioanilines according to DE-OS (German Published Specification) 2,734,574.
Compounds such as 1-mercapto-3-aminopropane, optionally substituted amino acids such as glycerol, alanine, valine, serine and lysine, and optionally substituted dicarboxylic 15 acids such as succinic acid, adipic acid, phthalic acid, 4-hydroxyphthalic acid and 4-amino-phthalic acid may also be used as compounds having at least two hydrogen atoms which are reactive towards isocyanates and have a molecular weight of from 32 to 399.
Compounds which are monofunctional towards isocyanates can be used as so-called chain terminators. These chain terminators are generally used in amounts of from about 0.01 to about 10 % by weight, based on the polyurethane solid.
Examples of such monofunctional compounds include monoamines 25 such as butyl- and dibutylamino, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine and cyclohexylamine; monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol; amyl alcohnls; cyclohexanol and ethylene glycol monoethyl ether.
39 Other auxiliaries and additives which can be used in the isocyanate polyaddition process together with urethanes of the formulae (I) and (II) and mixtures thereof include: blowing agents, catalysts, surface active additives such as emulsifiers and foam stabilizers, and reaction retarders.

Mo3632 3 2 t~

Water and/or any of the known highly volatile inorganic or organic blowing agents may be used to produce isocyanate addition products in accordance with the present invention.
Suitable organic blowing agents include: acetone; ethyl acetate; halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane and chlorodifluoromethane; and butane, hexane, heptane or diethyl ether. Possible inorganic blowing agents include, for example, air, C02 or N20.
A blowing effect may also be achieved by inclusion of compounds which decompose at temperatures above room temperature to split off a gas (for example, nitro~en) such as azo compounds (e.g., azocarboxamide or azoisobutyronitrile).
Other examples of blowing agents and details on the use of blowing agents are described in Kunststoff-Handbuch (Plastics Handbook), Volume VII, edited by Vieweg and Hochtlen, Ca~l-Hanser-Verlag, Munich 1966, for example on pages 108 and 109, 4~3 to 455 and 507 to 510.
Any of the known catalysts may be used in the isocyanate addition reaction of the present invention. Examples of suitable catalysts include tertiary amines, triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N'-N'-tetramethylethylenediamine, pentamethyl-diethylenetriamine and higher homologues (DE-OS 2,624,527 and 2,624,528), 1,4-diazabicyclo[2,2,2]-octane, N-methyl-N'-dimethylaminoethylpiperazines (DE-OS (German Published Specification~ 2,636,787), N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis-(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-~-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic am;dines (DE-OS (German Published Specification) 1,720,633), bis-(dialkylamino)alkyl ethers (U.S. Patent 3,330,782, DE-AS
(German Published Specification) 1,030,558 and DE-OS (German Published Specification) 1,804,361 and 2,618,280) and amide Mo3632 2~S2~3'1~

groups (preferably tertiary amines containing formamide groups according to DE-OS (German Published Specification) 2,523,633 and 2,732,292). Known Mannich bases of secondary amines (dimethylamine), aldehydes (preferably formaldehyde), ketones (acetone, methyl ethyl ketone or cyclohexanone), and phenols, (phenol, nonylphenol or bisphenol) may also be used as catalysts.
Tertiary amines containing hydrogen atoms which are active towards isocyanate groups which are useful as catalysts include: triethanolamine, triisopropanolamine, N-methyl-diethanolamine, ethyldiethanolamine, N,N-dimethylethanolamine, reaction products thereof with alkylene oxides (such as propylene oxide) and secondary-tertiary amines such as those described in DE-OS (German Published Specification) 2,732,292.
Other possible catalysts are silaamines having carbon-silicon bonds such as those described, for example, in German Patent Specification 1,22g,290 and U.S. Patent 3,620,984. Specific examples of appropriate silaamines are 2,2,4-trimethyl-2-silamorpholine and 1,3-diethyl-aminomethyl-tetramethyldisiloxane.
Nitrogen-containing bases such as tetralkylammonium hydroxides; alkali metal hydroxides such as sodium hydroxide;
alkali metal phenolates such as sodium phenolate; alkali metal alcoholates such as sodium methylate; hexahydrotriazines (DE-OS
(German Published Specification) 1,769,043) may also be used as catalysts.
The reaction between NCO groups and Zerewitinoff active hydrogen atoms is also accelerated greatly by lactams and azalactams, a complex first being formed between the lactam and the compound with the acidic hydrogen. Such complexes and their catalytic ac$ion are described in DE-OS (German Published Specifications~ 2,062,288, 2,062,289 and 2,117,576 (U.S. Patent 3,7~8,444) and DE-OS (German Published Specifications) 2,129,198, 2,330,175 and 2,330,211.

Mo3632 ~ 3 Organometallic compounds, in particular organotin compounds, may also be used as catalysts. Suitable organotin compounds include: sulphur containing compounds such as di-N-octyltin mercaptide (DE-AS (German Published Specification) 1,769,367 and U.S. Patent 3,645,927); preferably tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate and tin(II) laurate; and tin(IV) compounds such as dibutyltin oxide, dibutyl dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin ~aleate and dioctyltin diacetate.
All the above-mentioned catalysts may, of course, also be employed as mixtures. Combinations of organic amidines, am;nopyridines or hydrazinopyridines (DE-OS (German Published Specifications) 2,434,185 and 2,601,082 and German 2,603,834) are particularly useful.
Other catalysts which may be used and the details on the mode of action of the catalysts are described in Kunsttoff-~andbuch (Plastics Handbook~ Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, pages 96 to 102.
In the practice of the present invention, from 5 to 100%
by weight, preferably from 50 to 100% by weight, most preferably from 80 to 100% by weight of compounds (I) and (II) and mixtures thereof, based on the total amount of catalyst are used as the catalyst.
The catalyst or the catalyst mixture is as a rule employed in an amount of between about 0.01 and 10 % by weight, based on the total amount of compounds having at least two hydrogen atoms which are reactive towards isocyanates. In isocyanate/
epoxide combination resins containing no compounds having hydrogen atoms which are reactive towards isocyanates (as described, for example, in DE-AS (German Published Specification) 1,115,932, German Patent Specification 2,655,367, DE-AS (German Published Specification) 2,359,386, DE-OS (German Published Specification) 2430, European Patent Mo3632 f ~ 2 ~ ~ ~

Specification 223,087, DE-OS (German Published Specification) 2,432,952 (U.S. Patent 3,020,262), U.S. Patent 4,728,676 and European Patent Specification 27~,563), the catalysts are as a rule used in an amount of between about 0.001 and 10% by weight, based on the total amount of reaction mixture.
Surface-active additives, such as emulsifiers and foam stabilizers may also be included in the isocyanate addition reaction mixture. Suitable emulsifiers include: the sodium salts of castor oil; sulphonates and salts of fatty acids with amines, such as oleic acid diethylamine salt and stearic acid diethanolamine salt. Alkali metal salts or ammonium salts of sulphonic acids such as dodecylbenzenesulphonic acid or dinaphthylmethanedisulphonic acid, or of fatty acids such as ricinoleic acid, or of polymeric fatty acids may also be used in combination as surface-active substances.
Particularly preferred foam stabilizers are po~yethersiloxanes, especially those which are water-soluble.
These compounds are in general built up such that a copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. Such foam stabilizers are described, for example, in U.S. Patents 2,834,748 and 3,629,308. Polyoxyalkylene copolymers having multiple branches via allophanate groups such as those described in DE-OS (German Published Specification) 2,558,523 are particularly useful.
Reaction retarders (for example, acid substances or organic acid chlorides), known cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes), pigments, dyestuffs, known flameproofing agents (for example, tris(chloroethyl) phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate), stabilizers against the influences of ageing and weathering, plasticizers, substances having a fungistatic and bacteriostatic action, and fillers (such as barium sulphate, kieselguhr, carbon black or prepared chalk) may also be included in the isocyanate addition reaction mixture.
Mo3632 2 ~ ~ ~

Additional examples of surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyestuffs and fillers and also substances having a fungistatic and bacteriostatic action, and details on the method of use and mode of action of these additives are described in Kunststoff-Handbuch (Plastics Handbook) Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, pages 103 to 113.
The reaction components may be reacted by the one-stage process known to those skilled in the art, the known prepolymer process or the known semiprepolymer process using commercially available machinery. Equipment which is useful for carrying out the isocyanate addition reaction in accordance with the present invention is described in U.S. Patent 2,764,565.
Details about suitable processing equipment are discussed in Kunststoff-Handbuch (Plastics Handbook) Volume VII, edited by Vi~eweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, pages 121 to 205.
Known "external release agents" such as silicone oils, are often used for foam molding. However, it is also possible to use so-called "internal release agents", if appropriate, in combination with external release agents. Such mixtures are described, for example, in DE-OS (German Published Specifications) 2,121,670 and 2,307,589.
Cold-curing foams can also be prepared in accordance with the p~esent invention (compare British Patent Specification 1,162,517 and DE-OS (German Published Specification) 2,153,086).
It is, of course, also possible to prepare foams by block foaming or by the continuous laminator process which is known to those skilled in the art.
The products obtainable by the process of the present invention are useful as padding material, mattresses, insulating materials, coatings, rubbery materials and surface coatings.
Mo3632 Having thus described our invention, the following examples are given as being illustrative thereof. All parts and percentages given in these examples are parts by weight or percentages by weight, unless otherwise indicated.
EXAMPLES
Example 1 Preparation of a mixture of 0-(2-hydroxy-1-propyl)-3-(dimethylaminopropyl)urethane and O-(l-hydroxy-2-propyl)-3-(dimethylaminopropyl)urethane 21.6-2 9 (0.212 mol) of 3-(dimethylamino)propylamine were added dropwise to 21.62 g (0.212 mol) of propylene carbonate in a 100 ml three-necked flask at room temperature in the course of 1 hour. During this procedure, the mixture heated up to 60C. The mixture was stirred at room temperature for 1 hour and at 100C for 12 hours. A pale yellowish-colored liquid of a 40:60 mixture of 0-(2-hydroxy-1-propyl)-3-(dimethylaminopropyl) urethane and 0-(1-hydroxy-2-propyl)-3-(dimethylaminopropyl) urethane having a purity of greater than 95% was obtained. OH number: 274 mg of ~OH/g-ExamPle 2 Preparation of a mixture of 0-(2-hydroxy-1-propyl)-3-(diethylaminopropyl)urethane and 0-(1-hydroxy-2-propyl)-3-(diethylaminopropyl urethane. 20.40 9 (0.2 mol) of propylene ~arbonate were added dropwise to 26.00 9 (0.2 mol of 3-(dimethylamino)propyl-amine in a 100 ml three-necked flask at room temperature. During this procedure, the mixture heated up to 60C. The mixture was stirred at room temperature for 20 minutes and at 100C for 5 hours. A water-clear liquid of a mixture of 33 parts of 0-(2-hydroxy-1-propyl)-3-(diethylamino-propyl)urethane and 67 parts of 0-(1-hydroxy-2-propyl)-3-(diethylaminopropyl)urethane having a purity of greater than 95% was obtained.
Example 3 Preparation of a mixture of 0-(2-hydroxy-1-propyl)-3-(diethylaminopropyl)urethane and 0-(1-hydroxy-2-propyl)-3-Mo3632 ~ r ;3 2 ~

(diethylaminopropyl)urethane (as Example 2, but reversed addition of the starting materials).
26.00 g (0.2 mol) of 3-diethylaminopropylamine were added dropwise to 20.40 9 (0.2 mol) of propylene carbonate in a 100 ml three-necked flask at room temperature. However, the mixture had to be stirred at 100C for 20 hours to bring the reaction to completion. A slightly yellowish liquid of a mixture of 33 parts of 0-(2-hydroxy-1-propyl)-3-(diethylaminopropyl)urethane and 67 parts of 0-(1-hydroxy-2-propyl)-3-(diethylaminopropyl) urethane having a purity of greater than 95% was obtained.
Example 4 Preparation of a mixture of 0-(2-hydroxy-1-propyl)-3-(diethylaminoethyl)urethane and 0-(1-hydroxy-2-propyl)-3-(diethylaminoethyl)urethane. 20.40 9 (0.2 mol) of propylene carbonate were added dropwise to 23.20 g (0.2 mol) of 3-diethylaminoethylamine in a 100 ml three-necked flask at room temperature. During this procedure, the mixture heated up to not more than 62C. The mixtur2 was stirred at room temperature for 10 minutes and at 100C for 20 hours. A
water-clear liquid of a mixture of 45 parts of 0-(2-hydroxy-1-propyl)-3-(diethylaminoethyl)urethane and 55 parts of 0-~l-hydroxy-2-propyl)-3-(diethylaminoethyl)urethane having a purity of greater than 95% was obtained. -Example 5 Preparation of a mixture of 0-(2-hydroxy-1-propyl)-3-(morpholinopropyl)urethane and 0-(1-hydroxy-2-propyl)-3-(morpholinopropyl) urethane. 24.00 9 (0.2 mol) of propylene carbonate were added dropwise to 28.80 9 (0.2 mol) of N-(3-aminopropyl)-morpholine in a 100 ml three-necked flask at room temperature. During this procedure, the mixture heated up to not more than 45CC. The mixture was stirred at room temperature for 15 minutes and at 100C for 11 hours. A
yellowish liquid of a mixture of 24 parts of 0-(2-hydroxy-l-propyl)-3-(morpholinopropyl)urethane and 76 parts of 0-(1-Mo3632 hydroxy-2-propyl)-3-(morpholinopropyl)urethane having a purity of greater than 95% was obtained.
The materials used to prepare foams in Examples 6-9 were as follows:
Polyol 1: OH number 533;
viscosity 3400 mPas at 25C; made up of 25 parts by weight of a polyether having a hydroxyl number of 470 which was prepared by ethoxylation and propoxylation of o-toluylenediamine, 10 . 27 parts by weight of a polyether having a hydroxyl number of 440 which was prepared by propoxylation of a mixture of phthalic anhydride, sorbitol and diethylene glycol, 15 parts by weight of a polyether having a hydroxyl number of 630 which was prepared by propoxylation of ethylenediamine, 16 parts by weight of a polyether having a hydroxyl number of 450 which was prepared by propoxylation sf a mixture of sugar and ethylene glycol, 7 parts by weight of glycerol, and 10 parts by weight of tris(~-chloroethyl) phosphate as a flameproofing agent.
Polyol 2: OH number 520 mg of KOH/g;
viscosity: 1000 mPas at 25C; made up of 45 parts by weight of a polyether having a hydroxyl number of 380 which was prepared by propoxylation of trimethylolpropane, 25 parts by weight of a polyether having a hydroxyl number of 550 which was prepared by propoxylation of trimethylolpropane, 5 parts by weight of a polyether having a hydroxyl number of 875 which was prepared by propoxylation of trimethylolpropane, 10 parts by weight of glycerol, 15 parts by weight of diphenyl cresyl phosphate, as a Mo3632 flameproofing agent, 2 parts by weight of a commercially available polyether-polysiloxane foam stabilizer (OS 50, BAYER
AG, Leverkusen) and 1 part by weight of water.
Polyol 3: Ethylene oxide/propylene ox;de copolyether having an OH number of 45 which was started on trimethylolpropane.
Stabilizer 1: commercially available polyether-polysiloxane foam stabilizer (B8421, Goldschmidt AG, Essen).
Stabilizer 2: commercially available polyether-polysiloxane foam stabilizer (OS 20, BAYER AG, Leverkusen~
Blowing agent R11: Trichlorofluoromethane Catalyst 1: tin(II) octoate Catalyst 2: commercially available amine catalyst (Desmorapid) PS 207, BAYER AG, Leverkusen) Isocyanate 1: Methylenediphenyl 4,4'-diisocyanate crude product having an isocyanate content of 30.3%
and a viscosity of 200 mPas at 25C.
Isocyanate 2: 80:20 mixture of toluylene 2,4-diisocyanate and toluylene 2,6,diisocyanate ExamDle 6 Preparation of a rigid polyurethane foam The reaction components listed in Table 1, apart from the isocyanate, were weighed into and mixed in a cardboard container. After addition of the isocyanate, the mixture was stirred for the stated time using a high-speed stirrer at 2000/revolutions/minute and foamed in a mold. The cell size and cell structure were evaluated visually in accordance with a scale from 1 to 6, where 1 is the ~est and 6 the worst value.

Mo3632 a Tabl e 1:
Exampl eCompari son 6 Exampl e Di methyl cycl ohexyl ami ne ( pbw) - 1 . 3 Catalyst from Example 1 (pbw)4.0 Polyol I (pbw) 100 100 Stabilizer 1 (pbw) 1.2 1.2 Water (pbw) 0.8 0.8 Blowing agent R11 (pbw) 35 35 Isocyanate 1 (pbw) 154 154 Stirring time in seconds 10 10 Resting time in seconds 12 12 Setting time in seconds 42 40 Tack-free time in seconds 50 49 Cell size 2-3 2-3 Cel l structure 2-3 2-3 Gross density in kg/m3 30 28 Smell none of amine Exampl e 7 20 Preparation of a rigid polyurethane foam The reaction components listed in Table 2, apart from the isocyanate, were weighed into and mixed in a cardboard container. The amounts listed in Table 2 are parts by weight.
After addition of the isocyanate, the mixture was stirred for 25 the stated time using a high-speed stirrer at 2000 revolutions/
minute and foamed in a mold. The cell size and cell structure were evaluated visually in accordance with ascalefromlto6, where 1 is the best and 6 the worst value.

Mo3632 2 ~ ~ ~

Table 2:
Example Comparison 7 Example Dimethylcyclohexylamine - 1.7 Catalyst from Example 1 7.0 Polyol 2 103 103 Water 1.3 1.5 Blowing agent R11 15 15 Isocyanate 1 178 178 Stirring time in seconds 10 10 Resting time in seconds 24 20 Setting time in seconds 51 50 Tack-free time in seconds 70 80 Cell size 2 2 Cell structure 2-3 2-3 Gross density in kg/m3 33 32 Smell none of amine ExamDle 8 Preparation of a rigid polyurethane foam The reaction components listed in Table 3, apart from the isocyanate, were weighed into and mixed in a cardboard container. The amounts listed in Table 3 are parts by weight.
After addition of the isocyanate, the mixture was stirred for the stated time using a high-speed stirrer at 2000 revolutions/minute and foamed in a mold. The cell size and cell structure were evaluated visually in accordance with a scale from 1 to 6, where 1 is the best and 6 the worst value.

Mo3632 ~ 9 r~

Table 3:
Example Comparison 8 Example Dimethylcyclohexylamine - 1.5 Catalyst from Example 1 6.5 Polyol 2 103 103 Water 2.5 2.5 Isocyanate 1 194 194 Stirring time in seconds 10 10 Resting time in seconds 23 21 Setting time in seconds 49 49 Tack-free time in seconds 65 75 Cell size 2 2 Cell structure 2-3 2-3 Gross density in kg/m3 38 37 Smell none of amine ExamDle 9 Preparation of a rigid polyurethane foam The reaction components listed in Table 4, apart from the isocyanate, were weighed into and mixed in a cardboard container. The amounts listed in Table 4 are parts by weight.
After addition of the isocyanate, the mixture was stirred for the stated time using a high-speed stirrer at 2000 revolutions/ll~inute and foamed in a mold, where 1 is the best and 6 the worst value.

Mo3632 2 ~ 5 ~

Table 4:
Example Comparison 9 Example Catalyst 1 0.1 0.1 Catalyst 2 - 0.2 Catalyst from Example 10.4 Polyol 3 100 100 Stabilizer 2 1.2 1.2 Water 3.0 3.0 Isocyanate 2 38.5 38.5 Stirring time in seconds30 30 Rising time in minutes 6 5 Heating at 80C 2 hours 2 hours Cell structure 3 2-3 Gross density in kg/m3 30 29 Smell none of amine Mo3632

Claims (7)

1. A compound represented by one of the following formulae:

(I) and/or (II) in which R1 represents hydrogen or a methyl group, R2 and R3 which may be the same or different, each represents a C1-C10-alkyl radical or together represent a C2-C10-alkylene radical which can be interrupted by one or more hetero atoms and A represents an optionally branched C1-C10-alkylene radical or a C5-C10-cycloalkylene radical, provided that when R1 represents hydrogen and R2 and R3 each represent a methyl group, A does not represent -(CH2)3-.
2. The compound of Claim 1 in which R2 and R3 together represent a C2-C10-alkylene radical which is interrupted by an oxygen atom or the group NR4 in which R4 represents a C1-C6-alkyl group.
3. A composition in which at least one compound represented by formula (I) and at least one compound represented by formula (II) are present.
4. The composition of Claim 3 in which the weight ratio of the compound represented by formula (I) to the compound represented by formula (II) is from 1:99 to 99:1.

Mo3632
5. The composition of Claim 3 in which the weight ratio of the compound represented by formula (I) to the compound represented by formula (II) is from 80:20 to 20:80.
6. A process for the production of the compound of Claim 1 in which a) ethylene carbonate and/or propylene carbonate is reacted with b) an amine represented by the formula (III) in which R2 and R3 which may be the same or different each represent a C1-C10-alkyl radical or together represent a C2-C10-alkylene radical which may optionally be interrupted by a hetero atom at a temperature of from 0 to 160°C.
7. A process for the production of isocyanate addition products comprising reacting an isocyanate with an isocyanate-reactive compound in the presence of a catalyst which catalyst is the compound of Claim 1.

Mo3632
CA002052048A 1990-09-27 1991-09-23 Urethanes, a process for their preparation and their use as catalysts for isocyanate polyaddition processes Abandoned CA2052048A1 (en)

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DE4030515.5 1990-09-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705672A (en) * 1994-08-09 1998-01-06 Bayer Aktiengesellschaft Tertiary amines having carbonate and urethane groups
US5834579A (en) * 1995-08-03 1998-11-10 Bayer Aktiengesellschaft Tertiary amines having carbonate and urethane groups

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4412677A1 (en) * 1994-04-13 1995-10-19 Basf Ag Process for the production of polyurethane foams in the presence of aminoalkyl or aminophenyl imidazoles as a catalyst and the use of these catalysts for the production of polyisocyanate polyaddition products
EP2690118A1 (en) * 2012-07-27 2014-01-29 Basf Se Phosphorous compounds containing polyurethanes
JP6857076B2 (en) * 2017-04-26 2021-04-14 アイカ工業株式会社 Curing Accelerator Composition and Curing Acceleration Method for Water-Hard Polymer Cement Composition for Floor Coating

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705672A (en) * 1994-08-09 1998-01-06 Bayer Aktiengesellschaft Tertiary amines having carbonate and urethane groups
US5834579A (en) * 1995-08-03 1998-11-10 Bayer Aktiengesellschaft Tertiary amines having carbonate and urethane groups

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