CA1260012A - Polyamines and a process for their preparation - Google Patents

Abstract

POLYAMINES AND A PROCESS FOR THEIR PREPARATION

ABSTRACT OF THE DISCLOSURE
Polyamines containing primary amino groups are made by hydrolyzing an isocyanate with water in the presence of a solvent which is a carboxylic acid amide. The solvent must be used in a quantity of at least 10%, by weight solvent based on 100% by weight of isocyanate.
The weight ratio pf solvent to water must be from 3 to 200. A homogeneous phase is maintained during the hydrolysis which is carried out at temperatures of from 20 to 210°C. A not incorporable basic and/or metal catalyst may optionally be employed. The polyamines produced by this process are particularly useful for the production of polyurethanes.

Description

~;~6~0~
Mo-2839 LeA 24,119 POLYAMINES AND A_ ROCESS FOR THEIR PREPARATION
Background of the Invention _ This invention relates to a simplified one-step process for the preparation of polyamines containing primary amino groups.
It is known that aromatic isocyanates can be converted into primary aromatic amines by acid hydrolysis.
However, the amine resulting from this hydrolysis reacts with as yet unreacted isocyanate to form the corresponding urea thereby decreasing the amount of product amine. This secondary reaction cannot be suppressed even by using an excess of stron~ mineral acids. A recent example of this procedure is described in JP-P 55 007 829.
It is also known that isocyanates can be converted into amines by an acid or alkaline catalyzed reaction, as disclosed9 for example, in N.V. Sidgwick, The Organic Chemistry of Nitrogen, Clarendon Press, Oxford, page 236 (1966~ and in J. March, Ad~anced Organic Chemistry; Reactions 9 Mechanisms and Structure, McGraw-Hill Book Co., New York, page 658 (1968).
Sidgwick indicates that isocyanate groups can be hydrolyzed under alkaline conditions but no details of such a process are disclosed. J. March also speaks in general terms of the fact that the hydrolysis of isocyanates and isothiocyanates to amines can be catalyzed with acids and bases. The occurrence of isocyanates as intermediate products is also known to those skilled in the art. For example, isocyanates are obtained in the course o the Curtius or Lossen degradation of acid azides and hydroxamic acids and are decomposed with aqueous acids to form amine salts. A

Mo-2839 procedure of this kind has been described, for example, in Organic Synthesis, Coll. Vol. IV, 819 (1963) in which the preparation of putrescine hydrochloride is used as an example.
E. Mohr, J. prakt. Chem., 71, 133 (1905) was one of the first to observe that phenyl isocyanate is more rapidly attacked by dilute sodium hydroxide solution than by water at low temperatures. C. Naegeli et al., Helv. Chim. Acta, 21, 1100 (1938) report that 10 when phenyl isocyanates substituted with electron acceptors (such as nitro groups, halogen atoms or acyl groups) are hydrolyzed in moist ether or in acetone containing 1~ of water in the absence of acids or bases, the corresponding monoamines are obtained in the course 15 of a reaction lasting from several minutes to up to one hour. From 2,4-dinitrophenyl isocyanate the amine can even be obtained in hot water without solvent in a virtually 100% yield and without side reactions leading to urea formation.
In a process for the preparation of specified primary aromatic amines containing polyalkylene glycol ether segments described in DE-B 1,270,046, products obtained by the reaction of aromatic di- or triisocyanates with polyalkylene glycol ethers and/or 25 polyalkylene glycol thioethers (preferably those with molecular weights of from 400 to 4000) are reacted with secondary or tertiary carbinols and then subjected (optionally in the presence of acid catalysts) ~o thermal decomposition at high temperatures in an lnert 30 solvent. One disadvantage of this process, apart from the high decomposition temperature, is that combustible, readily volatile alkenes which are explosive when mixed with air are formed in the course of thermal decomposition so that appropriate safety measures are 35 r~quired.
Mo-2839 ~ ~ 6 ~

DE-B 1,694,152 (US 3,525,871) relates to ~he preparation of prepolymers containing at least two amino end groups by the reaction of hydrazine, aminophenylethylamine or other diamines with an 5 isocyanate prepolymer obtained from a polyether polyol and polyisocyanate (NCO/NH ratio = 1:1.5 to 1:5). Anv unreacted amine must be carefully removed in a subseuuent step of the process because the amine is a powerful catalyst in the reaction with polyisocyanates 10 and shortens processing ~imes, and may even act as a reaction component. A similar process is described in U.S. Patent 3,931,116.
Another method for synthesizing polyamines containing urethane groups is described in FR-P
15 1,415,317. In this process, isocyanate prepolymers containing urethane groups are reacted with formic acid to yield N-formyl derivatives which are saponified to aromatic amines having amino end groups. The reaction of isocyanate prepolymers with sulphamic acid according 20 to DE-P 1,155,907 also leads to compounds containing amino end groups. Relatively high molecular weight prepolymers containing aliphatic secondary and primary amino groups may be obtained according to DE-B 1,215,373 by the reaction of relati~ely high molecular weight 25 hydroxyl compounds with ammonia in ~he presence of catalysts under pressure at elevated temperatures.
According to U.S. 3,044,989 high molecular weight amines may be obtained by the reaction of relatively high molecular weight polyhydroxyl compounds with 30 acrylonitrile followed by catalytic hydrogenation.
Relatively high molecular weight compounds containing amino end groups and urethane end groups may also be obtained according to DE-A 2,546,536 and U.S. 3,865,791 by the reaction of isocyanate prepolymers with enamines, Mo-2839 - ~Z60~

~, aldimines or ketimines containing hydroxyl groups, followed by hydrolysis. Another method for the synthesis of aromatic polyamines containing urethane and ether groups is opening of the ring which occurs in the 5 reaction of isatoic acid anhydride with diols.
Polyamines of this kind have been described, for example, in U.S. 4,180,644 and DE A 2,019,432,

2,619,840, 2,648,774 and 2,648,825. Aromatic ester amines obtained by such methods have the disadvantage of 10 being insufficiently reactive for many purposes.
Low reactivity is also found in compounds containing amino and ester groups obtained according to U.S. 4,504,648 by the reaction of polyether polyols wi~h p-aminobenzoic acid ethyl ester and according to EP
15 32,547 by the reaction of polyols with nitrobenzoic acid chloride followed by reaction of the nitro groups to amino groups.
The reaction of nitroaryl isocyanates with polyols followed by reduction of the nitro group to 20 aromatic amine groups is also known (~.S. 2,888,439).
The main disadvantage of ~his process is the high cost of the reduction stage of the process.
It is also known that certain heteroaromatic isocyanic acid esters can be converted into 25 heteroaro~atic amines by basic hydrolysis. The conditions for hydrolysis disclosed by H. John in J. Prakt. Chemie 1_ , 314 et seq and 332 et seq (1931) for two quite specific heteroaromatic monoisocyanic acid esters are, however, both comple~ely unsuitable for the 30 conversion of polyisocyanate compounds into aliphatic and/or aromatic amines and dangerousO
Applicants' own processes disclosed in DE-A
2,948,419 and 3,039,600 are multistage processes for the preparation of polyamines by alkaline hydrolysis of Mo-2839 ~ 2 ~ 0~

isocyanate prepolymers using an excess of base (alkali me~al hydroxides) at low temperatures to form carbamates, acidification with equivalent or excess quantities of mineral acids or acid ion exchanger resins 5 accompanied by carbamate decomposition, and optionally neutralization of excess quantities of acid by means of bases, followed by isolation of the polyamines.
~ E-OS 3,131,252 discloses a process in which the carbamates obtained in a first stage by hydrolysis 10 with alkali metal hydroxides are decomposed by subsequent heat treatment to yield the polyamines.
One-step processes for the production of polyamines are described in DE-OS 3,223,400 (EP-97,299), DE-OS 3,223,398 (EP-97,29~) and DE-OS 3,223,397 15 (EP-97,290). In these one-step hydrolysis processes various solvent-catalyst combinations are employed.
"Ether solvents" are used together with tertiary amines as catalysts in DE-OS 3,223,400. Polar solvents such as dimethylformamide are used together with tertiary amines 20 or relatively large quantities of alkali metal hydroxides, alkali metal silicates or alkali metal cyanides as catalysts in specified amounts in DE-OS

3,223,398. Carbonates or carboxylates are used in specified amounts in polar solvents such as DMF in DE-OS
25 3,223,397 All of these processes for the preparation of polyamines are elaborate and expensive. Even in the last men~ioned, more simplified methods for the conversion of polyisocyanates to polyamines, further ~0 simplification would be desirable for obtaining polyamines even more economically with even better conversion rates of NCO/NH2 (i.e. higher NH2 numbers) by an even smoother reaction. A satisfactory process should have the following advanta~es compared with 35 conventional processes:
Mo-283~

~ 6~ 0 (1) no filtration required;
(2) no separation of a tertiary amine catalyst by distillation required;
(3) drastic reduction in the quantity of catalyst (both tertiary amines (according to DE-OS 3,223,398) and the inorganic, alkaline compounds such as KOH) required so that the catalyst could be left in the polyamine; and

(4) quantitative conversion of NCO into NH2 groups (high NCO/NH conversion rates, i.e.
high amine numbers close to the theoretical value);

(5) no removal of by-products required; and

(6) simple working up of polyamines and auxiliary substances.
Summary of the Inven~ion It has now been found, completely unexpectedly, that each of the above-listed advantages is obtained by 20 the one-stage hydrolysis of polyisocyanates to polyamines of the present invention.
This hydrolysis is carried out with a particular ratio of water to NCO and a particular ratio by weight of solvent to water using water-soluble 25 carboxylic acid amides as solvents and optionally, very small quantities of catalyst (no catalyst is less ~re~erred) under conditions such ~hat a homogeneous solution is maintained.
Such optimized conditions make it possible to use lower temperatures for hydrolysis.
In the process of the present invention, water-soluble solvents based on carboxylic acid amides, preferably carboxylic acid dialkylamides or lactams, are Mo~2839 ~ ~ 60 ~1~

employed in order that a substantially homogeneous solution of the reactants (i.e. isocyanate compounds and water) and catalyst may be obtained. A particularly suitable solvent is dimethylformamide and in some cases 5 also dimethylacetamide.
Detailed Description of the Inventio It is known from DE-AS 1,235,499 that solutions of isocyanate prepolymers in dimethylformamide may be converted into highly viscous solutions suitable for 10 spinning elasthane fibers or for coatings by reacting them with approximately equivalent quantities of water (80 to 120% of the theoretical amount, where 100%
corresponds to 1/2 mol of water per NCO, i.e. the water reacts with two hydroxyl equivalents). This reaction is 15 accompanied by chain lengthening via urea groups. The quite different reaction of isocyanate compounds with excess quantities of water to form low molecular weight amines in high yields was unexpected. It was particularly surprising that this reaction could be 20 carried out in the presence of the catalysts according to the invention which also accelerate the reaction of isocyanates with the reaction products formed.
It is also known that isocyanates react with dialkyl-formamides to form formamidines (H. Ulrich 25 et al, J.Org. Chem., 33, 3928-3930 (1968) and the literature quoted therein). This reaction does not interfere with the smooth hydrolysis to polyamines by the process of the present invention.
One considerable advantage of the process of 30 the present invention is the very low quantities of catalyst used. Consequently, there is no need to filter off catalyst or reaction products of the catal~st with the CO2 liberated in the reaction (e.g. ~OH giving rise to KHCO3 and K2CO3).
Mo 2839 ~ 2 ~0 ~

Since the catalysts useful in the present invention are readily soluble in the reaction medium, the problems which occur when using rapidly sedimenting alkali metal carbonates or bicarbonates (as in the case 5 of DE-OS 3,223,297) do not arise in the practice of the present invention. Since the catalysts -remain in solution or are fully miscible, they need not be filtered off. The catalysts remaining in the amine product do not normally cause any difficulties due to 10 the small quantities in which they are preferably used.
Since no salts or residues of catalyst need be removed after the product has been worked up, the process of the present invention is particularly suitable for the preparation of highly viscous or solid compounds 15 containing amino groups from which it is very difficult to remove undissolved residues of salt or catalyst material.
The catalysts of the present invention are also particularly suitable for the hydrolysis of isocyanate 20 prepoly~ers based on polyes~ers because under the mild reaction conditions employed during the hydrolysis reaction the ester groups are not split off to any significant extent.
Compared to alkaline hydrolysis processes for 2~ obtaining aminopolyesters from an isocyanate, the process of the presen~ invention is a significant improvement.
The catalysts of the present invention are inexpensive and commercially readily available. They 30 may also be separated from the product and used again or, in the preferred embodiment, they may be left in the product. If it is necessary to produce a product which is completely free from catalyst, the proce~s may even be carried out without a hot ;nccrporable alkaline and/or metal catalyst Mo-2839 600~

if the isocyanate, water and solvent are used in quantities such that the ratios required in the present invention (especially if the optimum proportion of solvent to water, the optimum ratio of water to NCO and 5 comparatively high temperatures are used) are satisfied.
The optimum ratios can be determined by a preliminary experiment. Comparatively high temperatures are used, preferably in the range of from above 80 to 100C.
Although the conversion rates obtained from such a 10 catalyst-free process are only about 2/3 the rate obtained with catalyst, they are still very high (advantageous) compared with those obtained by the catalyst-free method according to DE-OS 3,223,398. It is always preferable in the practice of the present 15 invention to work in the presence of catalysts even if only extremely small quantities of catalysts.
The present invention relates to a single stage process for the preparation of polyamines containing primary amino groups by the hydrolysis of compounds 20 containing isocyanate groups (preferably aromatic -,~x~anate gr~u~s) in media containing water, optionally with the addition of not incorporable alkaline and/or metal catalysts.
More specifically, the isocyanate groups of organic compounds containing isocyanate groups, preferably 25 aromatically bound isocyanate groups, based on isocyanate prepolymers or modified polyisocyanates having an isocyanate content of from 0.5 to 40 wt.
preferably 1.2 to 25 wt %~ in the c~se of isocyanate prepolymers and 5 to 20.5 wt.%, preferably 1.5 to 30 10 wt. % in the case of modified polyisocyanates, are hydrolyzed with 0.75 to 50 mol of water, preferably 1 to 35, more preferably 1.25 to 12 and most preferably 1.5 to 7.5 mol of water per equivalent oE isGcyanate.
This hydrolysis is carried out in the presence Mo-2839 ~1.2~)0~L~

of O to 1% ~y weight, preferably 0~00005 to 1% by weight of noL incorporable alkaline and/or metal catalysts, based on 100% by weight of isocyanate, preferably 0.0001 to 0.099% by weight of an alkaline catalyst, At least 10% by weight of carboxylic acid amides, preferably carboxylic acid dialkylamides or lactams, most prefer-ably dimethylformamide or dimethylacetamide, based on 100% by weight of isocyanate are used as solvent in the hydrolysis mixture. Optionally, 0.1 to 5% by weighL
based on 100% by weight of isocyanate compound, of a compound containing one or more than one hydroxyl andlor amino and/or thiol group attached to an aliphatic, cycloaliphatic or aromatic ~roup may be included. The solventlwater ratio by weight must be in the range of 3 to 200, preferably 5 to 150, more preferably 10 to 100 and most preferably >Z5 to 75. The hydrolysis mixture is maintained in a homogeneous reaction phase. The hydrolysis is carried out at a temperature of 20 to 210C, preferaoly 35 to 165C, more preferably ~0 ~o 150C and most preferably 80 to 130C.
A preferred embodiment of the invention is a process having the above features in which the iso-cyanate is hydrolyzed in the presence of 0.0001 to 0.099, preferably 0.002 to 0.08% by weig~t, based on 100% by weight of isocyanate of alkali me~al hydroxides, alkaline earth metal hydroxides, tetraalkylammonium hydroxides, alkali metal aluminates, alkali metal phen~lates, alkali metal thiophenolates, alkali metal mercaptides, alkali metal hydrogen sulphides, soluble alkali metal and alkaline earth metal sal~s of (iso)-(thio~cyanic acids and alkali metal ~-diketone enolates, andlor 0.0001 to 0.099, preferably 0.002 to 0.08% by weight, based on 100% by weight of isocyanate of carbonates or bicarbonates of alkali metals, and/or Mo-283~

6~0~

0.0001 to 0.099, preferably 0.0001 to 0.0099, more preferably 0.0002 t.o 0.008% by weight of alkali metal and alkaline earth metal salts of organic carboxylic acids including salts of formic acid as ~he alkaline catalyst. In an even more preferred embodiment the isocyanate is hydrolyzed with 1.25 to 12, preferably 1.5 to 7.5 mol of water per isocyanate equivalent using one of the above-listed not incorporable alkaline catalysts in the specified quantities while maintaining a carboxy-lic acid amide (preferably dimethylformamide/water) ratio by weight in the range of >10 to 150, preferably >25 to 75 at temperatures of 35 to 165C~ preferably 80 to 130C.
In another embodiment of the process of the present invention the isocyanate is hydrolyzed in the presence of 0.0001 to 0.99% by weigh~, preferably 0.001 to 0.099%
by weight of tertiary amino compounds (based on 100~/. by weight of isocyanate compound) using a water/NC0 ratio of from 1 to 7.5 mol of water per NC0 equivalent and a dialkyl carboxylic acid amide (preferably dimethylform-amidelwater) ratio by weight in the range of >10 to 150, preferably >25 to 75, at a temperature of 35 to 165C.
It is particularly preferred tha~ this process be carried out in the presence of 0.0001 to 0.099% by weight of ~ertiary amine compounds using a water/NC0 ratio of 1 to 24 mol of wa~er per NCO eq~ivalent and a dialkyl carboxylic acid amide/water (preferably dimethylformamide/water~ ratio by weight of >10 to 50 at a tempera~ure of 35 ~o 165C.
In another, less preferred embodiment of the invention, the isocyanate is hydroly2ed in the presence of 0.0001 Lo 0.0099, preferably 0.002 to 0.008~/. by weight of metal catalysts with preferably 1.5 to 7.5 mol of water per isocyanate equivalent while main~aining a Mo-2839 o~

- lZ -carboxyliL acid dialkylamide/water (preferably dime~hyl-formamide/water) ratio by weight of ~10 to S0, pre-ferably >Z5 to 50, at tempera~ures of 25 ~o 165C.
In the process of the present invention, the iso-cyanate may be hydrolyzed wiLhou~ a catalyst using a wa~er/isocyanate ratio of 1 to 25 mol of water per i50-cyanate equivalent and a carboxylic acid dialkylamide/
wa~er (preferably dimethylformamide/water) ratio by weight of >lC to 50, preferably >25 to 50, at Lempera-Lures of 35 Lo 165C, optionally under pressure.
The catalysts used in the inventive process have to be no~ incorporable, which mean that ~hey do no~ have any groups which can reac~ with NC0 groups.
In ~he various embodiments of ~he present inven-tion, ~he isocyanate compound is preferably an isocyan-a~e prepolymer having an isocyanate conten~ of from 1,5 to 10 wt.% or a modified polyisocyana~e, in particular a ure~hane-modified polyisocyanate having an isocyana~e content of from 1.5 to 20.5 wt.%, in particular 5 to 20.5 wt.%. Neu~ral salts may be included in thP hydroly-sis mixture. It is preferred to use 1 ~o 35 mols of wa~er, in par~icular l.Z5 to 12 mols of wa~er per equi-valen~ of isocyana~e.
The solven~ is pre~erably dim0~hyl~0rmamide used in quantities of 100 to 1000/. by weight, based on 100%
by weight of isocyanate compound.
Hydrolysis is preferably carried ouL a~ tempera-tures from 40 to 150~C, most preferably aL 80 ~o 130C
and preferably withou~ excess pressure. The solids con-cen~ra~ion of the reaction mixture subjec~ed ~o hydroly-sis is generally from 20 to 75 wt.%, preferably 25 to ~5 60 wt.%, mos~ preferahly 30 to 55 w~.%, Al~hough even lower sulids concentrations may be employed, this is less advantageous for practical reasons ~e.~. solven~
recovery).
Mo-2839 ~L2~QO~l~

The isocyanate hydrolyzed is preferably an isccyanate prepolymer conta~ing frornO.5 to 40 wt.%, preferably 1.2 to 25 wt.%, more preferably from 1.5 to 10 wt.% of aromatically bound isocyanate groups and based on relatively high 5 molecular weight, difunctional or higher functional polyether, polyester, polycaprolactone and/or polycarbonate polyols and diisocyanates or polyisocyanates modified with low molecular weight diols or polyols (molecular weight up to 399) and containing 10 1.5 to 20.5 wt. ~, preferably 5 to 20.5 wt. ~ of NCO.
The invention also relates to the polyamines obtained by the process according to the invention, particularly those containing 0.46 to 9.52 wt. % of primary, preferably aromatically bound NH2 groupsO
The present invention further relates to the use of the polyamines obtained by the process of the present invention for the preparation of optionally cellular polyurethane(urea)s by reaction with a polyisocyanate and optionally other compounds containin~
20 isocyanate reactive groups, optionally in the presence of known auxiliary agents and additives and/or solvents.
According to the invention, a compound containing 1, 2 or more hydroxyl and/or amino and/or thiol groups bound to aliphatic, cycloaliphatic or 25 aromatic groups may be added in minor quantities (i.e.
0.1 to 5 % for every 100 % of isocyanates). The addition of these compounds containin~ "H-active groups"
is advantageous because polyamines virtually free from monomeric polyamines may be obtained from isocyanate 30 compounds containing low molecular weight polyisocyanates (e.g. isocyanate semiprepolymers) without treatment of the isocyanate compounds by thin layer evaporation or s:imilar processes. Modified polyamines which contain various segments linked through Mo-2839 2 ~

- ~4 ~
urethane groups, thiourethane groups or urea groups can thus be obtained quite simply and without an additional reaction step.
A trifunctional or higher functional polyamine 5 can therefore be obtained from a difunctional isocyanate compound by using a trifunctional or higher functional compound containing "H active groups" in the isocyanate hydrolysis process.
The isocyanate compounds used in the process of 10 the present invention contain two or more aromatic, heterocyclic and/or aliphatic (preferably aromatic) isocyanate groups. These isocyanates include modified polyisocyana~es of the type obtained by partial conversion of isocyanate groups into urethane, urea, 15 biuret, uretdione, isocyanurate and/or uretoneimine groups and isocyanate prepolymers obtained by the reaction of polyvalent compounds in the molecular weight range of 62 to 129000 (prPferably 400 to 6,000) containing isocyanate reactive H groups with (excess) 20 quantities of aromatic polyisocyanates and (less preferred) semi-prepolymers made up of isocyanate prepolymers and additional low molecular weight polyisocyanates.
Examples of modified aromatic polyisocyanates 25 useful in the present invention include:
polyisocyanates containing urethane groups (obtained by modification with low molecular weight polyols); poly-isocyanates con~aining urea groups (e.g. by modi~ication with water, DE-P 1,230,778); polyisocyanates containing 30 biuret groups (U.S. 3,124,605 and 3,201,372, GB-P
889,050); polyisocyanates containing isocyanurate groups (DE-PS 1,022,789 and 1,222,067) and dimeric and oligomeric polyisocyanates containing uretdione or uretoneimine groups. These are known compounds or are Mo-2839 2 ~

obtainable by known processes. Several such uretdione polyisocyanates are mentioned in Analytical Chemistry of the Polyurethanes, Volume 16/III, High-Polymers-Series (Wiley 1969).
Such modified polyisocyanates containing urethane and/or urea and/or biuret and/or uretdione and/or isocyanurate and/or uretoneimine groups suitable for the process of the present invention generally have an isocyanate content of from 1.5 to 40 wt. %, 10 preferably from 10 to 25 wt. %. Polyisocyanates containing urethane groups ~by modification with low molecular weight (molecular weight 62 to 399) diols and/or polyols) and having isocyanate contents of from >1.5 ~o 20.5 w~. %, preferably 5 to 20.5 wt. ~ are 15 particularly preferred.
The most important isocyanate compounds useful in the process according to the invention are isocyanate prepolymers of the kind obtained in a known manner by the reaction of low molecular weight and/or relatively 20 high molecular weight compounds containing hydroxyl and/or amino and/or thiol groups as reactive groups (molecular weight 62 to about 12~000) with an excess of polyisocyanate.
The polyisocyanates used for the preparation of 25 the compounds containîng free isocyanate groups may in principle be any aromatic, aliphatic or heterocyclic di-or polyisocyanates of the kind described, for example, by W. Siefken in Justus Liebigs Annalen der Che~ie, 562, pages 75-136 (1949) and ~hose known in the art which are 30 men~ioned on pages 12 1:0 23 of DE-OS 3,223,397. Low molecular weight and/or relatively high molecular weight compounds having molecular weights of 32 and 60-12,000 containing hydroxyl and/or amino and/or thiol groups as reactive groups suitable for the preparation of Mo-2B39 ~o~

prepolymers and modified isocyanates are also described in these disclosures.
Isocyanate prepolymers which have been obtained from relatively high molecular weight polyols (molecular 5 weight of 400 to 12,000), preferably polyether polyols, optionally together with chain lengthening agents o the type described above (molecular weight 62 to 399) by a reaction with aromatic diisocyanates in an equivalent ratio of 1:1.5 to 1:2.8 (in particular about 1:1.5 to 10 1:2) are preferred for the process according to the invention.
The isocyanate content of the isocyanate prepolymers used in the process amounts to 0.5 to 30 wt. Z, preferably 1.2 to 25 wt~ %, in particular 1.5 to 15 10 wt. % with functionalities of 2 to 8, preferably 2 to 4 and most preferably 2 to 3.
So-called "semiprepolymers", i.e. mixtures of isocyanate prepolymers or modified polyisocyanates with other free polyisocyanates which may ha~e an even higher 20 isocyanate content, e.g. up to 40 wt. %, may also be used in the process of the present invention. For practical and economic reasons, however, the use of these semiprepolymers is in most cases not advisable.
The monomeric amine contents formed from the monomeric 25 polyisocyanate components are liable to interfere with numerous applications.
In the form of their modified isocyanates (in most cases free from urethane groups~ or in the form of their "semiprepolymers" or isocyanate prepolymers 30 (containing urethane groups), the compounds containing free isocyanate groups have a total isocyanate group content within the range of 0.5 to 40 w~. X, preferably 1.2 to 25 wt. % and most preferably 1.5 to lO wt. ~.

Mo-2839 Water i9 used as a reaction component, preferably in liquid form. In order to achieve substantial conversion of the isocyanate groups into NH2 groups, it is necessary to use at least one 5 mol of water per equi~7alent of ~co.

If substantially less than 1 mol (in particular <0.75 mol) of water is used, then prelengthening with 10 urea formation preferentially takes place. On the other hand, it has surprisingly been found that the use of a very large excess of water also leads to relatively high proportions of unwanted prelengthened products. This also occurs if the reaction mixture is monophasic. It 15 has been found tha~ the optimum quantity of water depends not only on the quantity of isocyanate groups to be converted but also on the quantity of solvent used.
This means that the quantity of water used for one equivalent of isocyanate is ~ 0.75 mol of 20 water, preferably ~0.75 to 50 mol of water, more preferably 1 to 35 mol of water, most preferably 1,25 to 12 mol of water. If, for example, a bifunctional isocyanate prepolymer with T 100 ~= 2,4-tolylene diisocyanate) having an isocyanate content of 3.6~ is 25 used, then the equivalent weight o isocyanate groups is about 1167. This means that 313.5 g of water, preferably 13.5-900 g, more preferably 18-630 g, and most preferably 22.5-216 g of water are used for about 1167 g of this prepolyrner. The lower limit of water in 30 this process is 0.75 mol of water, in most cases l mol of water and can be combined with the upper limits in any manner desired.
According to the invention, howe~er, the water/NCO ratio claimed must be used in conjunction with Mo-2839 6~

certain proportions by wei~ht of solvent to water.
These proportions by weight range from 3:1 to 200:1 but are preferably in the region of 5:1 to 150:1, especially from ~10:1 to 100:1, the optimum range being in most 5 cases from ~25:1 to 75:1.
This means that, for example, based on 1000 g of solvent (preferably dimethylformamide), the quantity of water used is in the range of 5 to 333 g.
It has been found ~hat if the other conditions 10 according to the invention are also observed, in particular if a relatively high proportion of solvent is used in the solvent/wa~er mixture (in particular a dimethylformamide/water mixture), a particularly advantageous NCO/NH2 conversion rate is obtained and 15 that the quantities of catalyst used may be minimal.
If the absolute quan~ity of water required is used and the more advantageous solvent/water ra~io is observed, the quantity of solvent is such that more than 10 % by weiaht, preferably ~ 1~0 % and most preferably us to 1000 ~ of solvents are used for 1~0 ~ by weight isocyanate component. It has been found that the minimum quantity of solvent required for achieving complete NCO/NH2 conversions depends upon the reaction temperature. The higher the reaction temperature, the 25 lower may be the quantity of solvent used. The quanti~y of water required (based on NCO~ is largely unaffected by ~hese factors.
If necessary, experiments may be carried out to determine the optimum ratios of NCO equivalents, water 30 and solvent for a particular isocyanate component within the general framework indica~ed.
Alkaline and/or metal catalysts havin~ no NCO reactive groups may ~e used in the present invention. mese compounds are capable of raismg the NH number of the amines in the product to a Mo-2839 2 ~

level above that obtainable without the use of catalysts.
The catalysts used may be solid or liquid but must be sufficiently soluble, preferably completely 5 sGluble in the reaction mlxture. Based on 100 ~ by weight of isocyanate component, the catalyst is generally used in a ~uantity of 0.00005-1 % by ~eight. Different types of catalyst have different preferred ranges of quantities.
The quantity of catalyst required is also dependent on 10 the solvent/water ratio. The catalyst requirement is least when the optimum solvent/water ratio is employed, but even then a certain surprisingly small amount of catalyst, is required for producing the highest possible NCO/NH2 conversion rates. Even if the water/solvent 15 ratio is not quite optimal, good results can still be obtained by increasing the quantity of catalyst. The quantity of catalyst required for complete conversion of NCO groups into NH2 groups also depends upon the reaction temperature. It is found that this quantity 20 should be higher at lower temperatures, e.~. l.5C, than at a higher reaction temperature, e.g. at 100C. If the amine yield is incomplete when a given quantity of catalyst is used, the yield may be increased by increasing the reaction temperature.
Basic inorganic and organic salts and in particular hydroxides (particularly preferred group) may be used as catalysts. These include salts of strong organic or inorganic bases with weak inorganic or organic acids which give an alkaline reaction in water.
30 Specific examples of such ca~alysts include: hydroxides of alkali metals and alkaline earth metals and tetraalkylammonium hydroxides (in particular NaOH and KOH) and soluble aluminates (such as sodium aluminate);
carbonates of alkali metals, in particular sodium Mo-2839 -```` ~1.26~

carbonate and potash; bicarbonates of alkali metals, in particular sodium and potassium bicarbonate; alkali metal and alkaline earth metals ~alts of mono and polycarboxylic acids free from isocyanate reactive 5 groups, including the salts of formic acid (pre~erably salts of monocarboxylic acids containing up to 18 carbon atoms) such as sodium formate, sodium acetate, potassium octoate and potassium stearate; alkali metal salts o~
phenols and thiophenols optionally substituted with 10 groups which are unreactive with NCO; soluble alkali metal and alkaline earth metal salts of weak acids such as cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, silicic acid, phosphorus-III- to -V-acids, hydrocyanic acid, hydrazoic acid, etc.; alkali 15 metal mercaptides and sulphides and hydrogen(poly)-sulphides; and ~-diketone compounds such as sodium, potassium or magnesium acetylacetonates and acetoacetates. Tertiary amines may also be used as catalysts but they are less pre~erred. The tertiary 20 amines used preferably have an aliphatic or cycloaliphatic structure, and mixtures of various tertiary amines may be used. Examples include compounds which are not completely water-soluble, e.g. the trialkylamines such as trimethylamine, triethylamine, 25 tripropylamine, triisopropylamine, dimethyl-n-propyl-amine, tri-n-butylamine, tri-isobutyl-amine, tri-iso-pentylamine, dimethylbutylamine, triamylamine, trioctyl-hexylamine, dodecyldimethylamine, dimethylcyclohexyl-amine, dibutylcyclohexylamine, dicyclohexylethyLamine, 30 tetramethyl-1,3-butane-diamine; and tertiary amines containing an araliphatic group, such as dimethylbenzylamine, diethylbenzylamine and -methylbenzyldimethylamine. Trialkylamines having a total of 6 to 15 carbon atoms in all the alkyl groups 35 (e.g. triethyl- to triamyl-amine and dimethylcyclohexyl-Mo-2839 amine) are preerred.
Suitable tertiary amines apart from the trialkylamines also include those which have an additional tertiary amino group or an ether group, in 5 particular in the ~-posi~ion to the tertiary group.
Examples include dialkylaminoalkyl ethers and bis-dialkylaminoalkyl ethers (US 3,330,782, DE-B
1~030,558), e.g. dimethyl-(2-ethoxyethyl)-amine, diethyl-~2-methoxypropyl)-amine, bis-(2-dimethyl-lO aminoethyl)-ether, bis-(2-diethylaminoethyl)-ether, bis-(2-diethylaminoisopropyl)-ether, 1-ethoxy-2-dimethyl-aminoethoxyethane, N-methyl-morpholine, N-ethyl-morpholine and N-butyl morpholine; also, permethylated polyalkylene diamines such as 15 tetramethylethylenediamine, tetramethyl-1,2-propylenediamine, pentamethyldiethylenetriamine, hexamethyl-triethylenetriamine and higher permethylated homologs (DE-A 2,624,527 and 2,624,528); also, diethyl-aminoethyl-piperidine, 1,4-diaza-(2 9 2,2)-bicyclooctane, 20 N,N'-dimethylpiperazine, N,N'-diethylpiperazine, N-methyl-N'~dimethylaminoethylpiperazine, N,N'-bis-dimethylaminoethylpiperazine, N!N'-bis-dimethylaminopropylpiperazine and other bis-dialkyl-aminoalkylpiperazines (mentioned e.g., in DE-A
25 2,636,787).
Preferred representatives of this group are the water-soluble compounds such as tetramethylenediamine, permethylated diethylenetriamine, N-methyl-morpholine, bis-2-dimethylaminoethylether and N-methylpiperidine.
Acylated tertiary amine derivatives such as l-dimethylamino-3-formylaminopropane, N-(2-dimethyl-aminoethyl)-propionamide), N-(2-diethylamino-ethyl)-benzamide and other tertiary amines containing amide groups (preferably formamide groups) according to 35 DE-A 2,523,633 and 2,732,292 may also be used.
Mo-2839 6~

Tertiary amines of the pyridine series and ~ertiary amines containing at least one aromatic group attached to ~he nitrogen atom are also effective, e.g.
dimethylaniline.
If the tertiary amines are not soluble in water, their boiling point should be below 250C, preferably below 200C.
Metal catalysts may also be used in the present invention but they are not preferred.
The polyvalent metal compounds described in the literature as catalysts for isocyanate chemistry may be used in the process according to the in~ention. These are preferably compounds of tin, zinc or lead, such as dibutyl tin dilaurate, tin octoate, zinc acetyl 15 acetonate and lead octoate. These are on the whole less preferred.
The solvent component may be an aromatic, aliphatic or cycloaliphatic carboxylic acid amide which is at least partly, preferably completely 20 water-miscible/water-soluble and has 1 10 carbon atoms in the acid moiety, e,g. dimethylformamide (DMF), formamide, diethylformamide, dime~hylacetamide, dimethylpropionic acid amide, benzoic acid dimethylamide and N-methylpyrrolidone. Carboxylic acid dialkylamides 25 are preferred, in particular dimethylformamide.
The solvent ~ay contain up to 75 wt. % of other aprotic dipolar solvents such as: water-soluble, tetraalkylated aliphatic ureas having 4 to 12 carbon atoms, e.g. tetramethylurea or tetraethylurea;
30 water-soluble, aliphatic or cycloaliphatic sulphones or sulphoxides having 2 ~o 10 carbon atoms, e.g.
tetramethylsulphone or dimethylsulphoxide; and water-soluble aliphatic or cycloaliphatic phosphoric acid amides, e.g. hexamethylphosphoric acid triamide.
Mo-2839 O~L~

- ~3 -These op~ional solvents may be mixed in any proportions. Among these optional solvents, it is preferred to use those which uncler normal pressure boil at 56 to 250C, preferably 64 to 165C because this 5 simplifies the working up process.
Solvents which are not completely miscible with water, such as propionitrile, methyl ethyl ketone, ethyl acetate or hydrocarbons may be used in minor quantities but the addition of such solvents is not preferred. It lO is preferred to use DMF as the only solvent.
The following limiting conditions of the process apply to the quantities (in particular the upper limits) of solvents to be used:
1. ~10, preferably 100 to 1000 % by weight of 15 solvent should Le used per 100 ~ ~y weight of isocyanate compound n the reaction mixture for hydrolysis.
2. Sufficient water and optionally solvent should be used to produce a substantially homogeneous (at the most slightly cloudy) or preferably completely 20 homogeneous, clear solution with the isocyanate compound at the reaction temperatures. It is particularly preferred to use sufficient water to form a monophasic mixture at all temperatures of the process but always within the ratio of solvent (~MF):water and of water:
25 NCO component mentioned above.
The catalytically active compounds are generally added to the solvents and water. They may in some cases be added to the co~pound containing isocyanate groups but this is not preferred.
To hydrolyze the NCO compounds to polyamines with a sufficiently high amine number (high conversion rate), it is advantageous to maintain a concentration of NCO compound of< 75, preferably< 55 wt % in the reaction mixture.
Mo-2839 v~

The degree of dilution is limited by the economics of the working up process and would in practice be in the region of a 3% solution.
However, it is necessary to use at least 5 sufficient solvent wi~hin the above-mentioned ratios of the quantities of water, solvent and isocyanate to ensure that the reaction mixture remains substantially homogeneous, preferably completely homogeneous.
According to a less preferred embodiment of the 10 process, compounds containing "H-active groups" and having two or more hydroxyl, amino and/or thiol groups may be added to the reaction mixture Such compounds have already been mentioned as starting components for the isocyanate compounds used in the process according 15 to the invention and are most preferably difunctional to optionally tetrafunctional compounds in the molecular weight range of 62 to 2000. Compounds of this type containing at least two primary hydroxyl groups, e.g.
ethanediol, butanediol, propanediol, polyethylene 20 glycols, trimethylol-propane or the like are preferred.
~ompounds containing different "H-active groups" may, of course, also be used, e.g. aminoalkanols.
Compounds containing only one H-active group ~ay be used as monofunctional chain breaking agents.
25 Methanol, e~hanol, cyclohexanol, cyclohexylamine, aniline or asymmetric dimethylhydrazine are examples of such agents.
The prelengthening reaction, i.e. the reaction of isocyanate with already formed amine to undergo chain 30 linking and form ureas, may occur as a side reaction of the process according to the invention. This side reaction can to a large extent be suppressed by carrying out the process in dilute solution, using catalysts and solvents in accordance with the invention and by Mo-2839 ~Z6~0~

maintaining relatively high reaction temperatures, e.g.
80 to 130C. Although it is preferred to keep these side reactions down as much as possible, it may be permissible on economic grounds to accept a certain 5 degree of prelengthening.
If the process parameters are sufficiently accurately observed, however, the method according to the invention enables the isocyanate groups to be virtually completely converted into NH2 groups.
The reaction according to the invention is preferably carried out in a homogeneous phase. Slight cloudiness of the reaction mixture may temporarily occur if the starting materials ~re incompletely dissolved due to the presence of slightly too much water or too much 15 isocyanate compound.
The presence of a multiphase mixture due to ~he addition of an excessive quantity of water and precipitation of the isocyanate prepolymer, however, results in unsatisfactory products. The optimum 20 proportions in which the starting components should be mixed in order that homogeneous mixtures may be obtained within the required proportions may be determined by a few preliminary tests.
As already men~ioned above, the reaction may be 25 carried out at temperatures from 20 to 210C. It is preferred, however, to employ temperatures in thè range of 35 to 165C, in particular from 80 to 130~C because this results in the best volume/time yields combined with high solubility and, surprisingly, the least amount 30 of urea lengthening. In special circumstances, it may be necessary to carry out the reaction under pressure in order that su~ficiently high temperatures may be obtained.

~o-2839 The onset of the reaction ~lay be recognized by the almost spontaneous liberation of CO2, which is observed to take place even at low temperatures, e.g.
10C. It is however much more advantageous for the 5 purpose of the invention to employ higher temperatures in order to suppress urea formation. It is important to ensuxe thorough and rapid mixing o the reactants to form a homogeneous solution. This may be achieved mainly by using solvents. The reduction in viscosity 10 obtained when elevated reaction temperatures are employed operates in the same direction. The reaction may be carried out batchwise or continuously.
The information disclosed in DE-OS 3,223,397, page 32, line 20 to page 35, line 10 applies both to the 15 continuous and the batchwise embodiments.
Working up of the end product may also be carried out continuously or batchwise. The reaction mixture is normally worked up by dis~illation, extraction or phase separation or a combination of these 20 methods. ~xtraction processes, optionally after dilution with water, may be carried out with solvents which are insoluble in water, such as methylene chloride or chlorobenzene, but these methods are not pre~erred.
Phase separation of the reaction mixture by 25 cooling occurs in some cases if hydrolysis has been carried out at relative~y high temperatures and in the presence of a relatively large quantity of water at the limit of solubility. Phase separation may be improved or indeed achieved by the addition of water. The 30 aqueous phase optionally containing solvent and in most cases also catalyst is separated from the polyamine phase. The aqueous phase is then in most cases ready for reuse.

Mo-2839 '~L26 The polyamine phase may contain residues of catalyst, some water and possibly solvent in addition to the polyamin~. These are removed as completely as possible by distillation, if necessary with application 5 of a vacuum or by thin layer distillation.
If the compound containing isocyanate groups still contains free (i.e. monomeric) isocyanate due to the method employed for its preparation, the monomeric amine formed from this monomeric isocyanate may in some 10 cases accumulate in signif~cant quantities in the water/solvent phase if the product is worked up by phase separation. The polyamine obtained by this simple method of working up is then virtually free from monomers. It may however be advisable to free the 15 solvent phase as much as possible from monomeric amine by working it up before it is used again.
The reaction mixture is preferably worked up without phase separation by distilling of the solvent or solventtwater mixture after termination of the 20 reaction (no more evolution of CO2 observed)O
Distillation is preferably carried out in a vacuum (e.g.
at l to 700 Torr) although an even higher vacuum (e.g.
0.001 to 1 Torr) may be applied or the removal of volatile residues. It has been found advantageous to 25 start wi~h a temperature in the region of about 60 -100C and subsequently to raise the temperature to 80 -lOnC. The solvent which is distilled off may be used again several times.
The polyamin~s obtained by the process of the 30 invention after the working up process are generally colorless to slightly colored, medium viscosity to high viscosity and in some cases relatively high melting products having an amino group content of from 0.19 to 15.23 wt. %. These polyamines may also contain groups Mo-2839 ~ ~6~V~

which were already present in the starting materials from which they were produced such as urethane and/or urea and/or uretdione and/or isocyanurate and/or biuret groups and/or uretoneimine groups and optionally ~ther 5 and/or acetal and/or carbonate and/or ester and/or thioether and/or dialkylsiloxane groups and/or the groups of polybutadienes. Additional linkages may be formed by side reactions. For example, urea groups may be formed from the ~lready saponified portions and 10 remaining isocyanate groups in the course of hydrolysis.
The quantity of primary aromatic amino groups present in the polyamines is at the most equal to the quantity of isocyanate groups present in the isocyanate compounds, i.e. about 0.19 to 15.23 wt. X of NH2 (when the 15 isocyanate content was 0~5 to 40 w~. %), preferably 0.46 to 9.52 wt. ~ NH2 (NCO content of 1.2 to 25 wt. Z) and most preferably 0.58 to 3.81 wt. % NH2 ~NC0 content of 1.5 to 10 wt. %).
In view of their low vapor pressure, the 20 polyamines of the present invention, which are preferably aromatic, are advantageously used as reactants for blocked or free polyisocyanates in the production of polyurethanes (polyurethane ureas), cellular or non-cellular polyurethane plastics or 25 polyurethane foams. These amines may also be combined with other, low molecular weight (molecular weight 32 to 399) and/or relatively high molecular weight (molecular weight 400 to about 12,000) compounds containing isocyanate reacti~e groups. Suitable starting 30 components for the production of polyurethanes by known processes are mentioned above in connec~ion with the preparation of the prepolymers as well as in DE-A
2,302,564, DE-A 2,432,764 (U.S. 3,903,679) and DE-A
2,639,0~3, 2,512,385, 2,513,815, 2,550,7g6, 2,550,797, Mo-2839 0~2 2550,833, 2,550,860 and 2,550,862. These disclosures also teach auxiliary agents and additives which may be used in the production of polyurethanes.
The present invention also relates to the use 5 of the polyamines of the present lnvention for ~he produc~ion of polyurethane(urea)s. They may be used, for example, for the production of elastomers~ coatings and threads and applied as solvent-free melts, solutions, dispersions or mix~ures of reactive 10 components.
The polyamines of the present Lnvention may also be used as coupling components for diazo dyes, hardeners for epoxide and phenol resins and all other known reactions of amines such ~s the formation of 15 amides and imides, etc.
The Examples which follow serve to illustrate the present invention. Quantities given are to be understood as parts by weight or percentages by weight unless otherwise indicated.
EXAMPLES
Example 1 The isocyanate compound used in this F.xample was an isocyanate prepolymer having an isocyanate content of 3.65% which had been prepared by stirring a 25 mixture of polypropylene glycol having an OH number of 56 and tolylene-2,4-diisocyanate in an equivalent ratio of NCO:OH = 2:1 at 80C for 3 hours.
A mixture of 1750 ml of dimethylformamide (DMF) and 50 ml of water ~DMF/H2O = 33.2:1) was introduced 30 into the reaction vessel and heated to 90~C with stirring. 500 g of the above-described isocyanate prepolymer was added at this temperature in the course of 20 minutes. Stirring was csntinued for 5 minu~es after all the prepolymer had been added (evolution of Mo-2839 ~o~

C2 rapidly died down) and DMF and water were then distilled off by application of a vacuum (ini~ially 19.5 mbar and later 0.13 mbar at 80 to 100C).
NH number (HC104): 31.1 mg KOH/g xample 2 A mixture of 1750 ml of DMF, 50 ml of water and 1 g of sodium chloride was introduced into the reaction vessel. The experiment was then carried out with the same isocyanate prepolymer in the same amount and the product 10 worked up as described in Example 1. The NH number (HC104) was found to be 31.3 mg KOH/g.
As Examples 1 and 2 illustrate, hydrolysis can be carried out relatively successfully with mixtures of DMF/H2O but the conversion rates are considerably lower 15 without catalyst than with the addition of (even small quantities of) catalyst (see Example 9)O
Example 3 (Comparative) A mixture of 1750 ml of DMF, 50 ml of water and 1 g of acetic acid was introduced into the reaction 20 ~ressel at 90C. The experiment was then carried out with the same isocyanate prepolymer in the same amount and the product worked up in the same way as in Example 1, a product havin~ an NH number (HC104) of only 28.4 mg KOH/g was obtained.
25 Examples 4 to 6 (Comparative) The isocyanate compound used in these Examples was an isocyanate prepolymer which was identical to the prepolymer from ExampLe 1 except that it had an isocyanate content of only 3.3%.
A mixture of 1.75 1 of acetone or 1.75 1 of dioxane or 1.75 1 of acetonitrile with 25 ml of water and 0.1 g of sodium hydro~ide was introduced into the reaction vessel with stirring at 90C or at the reflux temperature of acetone, respectively acetonitrile, and using 500 g of the above-described Mo-2839 ~;~60 prepolymer, the experiment was carried out and the product worked up as in Example 1.
NH numbers (HC104) When acetone was used :27.9 mg KOH/g 5 When dioxane was used :6.85 mg KOH/g when acetonitrile was used :26.9 mg KOH/g.
The conversion rates of NCO into NH2 were unsatisfactory (i.e. low NH numbers) in spite of the use of alkaline catalysts.
10 Example 7 (Comparative) A mixture of 17SO ml of methyl ethyl ketone, 50 g of water and 0.2 g of sodium formate was introduced into the reaction vessel at 90C. 500 g of the isocyanate prepolymer from Example 1 were added within 15 20 minutes. After the reaction mixture had been worked up as in Ex~mple 1, a product having an NH number (HC104) of 31.5 mg KOH/g was obtained. The OH number was distinctly lower than that obtained when solvents according to the invention are used.
20 Example 8 (Comparative) 1 1 of methyl ethyl ketone, 15.2 g of dimethylformamide, 30 ml of water and 1 g of sodium formate were introduced into the reac~ion vessel at the reflux temperature. 300 g of the isocyanate prepolymer 25 from Example 1 were added within 20 minutes. After the reaction mixture had been worked up as in Example 1, a product having an NH number (HC104) of 23.9 mg KOH/g was obtained.
Examples 9-22 These Examples demonstrate the catalytic properties of sodium hydroxide solution (NaOH).
Example 9 In this Example, a prepolymer having an isocyanate content of 3.9% prepared by stirring for 3 Mo-2839 ~260(~

hours a mixture of tolylene-2>4~diisocyanate and a polyester of adipic acid, ethylene glycol and butane-1,4-diol (molar ratio ethylene glycol:butanediol = 7:3) with an OH number of 56 at an NCO/OH ratio of 2:1 5 was used.
A mixture of 5.5 1 of DMF, 125 ml of water (DMF/water ratio = 41.7:1; 2.9 mol of water per isocyanate equivalent) and 0.25 g of NaOH (OoOl wt. %
based on the isocyanate prepolymer) was introduced into 10 the reaction vessel and heated to 90C. 2.5 kg of the polyether prepolymer described above which had been heated to 70C were added within 45 minutes. The product was worked up as in Example 1.
NH number (HC104) : 47.85 mg KOH/g 15 NH number (Ac~O/Py) : 47.9 mg KOH/g (Py = pyridine) S number (Ac20/Py) : 0.35 mg KOH/g (S number = acid number) TDA content (HPLC~ : 0.921% (HPLC = High Pressure Liquid Chromatography) DMF residual content(GC): 0.225 ~ (GC = Gas Chroma-tography) Example 10 A mixture, heated to 90C, of 1.75 1 of DME, 25 0.08 g of NaOH (0.016 wt. ~ based on the isocyanate pre-polymer) and 50 ml of water (DMF/H20 ratio = 33.2:1;
6.375 mol of water per isocyanate equivalent) was intro-duced into the reaction vessel. 500 g of the isocyanate prepolymer from Example 1 having an isocyanate content 30 of 3.65% were added within one minute. The product was worked up as in Example 1.
NH number (HC104) : 44.8 mg KOH/g NH number (Ac20/Py) : 46.4 mg KOH/g S number (Ac20/Py) : 0.1 mg KOH/g Mo-2839 ::IL26~0 Examples 11 and 12 A mixture of 1.1 1 of DMF, 0.05 g of NaOH
(O.01% by weight based on the isocyanate prepolymer) and 25 g of water (DMF/water ratio 41.7:1; 3.52 mol of water 5 per isocyanate equivalent) was introduced a~ 90C into the reaction vessel. 500 g of the isocyanate prepolymer from Example 4 containing 3.3~ NCO were added within 20 minutes. The product was worked up as in Example 1.
NH number (HCl04) : 47.4 mg KOH/g 10 NH number (Ac2O/Py): 47.6 mg XOH/g S number (Ac2O/Py): 0.09 mg KOH/g TDA content (HPLC) : 0.438 When 0.1 g of NaOH (0.02 wt. %, based on the isocyanate prepolymer) was used ins~ead of 0.05 g of 15 NaOH under otherwise identical conditions and using otherwise the same components, a product having an NH
number (HCl04) of 46.1 mg KOH/g was obtained.
Example 13 A mixture, heated to 90C7 of 1.1 l of DMF, 20 0.025 g of NaOH (0.005 wt. %, based on the isocyanate prepolymer) and 25 g of water (DMF/water ratio = 41.7:1) was introduced into the reaction vessel. 500 g of the isocyanate prepolymer from Example 1 having an isocyanate content of 3.6% (3,23 mol of water per 25 isocyanate equivalent) were added within 20 minutes.
The product was worked up as in Example 1.
NH number (HC104) : 46.7 mg KOH/g Example 14 A mixture of 1.75 1 of ~MF, 0.01 g of NaOH
30 (0.002 wt. %, based on the isocyanate prepolymer) and 50 g of water tDMF/water ratio = 33.2:1) was introduced into the reaction vessel and heated to 90C. 500 g of the isocyanate prepolymer from Example l having an isocyanate content of 3.6% (6.46 mol of water per NCO) Mo-2839 were added within 20 minutes. The product was worked up as in Example 1.
NH number (HC104) : 43.4 mg KOH/g NH number (Ac20/Py) : 49.15 rng KOH/g 5 S number (Ac20/Py) : 0.1 mg KOH/g Example 15 A mixture of 1.1 l of DMF, 0.025 g of NaOH and 25 g of water was introduced into the reaction vessel and heated to 90C. 500 g o the isocyanate prepolymer 10 from Example 4 having an isocyanate content of 3.3% NCO
were added within one minute and the mixture was then stirred ~or 20 m;nutes. The product was otherwise worked up as in Example 1.
NH number (HCl04) : 42.6 mg KOH/g 15 Example 16 An isocyanate prepolymer having an isocyanate content of 3.19% and obtained from a polyester with an OH number of 50 and tolylene-2,4-diisocyanate in an NCO/O~ ratio of 2:1 was used m this Example. me polyester used 20 was made from approximately equivalent a~unts o~ adipic acid and hexane-1,6-diol and had an OH numb2r of 41.
A mixture of 4.4 1 of DMF 9 100 g of water and 0.2 g of NaOX was introduced into the reaction vessel , and heated to 90C with stirring. 2 kg of the 25 above-mentioned isocyanate prepolymer ~at 60C) were added with stirring within 45 minutes. The product was worked up as in Example 1.
NX number (HC104) : 43.5 mg KOH/g NH number (Ac20/Py) : 43.85 mg KOH/g ~0 S number (Ac20/Py) : 0.4 mg KOH/g TDA content ~HPLC) : 0.81 %
Example 17 An isocyanate prepolymer having an isocyanate content of 2.34% and obtained from a polyester and Mo-2839 ~oo~

tolylene-2,4-diisocyanate in an NCO/OH ratio of 2:1 was used in this Example. The polyester was made from 1:1 adipic acid and diethylene glycol and had an OH number of 41.
A mixture, heated to 90C, of 1.75 1 of DMF, 0.05 g of NaOH and 50 ml of wa~er was introduced into the reaction vessel. 500 g of the above prepolymer were added within 30 minutes with stirring. The product was worked up as in Example 1.
10 NH number (HC10~) : 28.05 mg KOH/g TDA content (HPLC) : 0.206 %
Example 18 An isocyanate prepolymer having an isocyanate content of 3.4% and obtained from a polyether mixture 15 and tolylene-2,4-diisocyanate was used in this Example.
The polyether mixture had an OH number of 50 and a functionality of 2.5 and was a 1:1 mixture of trimethylol propane and a PO/EO polyether which had been started on propylene glycol.
2Q A mixture, heated to 90C, of 3.5 1 of DMF, 0.1 g of NaOH and 100 ml of water was introduced into the reaction vessel. 1000 g of the above-mentioned prepolymer were added within 40 minutes wlth stirring.
The product was worked up as in Example 1.
25 NH number (HC104) : 44.3 mg KOH/g NH number (Ac20/Py) : 43,5 mg KOH/g S number (Ac20/Py~ : 0.3 mg KOH/g TDA content (HPLC) : 0.087 %
Example 19 A prepolymer having an isocyanate content of 3.1% obtained by stirring for 3 hours at 80C
polytetramethylene glycol having an OH number of 56 and tolylene-2,4-diisocyanate in an NCO/OH ratio of 2:1 was used in this Example.
Mo-2839 o~

A mixture, heated to 90C, of 1.75 1 of DMF, 0.05 g of NaOH and 50 ml of water was introduced into ~he reaction vessel. 500 g of the above-mentioned prepolymer were added within 20 minutes. The product 5 was worked up as in Example 1.
NH number (HC104) : 39.5 mg KOH/g TDA content (HPLC) : 0.281 %
Example 20 A prepolymer with isocyanate content 2.8%
10 obtained by stirring for 4 hours at 80C (from an ester with OH number 56 (as in Example 9~ and diphenylmethane-4,4'-diisocyanate in an NCO/OH ratio of 2:1) was used in this Example.
A mixture, heated to 90C, of 1.75 1 of DMF, 15 0.05 g of NaOH and 50 g of water was introduced into the reaction vessel. A freshly prepared mixture of 500 g of the above-mentioned prepolymer and 200 g of DMF was added within 35 minutes. The product was worked up as in Example 1.
20 NH number (HC104) : 31.4 mg KOH/g NH number (Ac2O~Py) : 29.25 mg KOH/g S number (Ac20/Py) : O.2 mg ROH/g MDA-4,4' content (HPLC) : 1.48 %
Example 21 A prepolymer with isocyanate content 1.87Z
obtained by stirring for 4 hours at 80C from a polyetherdiol with an OH number of 28 (obtained by blockwise addition of 80~ propylene oxide followed by 2~ ethylene oxide to propylene glycol and using an NCO/OH ratio of 2:1) 30 and 2,4-tolylene diisocyanate was used in this E~ample.
A mixture, heated to 90C, of 1.75 1 of DMF, 0.05 g of NaOH and 50 ml of water was introduced into the reaction vessel. 500 g of the above-described prepolymer were added in 30 minutes. The product was 35 worked up as in Example 1.
Mo-2839 ~ 2 NH number (HC104) : ~3.7 mg/KOH/g Example 22 An NCO:OH = 2:1 prepolymer obtained by stirring for three hours at 80C of a polyethertriol with OH
5 number 28 obtained by the addition of 87 wt. D~ propylene oxide followed by 13 wt. DZ ethylene oxide to trimethylol-propane and 2,4-tolylene diisocyanate having an isocyanate content of 1.8% was used in this Example.
A mixture of 1.75 1 of DMF, 0.05 g of NaOH and 10 50 ml of water (12.9 mol of water per isocyanate equivalent; DMF/H20 ratio = 33. 2 :1 ) was introduced into the reaction vessel. 500 g of the isocyanate prepolymer described ahove were added in 30 minutes. The product was worked up as in Examp]e 1.
NH number (HC104 ) : 25 .15 mg KOH/g NH number (Ac20/Py) : 24 . O mg KOH/g S number (Ac20/Py) : O. 2 mg KOH/g Examples 23-25 The efficient action of sodium aluminate is 20 demonstrated in these Examples.
Example 23 A mixture of 1750 ml of DMF, 50 g of water and O . l g of sodium aluminate was introduced into the reaction vessel at 90C. 50Q g of the isocyanate 25 prepolymer from Example l having an isocyanate content of 3.65Z (ratio H20:NCO about 6.4:1) were added with stirring. The product was prepared and worked up as in Example 1.
NH number (HCl04) : 51.6 mg KOH/g 30 NH number (Ac20/Py) : 51.5 mg KOH/g S number (Ac20/Py) : 0.1 mg KOH/g TDA content (HPLC) : 0.81 D~

Mo-2839 o~

Example 24 A mixture, heated to 90C, of llOO g of DMF, 25 g of water and 0.01 g of sodium aluminate was introduced into the reaction vessel. 500 g of the 5 isocyanate prepolymer from Examp:le 4 having an isocyanate content of 3.3% (ratio H20:NCO =
approximately 3.5:1) were added within 20 minutes with stirring. The product was prepared and worked up as in Example 1.
lO NH number (HC104) : 47.15 mg KOH/g Example 25 A mixture, heated to 90C, of llOO g of DMF, 25 g of water and 0.05 g of sodium aluminate was introduced into the reaction vessel. 500 g of an 15 isocyanate prepolymer prepared by the same method as the isocyanate prepolymer from Example 1 but having an isocyanate content of 3.2~ were added with stirring (ratio H20:NCO = 3.65:1). The product was prepared and worked up as in Example l.
20 NH number (HC104) : 41.7 mg KOH/g Example 26 A mixture, heated to 90C, of 1.75 1 of DMF, SO g of water and 2.5 g of KHC03 (0.5 wt. %, based on the isocyanate prepolymer; DMF/water ratio by weight =
25 33.2:1; 7.05 mol of water per NCO) was introduced into the reaction vessel. 500 g of the isocyanate prepolymer from Example 4 havi.ng an isocyanate content of 3.3% were added within 20 minutes. The product was worked up as in Example l.
30 NH number (HC104) : 47.3 mg KOH/g Examples 27-28 These Examples demonstrate that the use of larger quantities of water lead to poorer results, i.e.
lower NH numbers due to lower NCO/NH2 conversion rates.
Mo-2839 .~2~VO~

Example 27 A mixture, heated to 90C, of 1.5 1 of DMF, 250 ml of water t32.32 mol of water/NCO equivalent;
DMF/water ratio = 5.9:1) and 0.05 g of KHCO3 (0.01 wt.
5 ~, based on the prepolymer) was introduced into the reaction vessel. 500 g of the isocyanate prepolymer from Example 1 having an isocyanate content of 3.6% were added within 20 minutes. The product was worked up as in Example 1.
10 NH number ~HC104) : 37.8 mg KOH/g NH number (Ac2O/Py) : 38.95 mg KOH/g S number (Ac2O/Py) : 0.1 mg KOH/g Example 28 A mixture, heated to 90C, of 1.5 1 of DMF9 250 15 ml of water (DMF/H2O ratio = 5.9:1) and 0.05 g of sodium forma~e was introduced into the reaction vessel. 500 g of the prepolymer from Example 4 having an isocyanate content of 3.3% were added within 20 minutes. The product was worked up as in Example 1.
20 NH number (HC104) : 33.7 mg KOH/g Example 29 A mixture, heated to 90C, of 1.75 1 of DMF, 50 g of water and 0.~4 g of sodium formate (HCO2Na) was introduced into ~he reaction vessel. 500 g of the 25 isocyanate prepolymer from Example 1 were added with stirring and the reaction was continued and the product worked up as described in Example 1.
N~ number (HC104) : 50.5 mg KOH/g NH number tAc2O/Py) : 48.4 mg KOH/g 30 S number (Ac2O/Py) : 0.1 mg KOH/g Examples 30 to 40 Isocyanate prepolymers obtained by stirring for 4 hours at 80C of a mixture of tolylene-2,4-diiso-Mo-2839 ~6 - 4~) -cyanate and a polyoxypropylene g:Lycol with OH number 32 which had been started on trimethylolpropane were used in these Examples. A product having an isocyanate content of 2,1Z was used in Examples 30 to 33. A
5 product with an isocyanate content of 2.3% was used in Examples 34 to 36, 38 and 39 and one having an isocyanate content of 2.2~ was used in Examples 37 and 40.
Example 30 A mixture, heated to 90C, of 1.1 1 of DMF, 25 ml of water and 0.025 g of NaOH was introduced into the reaction vessel with stirrin~. 500 g of a prepolymer described above having an isocyanate content of 2.1% was added at this reaction temperature with stlrring and the 15 reaction was then continued and the product worked up as in Example l.
NH number (HC104) : 30.8 mg KOH/g NH number (Ac20/Py) : 34,0 mg KOH/g S number (Ac20/Py) : 0.05 mg KOH/g 20 Example 31 A mixture, heated to 90C, of 1.1 1 of DMF, 25 ml of water and 0.01 g of NaOH was introduced into the reaction vessel with stirring, 500 g of the isocyanate prepolymer from Example 30 were added at this 25 reaction temperature with stirring and then reacted and worked up as in Example 1.
NH number (HC104) : 29.8 mg KOH/g NH number ~Ac20/Py) : 33.5 mg KOH/g S n~mber (Ac20/Py) : O.05 mg KOH/g 30 Example 32 A mixture, heated to 90CI of 1.1 1 of DMF, 25 ml of water and 0.005 g of NaOH was introduced into the reaction vessel with stirring. 500 g of the isocyanate prepolymer from Example 30 were added at this Mo-2839 6~

reaction temperature and reacted and worked up as in Example l.
NH number (HC104) : 31.1 mg KOH/g NH number (Ac2O/Py) : 32.1 mg KOH/g 5 S number (Ac2O/Py) : 0.05 mg KOH/g Example 33 A mixture, heated to 90C9 of 1.1 1 of DMF, 25 ml of water and 0.0025 g of NaOH (0.0005 wt. %, based on the prepolymer) was introduced into the reaction 10 vessel with stirring. 500 g of the isocyanate prepolymer from Example 30 were added at this temperature with stirring and reacted and worked up as in Example 1.
NH number (HCl04) : 29.4 mg KOH/g 15 NH number (Ac2O/Py) : 28.6 mg KOH/g S number (Ac2O/Py) : 0.05 mg KOH/g Virtually the same results were obtained when 0.0025 g of ~OH was used.
Example_34 A mixture, heated to 90C, of 1.1 1 of DMF, 25 ml of water and 0.005 g of KOH was introduced into the reaction vessel with stirring. 500 g of a prepolymer similar to that used in Example 30 and described above having an isocyanate content of 2.3% were added with 25 stirring at 90C and reacted and worked up as in Example 1.
NH num~er (HCl04) : 29.2 mg KOH/g Example 35 A mixture of 1.1 1 of DMF, 25 ml of water and 30 0.0025 g of NaOH was introduced into the reaction vessel with stirring at 45C, 500 g of the same isocyanate prepolymer as was used in Example 34 were added at this reaction temperature with stirring but stirring was then continued for 20 minutes (end of evolution of CO2). The 35 product was worked up as in Example 1.
Mo-2839 ~ ~ 6 Fxample 36 A mixture of 1.1 1 of DMF, 25 ml of water and 0.1 g of NaOH was introduced into the reaction vessel at 45C with stirring. 500 g of the same isocyanate 5 prepolymer as was used in Example 34 were added at this reaction temperature with stirring. Stirring was then continued for 25 minutes during which one sample was removed after 5 minutes. Both samples were worked up as in Example 1.
10 NH number (HCl04 after 5 min): 29.4 mg KOH/g NH number (HC104 after 25 min): 29.0 mg KOH/g This shows that even at 45C the reaction was completed 5 minutes after all the reactant had been added and that more prolonged stirring did not provide any advantages.
15 Example 37 A mixture of 1.1 1 of DMF, 25 ml of water and 0.05 g of KOH was introduced into the reaction vessel at 45C with stirring. 500 g of an isocyanate prepolymer similar to that described in Example 30 above but having 20 an isocyanate content of 2.2Z were added at this temperature with stirring. Subsequent treatment of the reaction mixture and working up were the same as in Example 1.
NH number (HC104) : 29.0 mg KOH/g 25 Example 38 A mixture of 1.1 1 of DMF and 25 ml o water was introduced into the reaction vessel at 90C with stirring. 500 g of the isocyanate prepolymer from Example 34 were added at this reaction temperature with 30 stirring. The product was worked up as in Example 1.
NH number (HC104) : 17.5 mg KOH/g When 0.2 g of l/lON NaOH were added to this reaction mixture after all the isocyanate prepolymer had been added and the mixture was then stirred at 90C for Mo-2839 ~6~0~L~

45 minutes, the product obtained after the reaction mixture was worked up as in Example 1 and had an NH
number of 17.8 mg KOH/g (HC10~ method). This showed that even without a catalyst, the reaction was completed 5 within 5 minutes after all of the isocyanate prepolymer had been added.
Example 39 A mixture of 1.1 1 of DMF and 25 ml of water was introduced into the reaction vessel with stirring at 10 a reaction temperature of 137C (reflux). 500 g of the isocyanate prepolymer from Example 34 were added within 27 minutes. The reaction temperature fell to 130C
(bath temperature 160 - 180C) on addition of the isocyanate prepolymer and reflux died down.
When the reaction mixture was worked up after a further 5 minu~es of stirring under reflux, a product having an NH number (HC104) of 20.7 mg KOH/g was obtained.
When the reaction mixture was worked up under 20 reflux after 30 minutes of stirring, a product having an NH number (HC104) of 21.3 mg KOH/g was obtained.
This shows that even without catalyst and at this temperature the reaction was completed within 5 minutes after all the isocyanate prepolymer had been 25 added.
Examples 38 and 39 also demonstrate that although the product obtained without the aid of a catalyst is superior to one prepared according to DE
3,223,398 without a catalyst, it had a high degree of 30 prelengthening (urea formation).
Example 40 (Comparison Example to Example 38) A mixture of 1.1 1 of DMF and 300 ml of water was introduced into the reaction vessel and heated to 90C with stirring. 500 g of the isocyanate prepolymer Mo-2839 2 ~

_ ~4 _ from Example 37 were added within 20 minutes with stirring. A gel-like polymer then separated which would not dissolve even in pure DMF or in acetic acid. When attempts were made to determine an NH number of the 5 insoluble material, the result obtained was< 2 mg KOH/g as the NH number.
This experiment demonstrates that the water/solvent tor water/DMF) ratios used in DE 3,223,398 and 3,223,397 give less favorable results than those 10 obtained in the process of the present invention. This means that the product obtained by the prior art process is virtually unusable whereas the process according to the invention provides useful liquid and soluble products with respectable NCO/NH2 conversion rates and 15 considerable NH numbers even when carried out in a manner which is not preferred.
Example 41 616 ml of DMF and 14 ml of H20 were introduced into a 1.3 1 autoclave and heated to 150C. 280 g of 20 the isocyanate prepolymer used in Example 37 were then added with stirring within 5 minutes, using a dosing pump. The temperature ~f the isocyanate prepolymer was 50C. Stirring was then continued for a further 5 minutes at 150C and the reaction mixture was cooled, 25 the pressure released and the solvent distilled off as in Example 1. A brown material having the following data was obtained:
NH number (HC104): 28.9 mg KOH/g ~H number (Ac20/Py): 27.1 mg KOH/g 30 S number: 0.05 mg KOH/g Molar masses: 3825, theoretical 3851 (determined by vapor pressure osmometry) TDA content: 0.288 wt. %

Mo-2839 .
~L~6001~

Example 42 (Comparati~Te) 600 ml of water were heated to 150C in a 1.3 1 autoclave, and 300 g of the isocyanate prepolymer from Example 37 heated to 50C were added within 10 minutes.
5 Stirring was continued for a further 5 minutes at lS0C
and the reaction mixture was then cooled, the pressure released and the water decanted from the product obtained. The product was a viscous rubber but was still partly soluble in a DMF/ethanol mixture at 80C.
The NH number of the part that was still soluble ~after removal of the solvent by distillation) was 11.1 mg KO~/g (HC104).
(Comparative) Example 42 was repeated with the exceptlon that 15 0.06 g of KOH were added to the water. The product obtained after working up was a swelled material completely insoluble in DMF. No NH number could be de~ermined.
~ le 44 20 a) Preparation of prepolymer 1218 g of toluylene diisocyanate (7 mol) were heated to 60C. 90 ~ of butane-1,4 diol were added within 40 minutes. The reaction product precipitated towards the end of the reaction. Stirring was then 25 continued for one hour at 60C. The pasty mixture was diluted with 2 1 of cyclohexane at 23C and suction filtered, washed with cyclohexane and petroleum ether and dried in a vacuum drying cupboard at 40C. The product melted at 130 to 131C and had an isocyanate 30 content of 19.0% (the calculated isocyanate content for a 2:1 adduct is 19.2%).
b) Preparation of polyamine A mix~ure of 3256 ml of DMF, 0.15 g of KOH and 74 ml of water was introduced into the reaction vessel.
Mo-2839 A suspension of 310 g of the above-mentioned isocyanate prepolymer in 600 ml of DMF was added with stirring at 90C within 20 minutes. 31 1 of CO2 were found ~o evolve (theoretical 31.4 1). The solvent was then to a 5 large extent distilled off and the product was precipitated from the liquid residue by means of a 10:1 mixture of water and methanol. The product was suction filtered, washed with water and dried.
NH number (Ac2O/Py): 274 mg KOH/g (Th.: 288) 10 Acid number (Ac2O/Py): 0.4 mg KOH/g Molar mass (vapor pressure osmometry): 395-400 (Th.:378) TDA value (HPLC): 0.352%
NH number (HC104): 264 mg KOH/g; m.pt.: 168-169C.
Example 45 A mixture of 1750 ml of dimethylformamide~ 30 ml of water and 0.01 g of potassium octoate ~0.002 wt. %
based on the isocyanate prepolymer) was introduced into the reaction vessel. The mixture was heated to 90C.
500 g of the isocyanate prepolymer from Example 9 heated 20 to 70DC, were added within 20 minutes and worked up as described in that Example. The polyamine had an NH
number (Ac2O/Py) of 47.95 mg KOH/g.

Mo-2839

Claims (16)

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

1. A one-step process for the production of poly-amines containing primary amino groups in which (a) an organic isocyanate having an isocyanate content of from 0.5 to 40 wt%
is hydrolyzed with (b) from 0.75 to 50 mols of water for each equi-valent of isocyanate groups in (a) in the presence of (c) at least 10% by weight of carboxylic acid amides based on 100%. by weight of (a) and (d) 0-1 % by weight of not incorporable basic and/or metal catalyst based on 100 % by weight of (a) in which the weight ratio of (c) to (b) is from 3 to 200, a homogeneous phase is maintained during the hydro-lysis and the hydrolysis is carried out at a temperature of from 20 to 210°C.

2. The process of Claim 1 in which isocyanate (a) contains aromatically bound isocyanate groups and is an NCO-prepolymer or modified polyisocyanate.

3. The process of Claim 1 in which isocyanate (a) has an isocyanate content of from 1.2 to 25 wt.%.

4. The process of Claim 1 in which catalyst (d) is present in an amount of from 0.0001 to 0.099 % by weight.

5. The process of Claim 4 in which catalyst (d) is selected from alkali metal hydroxides, alkaline earth metal hydroxides, tetraalkylammonium hydroxides, alkali metal aluminates, alkali metal phenolates, alkali metal thiophenolates, alkali metal mercaptides, alkali metal hydrogen sulfides, soluble alkali metal salts of cyanic, thiocyanic, isocyanic and isothiocyanic acids, alkaline earth metal salts of cyanic, thiocyanic, isocyanic and isothiocyanic acids, alkali metal .beta.-diketone-enolates, alkali metal carbonates, alkali metal bicarbonates, alkali metal salts of organic carboxylic acids and alkaline earth metal salts of organic carboxylic acids.

6. The process of Claim 5 in which 1,5-12 mols of water (b) per equivalent of (a) are used, the solvent (c) is a carboxylic acid dialkylamide, the weight ratio of (c) to (b) is 10 to 150 and the hydrolysis is carried out at 35-165°C.

7. The process of Claim 6 in which the weight ratio of (c) to (b) is 25 to 75.

8. The process of Claim 1 in which the solvent (c) is dimethylformamide or dimethylacetamide.

9. The process of Claim 1 in which (e) from 0,1 to 5% by weight of a compound containing at least one hydroxyl, amino and/or thiol group for every 100% by weight of (a) is present during hydrolysis.

10. The process of Claim 1 in which the hydrolysis is carried out at 40 to 150°C.

11. The process of Claim 1 in which a catalyst (d) is included, from 0.0001 to 0.99% by weight of tertiary amine based on every 100% of isocyanate (a) is used as catalyst (d), from 1 to 24 mols of water for i each equivalent of isocyanate (a) are used, and the weight ratio of (c) to (b) is 10 to 100.

12. The process of Claim 11 in which the solvent (c) is dimethylformamide and from 1 to 7.5 mols of water are used for each equivalent of isocyanate (a).

13. The process of Claim 1 in which from 0.0002 to 0.008% by weight metal catalyst (d) 2 to 7.5 mols of water for each equivalent of isocyanate and a weight ratio of (c) to (b) from 10 to 50, and a temperature of from 35 to 165°C are employed.

14. The process of Claim 1 in which from 1 to 25 mols of water are used (b) for each equivalent of isocyanate, the solvent (c) is dimethylformamide which is used in a quantity such that the weight ratio of (c) to (b) is from 10 to 75 and the temperature is from 35 to 165°C.

15. The process of Claim 1 in which the isocyanate (a) is an isocyanate prepolymer having an isocyanate content of from 1.5 to 10 wt. % or a urethane modified polyisocyanate having an isocyanate content of from 1.5 to 20.5 wt. %.

16. A polyamine containing 0.46-9.52 wt. %
primary NH2 groups produced by the process of Claim 1.