CA1328276C - Polyaminohydroxyl compounds containing urethane and/or urea groups and processes for their preparation and use - Google Patents

Abstract

POLYAMINOHYDROXYL COMPOUNDS CONTAINING
URETHANE AND/OR UREA GROUPS AND PROCESSES
FOR THEIR PREPARATION AND USE
ABSTRACT OF THE DISCLOSURE
Polyaminohydroxyl compounds having molecular weights of from 200 to 20,000 and a functionality greater than 1 but less than or equal to 8 containing 0.165-16.5 wt. % amino and hydroxyl groups and 0.295-29.5 wt. % urethane and/or urea groups are produced by hydrolyzing the corresponding NCO prepolymer containing OH groups. The equivalent ratio of amino groups to hydroxyl groups in these polyaminohydroxyl compounds is from 99:1 to 0.1:99.9. Groups which are inert with respect to amines and isocyanates may optionally be present in the polyaminohydroxyl compounds in quantities such that the equivalent ratio of amine groups to inert groups 16 from 100:0 to 33.?:66.? and the equivalent ratio of hydroxyl groups to inert groups is from 100:0 to 33.?:66.?. These polyaminohydroxyl compounds are useful in the production of polyurethanes.
The polyaminohydroxyl compounds in which the difference between the sum of amino groups plus hydroxyl groups plus inert groups and the sum of hydroxyl groups plus inert groups is 2 ? 0.25 are particularly suitable for producing molded polyurethane articles by a RIM process.

Description

Mo-2~37 POLYAMINOHYDROXYL COMPOUNDS CONTAINING
URETHANE AND/OR UREA GROUPS AND PROCESSES
FOR THEIR PREPARA~ION AND USE
BACKGROUND OF ~HE INVENTION
This invention relates to compounds containing primary amino groups attached to the molecular skeleton by urethane and/or urea groups and also hydroxyl groups and optionally isocyanate inert groups and process is for their preparation and use.
According to EP-B 81,701, elastic polyurethane molded products having a compact surface layer are obtained from polyethers with molecular weights of from 1800 to 12,000 in which the isocyanate reactive groups contain at least 50% primary and/or secondary amino end groups (and possibly also hydroxyl groups). The disclosed polyethers may be obtained by the pressure amination of polyether polycls or by the hydrogenation of adducts of acrylonitrile and polyether polyols or by the reaction of polyols with isatoic acid anhydride or by the hydrolysis of isocyanate compounds according to DE-A
2,948,419. The polyethers may also be mixed, for example, with polyether polyols to form a polyether mixture having the composition claimed. Suitable amino polyethers may also be obtained by partial pressure hydrogenation in the presence of ammonia. These amino-polyethers may contain, for example, 80 equivalent percent of amino groups and 20 equivalent percent of hydroxyl groups.
In accordance with U.S. Patent 4,58~,840, issued May 13, 1986 polyoxyalkylene-aryl polyamines may be obtained by reaction of polyoxyalkylene polyols with aromatic amines and hydrogen under pressure in the presence o~ catalysts containing nickel, cobalt, copper or manganese.
Amino compounds of this kind may also be obtained for example, according to U.S. Patent 4,386,218 : ; ~ .

F ~ i, .
: ~ . ; .: ~, . ' ' ' . :

issued May 31, 1983 by hydrolysis of the corresponding preliminary isocyana~e stages (in particular isoscyanate prepolymers). These compounds are a very suitable starting material ~or the preparation of polyurethane (urea) elastomers.
The higher molecular weight compounds which are particularly suitable for this purpose, however, have relatively high viscosities, e.g. in the region of 10,000 to 100,000 mPas/25~C, and are therefore very difficult to process. This high viscosity is due to the fact that the preferred starting compounds for the preparation o~ the preferred amino compounds are isocyanate prepolymers which are obtained by the reaction o~ polyols (preferably polyether polyols) with excess quantities of polyisocyanates and contain urethane groups. These isocyanate prepolymers have a substantially higher viscosity than the underlying polyether polyols (generally about twice the viscosity~.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide compounds for the production of polyurethanes (ureas) which compounds have a considerably lower viscosity than the known compounds.
It is also an object of the present invention to provide processes for making such polyaminohydroxyl compounds and for using them in the production of polyurethane (ureas).
These and other objects which will be apparent to those skilled in the art are accomplished by hydrolyzing isocyanates containing specified amounts of isocyanate~ hydroxyl, urethane and/or urea groups to form the corresponding polyaminohydroxyl compounds. These compounds may then be reacted with polyisocyanates to form polyurethanes (ureas) LeA 25 534 -2-.
, . . ,~:

.

1 32~276 `

DETAILED DESCRIPTION ~F T~ INV~NTION
The present invention relates to compounds containing urethane and/or urea groups and primary amino groups, and hydroxyl groups and optionally inert groups 5 and having molecular weights of from 200 to 20,000, preferably higher molecular weight compounds in the moleeular weight range of from 400 to l2,000 ~nd most preferably wi~hin the molecular weigh~ range o~ from 1000 to 7000, having ~ func~ionality from >1 to 89 10 preferably from 1.5 to 6 and most preferably from 2 to 4 which contain a) amino and hydroxyl groups in quantities of from 0.165 to 16.5 wt. ~, preferably 0.3 to 10 wt. Z, most preferably 0.4 to 5 wt. ~, with the equivalent ratio of amino groups to hydroxyl group~ being in the range of from 9~:1 to 0.1:99.9, preferably from 95:5 to 5:95, more preferably from 80:20 to 20:80, and mofit preferably from 66.6:33.3 to 33.3:66.6, b) opt~onally ~mino ~nert and isocyanate inert end groups ("inert groups") in quant~ties ~uch ~hat the equivalent ratio of amino groups to the optionally present inert groups iB in the range of from 100:0 to 33.3:66.6, preferably from 100:0 to 80s20, mo~t preferably from 100:0 to 90:10 and that the equivalent ratio of the hydroxyl group~ to the inert groups lies in the range of from 100:0 to 33.~:66.Z, preferably from 100:0 to 80:20, most preferably from 100:0 to 90:10, and c) urethane and/or urea groups preferably in quantities o from 0.295 to 29.5 wt. X.

.
, :

` -" 1 328276 The equivalent ratio of amino groups to the sum of hydroxyl groups and optional ~nert groups lies in the range of from 1:99 to 99.9:1, preferably from 5:95 to 95:5, more preferably from 20:80 to 80:20 and most 5 preferably from 33.~:66.~ to 66.~:33.~.
The presence of inert groups may be obtained in particular by a simple reaction of the OH andtor amino groups with monofunctionally react~ng eompounds accompanied by partial "blocking" of the functional 10 groups of polyvalent compounds such a~ triols or tetrols (e.g., by acylation or by reaction with monoisocyanat2s or by me~hoxylation or esterlfication with inorganic monofunctional acids). This 9Iblocking~ of the functional groups i8 preferably carried out before the 15 reaction with the di- or polyisocyanates to form hydroxyl- containing isocyanate prepolymers.
Thi8 invention further relates to c~mpounds in the molecular weight range of from 200 to 20,000, preferably relatively high molecular weight compounds in 20 the range of from 400 to 12,000, most preferably from 1000 to 7000 9 with an average functionality of from>l to 8, preferably from 1.5 to 6, mc)st preferably from 2 to 4, having a hydroxyl plu8 amino group co~tent of from 16.5 to 0.165 wt. ~, a urethane group ~NHCOO) and/or 25 urea group (Nn~CO~I) content of from 29.5 to 0.295 wt. Z, and an equivalent ratio of NH2 groups to OH group~ in the range of from 99:1 to 0.1:99.9, preferably frQm 80:20 to 20:80, most preferably from 66.6:33.3 to 33.3:66.6.
The inventlon relates preferentially to compounds containing uret~ane and urea groups carrying primary amino group~, hydroxyl groups and optionally inert groups in accordance with the above defini~ion which further contain polyether group~. Particularly 35 preferred compounds correspond to formul~ tI3 Le A 24 534 , 1 3~8276 1 1 ~" lX (R )m~~ -X-~-NH-R ~tNH2)qlr ~HO-(R O)n~R -X ~ R O
[X-(R O)o-R ~Y] 8 ( I) in which X represen~s NH or 0, Y represents H, a monovalen~ organic group (e.g. an 10 alkyl, aryl or alkoxy group~ or preferably ~
[-OCONH-monovalent group~ or a l-NHCONH-monovalent group] (the monovalent group being e.g~ alkyl, aryl or alkoxy), R represen~s a group obtained by lthe removal of (p + r + s) XH groups from a (p ~ r ~ s)-valent ; polyamlne, polyaleohol or amino alcohol, l represent~ an optionally alkyl- or aryl-~ubstituted C2-C4-alkylene group, in particular an ethylene ; and/or 1, 2-propylene group, 20 R represents a ~q + l)-valent group a8 ob~ained by the removal o ~q + 1) NCO groups from a (q + l)-valent polyisocyanate, q has a value of from 1 to 2, ` n, m, o are 80 cho~en that the molecular weight is in J 25 the range of from 200 to 20,000, preferably 400 to 12,000, and p, r, ~ are ~o chosen that (p + r ~ 6) - 2 to 8, . pseferably 2 to 6, mos~ preferably 2 to 4, and p:8 e 100:0 to 33.~:66.~, preferably 100:0 to 80:20, moet preferably 99~1 0ol to 90:10, r:p - 99:1 to Q.1:99.9, preferably 95:5 to 5.95, mQre preferably ~0;20 to 20:80 and most preferably 66 . ~: 33 . ~ to 33: ~: 66 . ~, and r: s~ 100: 0 to 33 . ~: ~6 . ~, preferably 100: 0 to 80: 20, m~st preferably 99.9:0.1 to 90:lû.

~: _24 5 34 . ~ : , ~ .

1 32~276 The compounds of the present inven~ion in which the sum of the equivalents of primary amino groups, OH
groups and op~ional inert groups minus ~he ~um of the equivalents of OH groups ~ optional inert groups has a value of 2~0.25, preferably about 2~0.1, are most preferred. In the ca~e of polyether compo~nd~
corresponding tv formula (I), this means that the ~Talues of (r ~ 8 -t p) minus (p + s) result in a value of 2 ~ 0 . 25 ~ preferably 2 + 0 .1.
The present invention also relate~ to mixtures made up of (a) 75-1~0 wt. X of the polyaminohydroxyl compound(s) of the presen~c inven~ion, particularly the polyether compounds correspondlng to formula (I) as lS defined above, tb) 0 to 5 wt. X nf compounds corresponding to formula (II) or low molecular weight or relatively high molecular weight secondary products of those compounds corresponding to formula (II) (resulting from hydroly~is of the free polyisocyanates used for the preparation of the enmpounds corresponding to formula (I) and still pre~ent (in minor quantities) in addition to the isocyanate prepolymers containing OH groups and op~ionally inert groups) R (NH2)q+1 (II), and ~c) 0 to 20 wt. Z starting compounds ~polyols or aminopolyol~ optionally containing iner~ groups, in particular polyether compounds (III) corresponding to the 8t8rting compounds from which the polyaminohydroxyl compound (a) was produced, preferably 3tarting compounds containing ~ner~
groups and obtained by the modifieation of polyols ~ Li~ 6 ~ .
' , , ' ' ': ' ' -' , ' ' , ' , ,~ ' ` ' , ' , : . , .

.. ... -, - . . ,, .. , . . , , . ~ ., . . , . .. 1 . ..

or aminopolyols (compound ~IV), X c 0;
compound (IV), X = NH). The preferred polyethers (c) are repre~ented by ~he formula / lX-(RlO)m Rl XH]r lH0-(R O)n~R -X ]- R (III~, ~[X-(RlO)o Rl-Y~

and/or /[X- (RlO)m--Rl -X}I]r [H0-(RlO)n-Rl-X ~ R 1 1 (IV), ~X-~R 0)0 R -XH]~

in which X~ R, Rl, R2, ~, m, o, p, q9 r, 8 and Y ha~e the meanings define~ abo~e.
The pre~ent invention also relates ~o a process for the preparation of the above-mentioned, new compounds. In this proces~ isocyanate c~mpounds which contain urethane and/or urea groups and in addition contain hydroxyl groups and optionally NC0-inert groups and 25 have a functionall~y of from~ 1 to 8, preferably from 105 to 6, in particular 2 to 4, which compounds contain from 0.3 to 25.9 wt. X, preferably from 0.4 ~o 15 w~. X, in particular from 1 to 13 wt. a 0~ free isocyanate groups and contain hydroxyl groups and optionally 30 isocyanate inert groups as well as urethane and/or urea groups, preferably from 0.295 to 29.5 wt. Z urethane and/or urea groups, in which the ratio of isocyanate groups to ~ydroxyl groups is in the range of from 90:1 to 0.1:99.9, preferably from 95:5 to 5:95, more 35 preferably from 80:20 to 20:80, most preferably from .
~: Le ~ 24 s34 _7_ 66 . ~: 33 . ~ to 33 . ~: 66 . ~, and ~he ratio of i~ocyanate groups to inert groups is f~om 100:0 to 33.~:66.Z, preferably from 100:0 to 80:20, most preferably from 100:0 to 90:10~ and the r8~io of hydroxyl groups to 5 inert groups is from 100:0 to 33.~:66.~, preferably from 100:0 to 80:20, most preferably from 100:0 to 90:10 are hydrolyzed. These i~ocyanate~ are hydroly~ed to f~rm the compounds of the present invention with at least 0.75 mol of water per NCO group, preferably with more 10 than 1 mol of water per NCO group. The hydroly~is may be carried out in the presence of catalysts based on bssic compounds, tertiary amines or metal catalyst~ (preferably ba~ic compounds) and optionally in the presence of solvents, with or without isolation of 15 an intermediate stage. The polyaminohydro~yl compo~nds obtained may be lsola~ed, e.~. by phase 6eparation or extractlon, opt~onally after the usual methods of purification.
In one preferred embodiment of the proces~ of 20 the present invention, the isocyanate starting material containing hydroxyl groups i~ mixed with water and a base to be converted into a reaction mixture containing compounds carrying c~rbamate groups. The compounds of the present invention may be recovered from thi~
25 reaction mixture by decomposition of ~he compound6 containing carbamate groupc by a heat treatment at ~emper~ture8 from room temperature to 200C and/or by treatment with an acid and/or by extraction wi~h an organic solvent.
In another preferred embodiment of the process, the isocyanate containing NCO and OH groups is directly hydrolyzed with water in a 8ubs~antially homogeneous phase at a temperature in the region of 25C ~o 210C in the presence of a ba~ic catalyst and in th presence of 35 an at ~ea~t partly water ml6cible, preferablv aprotic-di-polar solvent such as dimethylformamide, Le A 24 534 -8-- , ;.......... . .
. ~. . . , ~ . ~ . .

.. : : ; , . - : .

1 32~276 This invention also relates to the use of the new compounds as starting compounds for the production of foamed or unfoamed polyurethane polyureas, in particular for the production of molded elastomeric polyurethane-polyurea products having a surface skin (~or the motor car industry) by the RIM process using closed molds.
U.S. Patent 4,501,873, issued February 26, 1985, discloses relatively high molecular weight aromatic polyamines optionally containing residues of low molecular weight compounds carrying isocyanate reactive end groups, e.g. OH groups, which polyamines are prepared by a one-shot process (without previous formation of an isocyanate prepolymer) carried out at temperatures of 15 from -20C to 175C, in which polyisocyanates, relatively high molecular weight polyols with molecular weights of from 400 to 10,000 and optionally low molecular weight polyols in the molecular weight range of from 62 to 399 are simultaneously mixed in certain proportions in the presence of excess quantities of water, optionally in the presence of water-miscible solvents and optionally in the presence of catalysts. The mixtura is heated i~
necessary and the amine product is then separated.
The compounds of the present invention are preferably relatively low viscosity compounds but may be medium to high viscosity compounds or even solid or ¢rystalline compounds with a high melting point if they have been prepared from very short-chained starting materials. They contain amino groups and hydroxyl groups and may also contain isocyanate inert end groups. Theses compounds are prepared by hydrolysis of previously formed corresponding isocyanate compounds containing terminal isocyanate groups, hydroxyl groups and optionally inert groups. These previously formed isocyanate compounds may be obtained by the (partial) reaction of di and~or LeA 24 534 -9-. , , : . . ~ ~, ~ .
- ~- . i - .

1 3~87.76 polyisocyantes with polyols or aminopolyols in the molecular weight range of from 62 to 100,000 to form so-called isocyanate prepolymers still containing specified quantities of hydroxyl groups.
The compounds of the present invention are advantageous becaus~ they contain fewer ~ree, low molecular weight di- and/or polyamines (from the di- or polyisocyanates) and a smaller quantity of polyol starting materials (which have not yet reacted with the polyisocyanates in the simultaneous reaction) and have a more clearly defined structure as a whole and yet a relatively low viscosity (compared with the given starting materials).
The isocyanate compounds to be used in the process of the present invention are isocyanate prepolymers obtained in a known manner by the reaction of low molecular weight (molecular weight 62 to 399) and/or relatively high molecular weight compounds (molecular weight 400 to abouk 12,000~ containing hydroxyl and optionally amino and optionally thiol groups as reactive groups with polyisocyanates. However, in this reaction, the formation of isocyanate prepolymer is stopped before all of the OH, SH and/or NH2 groups have reacted and the incompletely reacted isocyanate prepolymers obtained are then hydrolyzed to convert their isocyanate groups into amlno groups.
The polyisocyanates used for the preparation of the compounds containing free isocyanate groups may in principle be any aromatic, aliphatic (including cycloaliphatic or araliphatic) or heterocyclic polyisocyanates (including diisocyanates). Low molecular weight and/or relatively high molecular weight compounds suitable for these reactions, which contain hydroxyl and/or amino and/or thiol groups as reactive groups and 35 have molecular weights in the range of 32 to 12 ! 000 . Di-LeA 24 534 -10-~ ~ 4 ,, . . , ; .

1 3~76 and/or polyisocyanates having an average isocyanate functionality of from 2 to 3 are preferred.
Aromatic di-/polyisocyanates are particularly preferred, especially 2,4- and/or 2,6-toluylene diisocyanates and 4,4'- and/or 2,4'-diisocyanato diphenyl- methanes, in particular 2,4-toluylene diisocyanate. -Examples of modified polyisocyanates suitable for the preparation of urethane- and/or urea-modified prepolymers include polyisocyanates containing urethane groups (obtained by modification with low molecular weight polyols), polyisocyanates containing urea groups (modification with water), polyisocyanates containing biuret groups, polyisocyanates containing isocyanurate groups and dimeric and oligomeric polyisocyanates containing uretdione or uretoneimine groups. These compounds are known or obtainable by known methods.
Numerous 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 uretone-imine groups suitable for the preparation of the NCO- and OH-containing isocyanate component ussd in the process of the present invention normally have an isocyanate content of from 5 to 40 wt. %, preferably 10 to 25 wt ~.
.

LeA 24 534 -11-~. :
: . . . .
, , , -` ~ 1 328276 The low molecular weigh~ and/or relatively high molecular weight9 polyfunctional compound8 in the molecular w~ight of 32 and ln the range of 60 to 20,000 containing hydroxyl and/or amino and/or thiol groups 5 whlch are to be reacted with the polyisocyanate~ to prepare the isocyanate prepolymer containing NCO and 9H
groups ~nd urethane and/or urea groupR may stilL contain end groups which are inert in isocyanate addition reactions. These inert end group~ are preferably 10 introduced by the con~ersion of a certain proportion of the hydroxyl and/or amino and/or thiol groups into inert groups by known methods which may be found in literature. These methods include, for example, the convers~on of OH groups in the 6tarting polyol into 15 ether groups (e.g. with dimethylEulpha~e), in~o ure~hane groups (wlth mono~socyanate~) or into halide groups (with halogenating agent~). The amino groups may be converted into ureas with monoisocy~nates or into azomethine groups with ~etones. The inert groups are 20 prefersbly introdueed before the reaction with the di-/poly- isocyanate~. The preferred reactants for introduction of ~nert groups are monoisocyanates.
The compounds containing hydro~yl and/or amino groups and optionally inert groups (in the conte~t of 25 isocyanate addition reactions) are converted into the prepolymer reaction component by reaction wi~h ~
polyi~ocyanate. In this proce6s, the isocyanate reactive groups (e.g. OH groupæ) are only partially reacted with the isocyanate groups of the poly-30 isocyanates, and the lsocyanate groups are hydrolyzed toform primary amino groups before they have completely reac~ed with the OH and amino groups (or also thiol groups).
The isocyanate prepolymers uEed in the proce~s 35 of the preRent invention are preferably the type .e A 24 534 ~ . . .

: . - ' :.: ~

` ` 1 328~76 obta~ned from relatively high molecular weight, di~unctional or higher functional polyols (molecular weight 400 to 12,000~, preferably polyether polyols, optlonally in the presence of chai~-lengthening agents 5 of the type described above (molecular weights preferably 60 ~o 399) by incomplete isocyanate prepolymer formation with aromatic di- and/or polyisocyanates (preferably diisocyanates). As already mentioned, not all the hydro~yl groups react wi~h the 10 polyisocyanates. For the desired reaction of one hydroxyl group equivalent~ it is preferable to use one mol of a diisocyana~e so that the hydroxyl group is converted into an NCO-containing end group attached through a urethane group:
15 -OH + OCN-D-NCO ) -OCO-NH-D-NCO (D c residue of a diisocyanste).
The isocyanate content of the i~ocyanate prepolymer which contains NCO and OH groups and optionally N~O-inert end groups used in the process of 20 the present invention is about 0.1 to 25.9 wt. ~, preferably 0.3 ~o 20 wt. X, most preferably 0.5 to 12 wt. X NCO.
Particularly preferred prepolymers are those which have been prepared from toluylene diisocyanates or 25 diphenylmethanediisocyanates and polyhydroxyl eompounds in qu~ntitie8 such that 33.~ to 99.~, preferably 50 ~o : 85, more preferably 50 to 66.~ equivalent percent of the hydroxyl groups (in the NCO/OH ratio 201) undergo reaction. Vse of such quantities results in 30 arithmetically half of the NCO groups put into the reaction remaining free and 66.Z ~o 0.1 equivalent percent, preferably 50 to 15, most preferably 50 to 33.
equivalent percent of the hydroxyl groups originally present remaining free.

Le A 24_S34 . . .. . .
,, ., ', , . ' . , ~ ~82~
For example, 1 mol of diol HO-I-OH is reacted with 1 mol of diisocyanate OCN-D-NCO until 50% of the OH
groups ha~e reacted with the (total~ quantity of diisocyanat~ groups (i.e. in an OH/NCO ratio o~ 1:2, based on the total quantity o~ hydroxyl groups) and 50%
OH groups remain. This reaction may be represented by the equation:

HO-I-OH + OCN-D-NCO--~ HO-I-OCONH-D-NCO (1) (1 mol) (1 mol) It is preferred to react 1 mol of triol HO-T-OH
b~I ~
with 2 mol of diisocyanate so that 66.6% of the OH groups react with the (total) quantity of diisocyanate (i.e. at an OH/NCO ratio of 1:2) and 33.3% of the OH groups remain. This reaction may be represented by the following equation:

HO-T-OH + 2 OCN-D-NCO~ HO-T-ONHCO-D-NCO
l l (2 OH O-NHCO-D-NCO
The formulae given above are idealized formulae but compounds corresponding to these idealized formulae predominate in the mixture of possible reaction products.
Relatively uniform compounds containing amino/hydroxyl groups are therefore obtainable (after hydrolysis), in contrast to the products of the one-shot/simultaneous process of U.S. Patent 4,501,873, issued February 26, 1985.
Isocyanate prepolymer formation may be stopped at the desired stage by monitoring the isocyanate content. I~ the OH/NCO reaction were allowed to go to completion, the product obtained in the first equation (diol ~ diisocyanate) would be a high polymer LeA 24 534 -14-.:, :~, -polyureshane, in the second equation an i~ocyanate prepolymer (with relatively low i~ooyanate content~ and in the ~hird equa~ion 5below) an O~ prepolymer.
If 1 mol of ~he triol OH-T-OH reazted with 1 mol OH

of di;socyanate until 33 equivalent percent of the OH
groups have reac~ed with ~he (~otal~ quantity of 10 dii~ocyanate ti.e~ in the partlcular OH/NCO ratio of 1:2), then 66.6X of the OH group6 are still free.

OH T-OH ~ OCN-D-NCO~-~ OH-T-OCONH-D-NCO (3) OH OH
The polyhydroxyl compounds, e.g. a triol T (OH)3, could have part of their hydro~yl groups converted`into isocyanate inert groups prior to their reaction with di and/or polyisocyanate~. For example, 20 such polyhydroxyl compounds may be reacted with monoisocyanate~ R " '-N~O ~R~.= organic residue) to con-vert them to a compound of the type corresponding to the formula HO-T-OH
OCO~HR''' ~T = triunctional residue of the triol ~i~hout OH groups) which is then sub~ected to the isocyanate prepolymer-ization reaction of the present invention to form the 30 NCO/OH prepolymer.
Such modifieation to form ~CO iner~ groups could be carried out to only a minor e~tent, i.e. with only a proportion of th~ molecules. Modification ~o lnclude lnert groups reduces the functionali~y o ~he 35 compound9 often resulting in a reduction in vi~cosity of the amino/OH compound mixtures of the present invention.
A 60tening effect and modification of the properties of polymers used for the production of polyurethane ureas by a polyisocyanate polyaddi~ion proces& (in particular 5 re ulting in improved plasticity and a less rlgid molecular ~tructure and combination of propertie~) are thus achieved.
It is also preferred for purposes of reaction kinetic to prepare the prepolymer component from 10 polyhydroxyl-polyamine oompounds of the kind obtainable by partial replacement of ~he hydroxyl groups in polyhydroxyl compounds by primary, aliphatically bound amino groups by means of ~o~called "ammonia suppreæsion of the polyolfi" rather than polyhydroxyl compounds.
15 Formation of the prepolymer from such aminopolyols is preferably carried out under reaction conditions such that all of the amino groups react wifh the dii~ocyanate(s) in proportion~ of NCO:NH2 = 2:1 60 that arithmetically half the NCO groups put into the process 20 remain free and preferably mo~t of the hydroxyl groups remain unreacted. ThiB can be achieved relatively easlly since hydroxyl groups react much more slowly than amino groups. It i~ possible to take advantage of a certain differential reactivity in polyols by using more 25 rapidly reacting primary hydroxyl groups or more slowly reacting Recondary hydroxyl groups in the polyols.
The prepolymer con~aining NCO and OH groups required for preparation of the amine compounds of the present in~ention may be obtained by reaction of 30 polyisocyanates with compounds containing hydroxyl groups ~nd optionally amino groups and optionally isocyanate inert groups. This reaction i8 carried out by combining the polyiso~yanates with the i~ocyanate reactive componen~s and preferably s~irring. The 35 reaction is generslly carried out at temperatures of Le A 24 534 " - ~ , ' ' :

.
. . , ~, ~ , , .

" 1 328276 20C to 120C but may be carried out at a lower temperature, if for example, the amine ~tarting components are highly reaetive and readily undergo cros8-link~ng (e.g. aminopolyols containing 5 aliphatically bound primary or secondary amino groups).
A preferred temperature range for the polyhydroxyl compounds i8 from 25~C to 80C, part~cularly from 40C
to 70CC. The reaction time depends upon the react~vities of the components, the reaction 10 temperature~ the desired isocyanate content, ~he desired isocyanate monomer content, the absence or presence of catalystQ, etc. The reaction times required for polyol~
or aminopolyols containing aromatic amino groups are generally from 30 minutes to 12 houræ, preferably l from 15 to 12 hours, most preferably 2 to 5 houræ. For aminopolyols containing aliphatic ~mino groups, very much ~horter reaction times may be sufficient (e.g. 1 to 30 minutes) Rt room temperature.
The prepolymers obtained contain both OH group~
20 and NCO groups. They are therefore capable o~ ~urther reaction and should be worked up rapidly. The degree of urgency for the rapid use of the~e prepolymers depends upon their reactivity. The progre~s of the prepolymer forming reaction should be contlnuously monitored by 25 guitable methods such as NCO titration or infra-red measurement of the NCO content. It i8 often advisable to take measures immediately after ~ermination of the reaction to en~ure the stability of the prepolymers containing NCO and OH groups. These measures may 30 include: lowering of the temperature of the p~epolymer after the reaction; the use of starting compounds differing substantlally in the reactivity of their isocyanate reactive groups (e.g. polyethers containing (more highly reactive) primary and (less reactive) 35 secondary hydroxyl groups or polyether aminopolyol~ in le ~ 24 534 . ., .. -: : ~.

1 32~276 which the aliphatic amino groups undergo virtually selective reaction); or stabilization of the prepolymers with a substance known in the art for thi6 purpose (acids, acid chlorides, e~c.).
5 Immed~ate treatmen~ of the isocyanate prepolymer ~o hydrolyze it to the amine co~pound i8, however, generally desirable even when ~uch stabilizing m~asure~
are taken.
The prepolymer compound containing NC0 and 10 hydroxyl groups is converted into the compound of the present invention containing amino and hydroxyl groups by hydro~ysis with water optionally in the presence of hydrolyzing cataly6t~ and optlonally 801vent8.
The quantity of water used to hydrolyze the 15 isocyanate groups into primary amino groups, based on one equivalent of isocyanate groups is 0.75 mol of water, preferably 0.~5 to 50 mol of water, more preferably 1 to 35 mol of water and ~08t preferably 1.25 to 12 mol of water.
The hydrolyzing catalyst6 may be inorganic or organic basic compound~ ~nd may be soluble or insolubleO
Examples of suitable hydrolyzing catalysts include:
hydroxides of elements of the lst~ 2nd and 3rd Main : Group~ and oxides of the l~t and 2nd Main Group of the 25 Periodic Table of Element~, in par~icular hydroxides of the 1st and 2nd Main Groups, such as sodium and po~assium hydroxide; carbonates and bicarbonates, preferably of metals of the 1st Main Group, such as sodium and potassium bicarbonate or soda and po~ash;
30 carboxylates, preferably of monobasic carboxylic acids (such as formic~ acetic or ethylhexanoic acid) with metals of the 1st and 2nd Main Group~ of the Periodic Table of Elements, in particular of the 1st Main Group, such as potassium acetate, potassium octoate or 35 potassium ethyl hexanoate; carbonates, bicarbonates and - . , .

carboxylates of organic trialkylammonium salts;
car~onates, bicarbonates, carboxylates and hydroxides of organic tetraalkylammonium-(C1-C18-alkyl) groups; any alkali metal and alkaline earth metal salts of weak acids such as silicic acid, hydrocyanic acid, cyanic acid, thiocyanic acid, isocyanic acid, isothiocyanic acid and hydrogen sulphide which are strongly basic in reaction due to hydrolysis in water. WatPr-soluble alkali metal salts derived from acids such as ethylene 10 diaminotetracetic acid, nitrilotriacetic acid, cyclohexylene tetracetic acid, hydroxyethylethylene-diaminotriacetic acid, 2-hydroxy-1,3-diaminopropylene-tetracetic acid, diethylenetriaminopentacetic aaid, cyclamotetracetic acid, etc. and aminopropriono-15 carboxylic acid salts of the type mentioned in DE-A
2,451,013, such as the potassium salt of morpholine-N-propionic acid and dipotassium salts of piperazine-N,N'-dipropionic acid and N-cyclohexylnitrilodipropionic acid are also suitable catalysts. The alkali metal salts of 20 mercaptans such as sodium N-butylmercaptide, lithium decylmercaptide, lithium 2-ethyl-6-hydroxyethyl-mercaptide, sodium carboxymethylmercaptide, potassium phenylmercaptide and the potassium salt of 2-aminothio-phenol as well as other mercaptides mentioned in Canadian 25 Patent 1,015,090 issued August 2, 1977 may also be used.
Tertiary amines may also be used as basic catalysts according to the invention. Those having an aliphatic or cycloaliphatic structure are preferred and mixtures of various tertiary amines may also be used.
30 Examples include amines which are in most cases not completely soluble in water; trialkylamines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, dimethyl-n-propylamine tri-n-butylamine, triisobutylamine, triisopentylamine, 35 dimethybutylamine, triamylamine, dioctylhexylamine, LeA 24 534 -19-.~ .
- . ~ . .. . . , - .. .. . - . .

., . ~ . .

,~ . : . . : . , .

1 ~2~2~6 dodecyldimethylamine, dimethylcyclohexylamine, dibutyl-cyclohexylamine, dicyclohexylethylamine and tetramethyl-1,3-butanediamine and tertiary amines containing an araliphatic group~ e.g. dimethylbenzylam~ne, S diethylbenzylamine and -methylbenzyl-dimethylEmine are suitable.
Trialkylamines containin~ a total of 6 to 15 carbon atoms, e.g. triethylamine to triamylamine or dimethylcyclohexylamine are pxeferred.
Aside fxom the trialkylamines, tertiary amines whlch have an additional tertiary amino group or an ether group, e6pecially in the ~-position to the tertiary group may al80 be used. Examples includ~:
dialkylaminoalkyl ether~ and bis-dialkyaminoalkylethers 15 (U.S. 3,330,782, DE-B 19030,558) 6uch as dimethyl-(2-ethoxyethyl)-amine, die~hyl-(2-metho~ypropyl)-amine, bis-(2-timethylaminoethyl~-ether, bis-(2-diethylamino-ethyl)-ether, bi~-(2-diethylaminoethyl)-ether, bis-(2-dlethylamlnei~opropyl)-ether, 1-etho~y-2-20 dimethylamin~etho~yethane, N-methyl-morpholine~ N-ethyl-morpholine and N~butylmorpholine; penmethylated polyalkylenediamines ~uch as tetramethylethylenediamine, tetramethyl-l, 2-propylenediamine, pentamethyldiethylene-triamlne, hexamethyltriethylenetetramine and higher 25 permethylated homologs (DE-A 2,264,527 and 2,264,528);
diethylaminoethylpiperidine, 1,4-diaza-~2,2,2)-bicyclo-octane, N,~'-dimethylpiperazine~ N-methyl-N' dimethyl-aminoe~hylpiperazine, N,N'-bis-dimethylaminoethyl piperazine, N,N'-bi6-dimethylaminopropylpiperazine, etc;
30 bis-dialkylaminoalkylpiperazine~ (disclosed in DE-A 2,636,787)~ N-dialkylaminoethylmorpholines (disclosed in EP-A 54,219)~ 4-dialkylaminopyridine and 4-pyrrolidinopyridine ~uch a~ those disclosed in Angew.
Chem., 90~ 602 ~1973); and the dislkylamino-35 alkyloxyazolidines disclosed in DE-A 3,033~832.

-:

Preferred compounds from th~s group are water-soluble compounds such as tetrame~hylethylenediam~ne, permethylated diethylene triamine, N-methylmorpholine, 2 (2-dimethylaminoethyl)-ether and ~-methylpiperidine.
The following are also suitable hydrolysis catalysts: textiary amino compounds containing urea groups such as these di~closed in DE-A 3,027,796; the acylated tertiary amino compounds disclosed in DE~A
2,425,448, 2,523,663 and 2,732,292; the perhydro-10 triazin2s containing tertiary amino groups disclosed in DE-A 2,422,335; the tetramethylguanidine and 1,3-bi~-~dialkylaminoalkyl)-guanidines disclosed in EP 33,879 (DE-A 3,003,978); the penta-substituted guanidines disclosed in CA-A 918,675; the catalysts containing 15 guanidine groups disclosed in DE-A 3,018,023; the tetrahydropyrimidines disclosed in DE-B 2,439,550 and JP-B 71 02 672s the substituted cyclic and acyclic amidines di~closed in DE-A 1,950,2G2; the cycllc amidines disclosed in DE-B 1,745,418 (U.S. 3,769,244), 2~ U.S. 3,814,707 and DE-A 3,041,834; and the cyclic propionitrile~ disclosed ~n DE-A 294199304.
It is preferred to use tertiary amines which have a marked hydrolyti~ stability which may be recovered unchanged and which are water-~oluble and/or 2S boil at temperatures below 200C at normal pressure.
The hydrolytic s~ability and/or solubility in water i8 often improved if the ~mine compound ls present in the salt form. The salts of the~e amines with weak acids (such as carbonic acid) may al80 be used in the process 30 of the present invention if these ~alts are stable. The 8alt8 of oleic acid or ricinoleic acid may also be used.
Aza-crown ethers and cryptands containing tertiary amine nitrogen atoms may also be used as tertiary amines in the pr~cess of the present invention but, are le5s 35 pre~erred due to their cost.

Le ~ 24 53~

-. ' , ' ' ..

In addition ~o the above-described catalysts, the reac~on components for the process of the present invention may include metal compounds which act as Lewis acids kn~wn in polyurethane chemlstry a~ urethanizat~on 5 catalysts. These i~clude the known lead, zinc and tin compounds, in particular tin ~ompounds and especially those tin compounds which are hydrolytically stable such as the catalysts described in EP-A 45,090, DE-A
2,657,413, 2,547,526 and 2,722,658.
Other catalytie~lly acti~e compounds ~uitable for the process of the present invention are described in DE-B 2,759,398, column 6, line 52 to column 7, line 54, and in Kunst~toffe-Handbuch, Volume VII, published by Vieweg and HYchtlen, Carl-Hanser-Verlag, Munich 1966, 15 e.g. on pages 96 to 102.
Insoluble catalyRts ~uch as those of the ~ lite or bentonite type disclosed in EP-A 99,537 (U.S. 4,525,534) may al~o be usedO
Solvents useful in the proce~ of hydrolysis 20 should be at least partly miscible ~ th water and may be selected from ~he following classes of solven~so water-soluble, aliphatic or cycloaliphatic acid 2mides containing 1 to 10 carbon atom~ ~uch as dime~hyl-formamide ~DMF), diethylformamide, N-methyl-25 pyrrolidone, dimethylacetamide, caprolac~am andformamide with dimethylormamide~ dime~hylacetamide ~nd N-methylpyrrolidone being preferred (especially DMF)~
wster-~oluble ether~ of ethylene glycol (e~g. e~hylene glycol dimethylether and ethylene glycol diethylether), 30 of diethyleneglycol, (e.g. diethylene glycol dimethylether and diethylene glycol monome~hyl monobutylether), of triethyleneglycol (e.g. triethylene glycol dimethylether) and of propylene glycol; cyclic ethers ~uch as tetrahydrouran, alkyl-~ubstituted 35 tetrahydrofura~s (e.g., 2,5-dimethyltetrahydrofuran) and ~e ~ 24 534 -~2-' -;

dioxanes such as 1,4-dioxane; water-soluble, tetra-alkylated aliphatic ureas and optionally also thioureas having 4 to 12 carbon atom6, e.g. te~ramethylurea or tetraethylurea; water-soluble, aliphatic or 5 cycloaliphatic sulphones or Rulphoxides cont~ining 2 to 10 carbon atoms, e.g. ~etramethylene~ulphone and dimethylsulphoxide; water-soluble, aliphatic or cycloallphatic phosphoric acid amlde8, e.g. hexamethyl phosphoric acid tr~amide; acetonitrile and par~ially lû water-~oluble propionitrile; water~oluble ketcnes such as ace~one and partially water-soluble ke~ones such a~
methyl ethyl ketone The 801vent8 may al~o be mixed in any proportion6. Among the solvents mentioned above, those 15 wnich boil at 56 to 250~C at normal pressure, preferably at 64 to 165C, are preferred because ~he hydrolysic products obtained are more easily worked up.
Preferred water-miscible solvents are dime~hyl-formamide, dimethylacetamide, acetonitrile, acetone, 20 methyl ethyl ketone and 1,4-dioxane. DMF is particularly preferred.
The addi~ion of solvents con~aining isocyanate reactive groups is less preferred. These include alcohols 8uch as i-propanol, t-butanol and ethyl glycol.
It is also less preferred to add Rubstantially water~in601uble co-~olvent~ to~the mainly water-soluble solvent6. ~xample~ of ~uch co-solvents include chlorinated and/or fluorinated aliphatic hydrocarbons 8uch as di-$ tri- and ~etrachlorome~hane~ trichloro-30 fluoromethane, trichloroethane~ aliphatic and aroma~ic hydrocarbons such as hexane and heptane and hydrocarbon mixtures of the llgroin or gasoline series, benzene, toluene, xylenes and higher alkylated arom~tic compounds; and halogenated or nitrated aromatio 35 compounds such a6 chlorobenzene or nitrobenzene.

Le A 24 534 ~- -23-" ., i . ~ . :

~` ~ 32~276 The 801vent if used ~hould preferably be 60 tG100% of a ~olvent which is at least partly, preferably entirely water-miscible and contain cyclic or acyclic amide, ether, urea, ~ulphoxide, sulphoneg phosphoric S acid amlde, nitrile or keto group~. Up to 40~ of the solvent may be any of the solvent6 which have been described as less suitable.
The hydroly~is reaction mixture may (preferably) be a homogeneous, monophasic mi~ture or it 10 may be a dispersion or emulsion. Working up of the product i~ generally easiest~ however, when the mixture containing the polyamino hydroxyl product i~ a two phase reaction mixture which can easily be separated mechanically.
The hydrolytic conversion of the prepolymer containing ~CO and OH groups and opt~onally NCO inert groups into the end product containing NH~ and OH groups and optionalIy NCO inert groups may be carried out by various methods already known in the art for the 20 hydrolysi~ of iEocyanate compounds. Examples of specific hydrolysis processes include: catalyti~
carbamate formation and recovery of the amlne with excess acid; catalytic carbama~e forma~ion and recovery of the amine with the equivalent quantity of acid;
25 catalytic earbamate formation and recovery of the amine by a) heat treatment of the reaction mixture or b) extraction ~ith a solvent; and catalytic hydroly~is of NCO ccmpounds to NH2 compounds in the presence of highly polar solvents containing amide group~. Each of these : 30 methods includes the hydrolytic conversion of NCO groups into NH2 groupsO The first three may include an intermediate stage ~carbamate) but the last does not, Each of these methods i~ a preerred embodiment of the above-described general process~

,Le A 24 _34 ~ . . .. . .
. : . . .

~ 1 32~276 The carbamate formation and recovery o~ the amine with excess acid process may be carried out as follows.
In the first step, an NCO/OH prepolymer containing urethane and/or urea groups is converted into the corresponding carbamate at a temperature of 0 to 40C
by its introduction into an aqueous alkali metal hydroxide solution or alkaline earth metal hydroxide solution or suspension or other basic catalyst in an amount such that the equivalent ratio of hydroxide to NC0 groups is equal to or greater than 1:1. In a second step, the carbamate is converted into the free amine by the addition of an acid ion exchanger or a strong acid (optionally in excess) with liberation of carbon dioxide.
The mineral acid possibly present in excess is neutralized by the addition of base, and the poly-hydroxylamine obtained is separated from the reaction mixture in a known manner.
The acid ion exchangers useful in the process of the present invention may be any substanc0 containing mobile acidic hydrogen atoms in an insoluble polymeric structure. Particularly suitable polymeric acids are ion exchange resins which have a styrene/divinylbenzene skeleton as the polymeric basis to which sulphonic acid groups are attached as acid functions.
In this process, the prepolymer is generally first dissolved in a water-miscible, inert solvent.
Examples of suitable solvents include acetone, tretrahydrofuran and dioxane. The prepolymer may be used in a quantity of, for example, 1 to 4no parts for every 100 parts of solvent. The prepolymer is advantageously slowly introduced with stirring (preferably within 30 to 120 minutes) into an agueous solution of an alkali metal hydroxide or alkaline earth metal hydroxide adjusted to a temperature of about 0 to 40C. The concentration of alkali metal or alkaline earth metal solution is LeA 24 534 -25-~ ' . .
. . .

~ 3~76 pre~erably 1 part by weight of base to 5-20 parts by weight of water. Inorganic and oryanic ammonium hydroxides te.g. tetraalkylammonium hydrsxide) are also suitable, but NaOH and KOH are preferred.
If the process is carried out without solvent, the isocyanate prepolymer, which should be at as low a viscosity as possible (preferably up to about 5000 mPas) and may have been previously heated (e.q. 30 to 90C) is added in a finely divided form (e~g. by injection through a nozzle) with rapid stirring. The quantity of water is increased if necessary to facilitate stirring (e.y. by a factor of 1.1 to 100).
~he quantity o~ alkali metal hydroxide or alkaline earth metal hydroxide used is preferably calculated so that at least a small quantity of free base is left after the reaction has been completed. The ratio of NC4:0H ions is preferably in the range of 1:1.01 to 1:1.30 with alkali metal hydroxide being preferred. The concentration of residual base must not be too high because otherwise urethane groups present in the prepolymer after ~ormation of the carbamate would also be hydrolyzed. A commercial emulsifier is advantageously added in quantities of from 0.1 to 1 part by weiyht (based on 100 parts of reaction mixture) to improve the homogeniety of the solutions. Vigorous stirring i5 recommended when mixing the isocyanate component with the hydroxide component. Stirring is preferably continued for about 15 to 180 minutes at O to 20C after all of the prepolymer has been added.
In the second step, the carbamate solution or suspension is combined with the ion exchanger at a rate depending on the vigorousness of gas evolu~ion and the size of the apparatus (10 to 300 minutes) (See U.S~
Patent 4,525/590, issued June 25, 1985).

LeA 24 534 -26-.~

:. , . ~ ~

` f~'`
~ 328276 When ion exchange re~ins are used, working up of the end product is very ~imple. More particularly, if the polyaminohydroxide compound is soluble 9 the reaction product is filtered and the amine solution is 5 freed from solven~ by di~tillatlon. If the polyamino-hydroxyl compound is only ~paringly soluble, R ~uitable Rolvent may be added until the amine goes into ~olution and the filtering/distilling process described above ls then carried out. If the polyaminohydroxyl compound is 0 insoluble, it is filtered from the liquid medium and the residue i~ treated with a suitable ~olvent until the amine dis~olves, and the process described above is then carried out.
The sol~ents used may be aprotic-dipolar, 15 water-miscible solvent~ ~uch as N-methylpyrrolidone, dimethylformamide and dimethylsulphoxide.
All OI' the polyaminohytroxyl compounds obtained are free from traces of volatile constituents at 0.01 to 0.1 Torr/60 to 100C.
Specific exæmples of suitable commercially a~ailable acid ion exchangers are Lewatit SC 108, S 100, SP 112, and SP 120 ion exchangers, and Lewasorb A 10 ion exchange resin. Each of these ~6 available from Bayer AG.
When the carbamate ~olution or su~pension i~
acidified by means of a mineral acid, ~tirring i~
preferably cont~nued at 0 to 20C for about 15 to 180 minute~ after all of the prepolymer has been added.
Concentrated mineral acid (e.g. sulphur~c or phosphoric 30 acid, preferably ~C13 i6 then added with vigorou6 ~tirring and cooling as rapidly as the rate of evolu~ion of CO~ allows. The equivalent ratio of acid ~o base is preferably in the region of about 1.2:1 to 2.5:1, more preferably from 1.5:1 to 2.0:1, ~o that khe reaction 35 product i8 mildly acid (pH preferably below 6, in kÇL2~ 27-..

1 ~28276 particular about 5 . 5 to 1 ) . Excess mineral acid i8neutralized by the addition of base (preferably an alkali metal hydroxide).
Subsequen~ working up may be carried out ln 5 ~everal wayR~ For example, if two phases develop (in the case of ~hort chained and hydrophobic polyamines), namely a polyaminohydroxyl compoundl ~olvent and a solvent/~al~/water pha~e, then the aqueous phase may be separated off by mean6 of a ~eparating funnel. Thi8 aqueous pha~e may then be di~carded or e~tracted with dichloromethane, for example, in an amount such as 250 ml CH2C12 to 1 liter of aqueou~ ~olution.
If two pha~es do not form, 500 ml of dichloromethane, for example, may be added to 1 liter of 15 reaction mixture and the whole mixture ~ vigorously ~haken in a ~eparating funnel. When the two phases have been left to settle, the ~olution contain~ng 601vent in addition to the polyaminohydroxyl compound i8 6eparated off. Sol~ent-free polyaminohydroxyl compound may be 20 obtained by removal of all the volatile constituents by distillation.
The entire reaction mixture may al80 be freed from volat~le constituents at 13 to 26 mbar/40 to 60C
bath temperature. The oily residue obtained ~till 25 contains alkali metal salts and i2 taken up with organic solvents ~ueh 88 CH2C12, methanol, ethsnol, dioxane, etc. and separated'from undisfiolved salt by filtration (paper filter, pressure filter~.
For polyaminohydroxyl compound~ based on 30 isocyanate prepolymer~ which are resinous at room temperature, the aminopolyether may be precipitated from the reac~ion mixture with saturated sodium chloride solutlon. The polyamine may then be isolated by decanting, dried, red~ssol~ed in organic ~olvent and 35 f~l~ered from in~oluble salts. The solven~ iB then di~tilled off.
~e A 24 ~34 -28-..

~ , :
. - - . .

1 32~276 In a second embodiment of the process o the present inventio~, an equivalent quantity of acid is u~ed to recover ~he am~ne (See U.S. Patent 4,525,590).
In this process, as a fir6t step, an i~ocyanate 5 prepolymer containing urethane and/or urea groups as well as hydroxyl groups and optionally isocyanate inert groups i8 conYerted into the eorrespond~ng carb~mate at a temperature of 0 to 40C by introduction of the prepolymer into an aqueous 601ution of base (preferably 10 an alkali metal hydroxide solution). In a ~econd ~tep, the carbamate i6 combined with a quantity of strong acid equivalent to the quanti~y of base to be directly converted into the free amine. The base i9 oonverted into the corresponding acid salt and the free amine is 15 then i~olated in known manner.
If the isocyanate prepolymer is used in the form of a solution in an isocyanate inert solvent, the ~olvent may be used, for example, in a quantity of 100 parts to 1-400 part~ of isocyanate prepolymer.
soth the compounds containing i~oeyanate groups and their ~olutions are pr~ferably maintained at temperature~ of 45 to 70C to increase their reaction velocity and enable them to be more finely diætributed ~n the solution of base provided.
The quantity of base i6 generally from 0.3 to 2.0 equivalents per NCO group. It may, of course, be : considerably higher in some cases but ~his is no~
advantageous for practical reasons. The quantity of baBe i8 generally calculated to ensure that a certain 30 quantity o ~ree base i8 left over after the reaction has been completed. If bases containing hydroxyl ions are used, such as alkali metal hydroxides, then the NCO:OHe ratio should generally be in the region of from 1:1.2 to 1:1.8, most preferably from 1:1.4 to 1:1.6 mol.

Le A 24 534 -29-:
, , ~. , ,.. .... .. :. , :.. . .. ..
. ., ,. . .. .- . ~ . . .

The quantity of OHe ions used could, however, be le~ than the s~oichiometric quantity corresponding to the isocyanate groups. In that case, the products obtainet are prelengthened via urea groups. Thi8 may be 5 ad~antageoug or certain purposes. An OH~:NCO ratio of >0.3:1 may be used in such casea.
If compounds containing tertiary amino groups are u~ed, the ratio of NC0 groups to tertiary amine groups used i8 pre~erably in the range of 1:1.01 to ~0 1:1.5, more preferably 1.1:1.3. Larger quantities of amine may however be used.
To im2rove ~he homogeneity of the reaction mixture, it i6 advantageou~ to add a commercial emulsifier ~n a quantity of 0.05 to 1 part by weight9 15 preferably about 0.1 to 0.5 parts by weight (based on 100 parts of reaction mixture).
Stirring i8 preferably continued for about 15 to 180 minutes ~t 10 ~o 25C after all the i ocyanate prepolymer has been added, and ~he carbamate reaction 20 mixture i8 then treated with acid. This acid treatment may be carried out by ei~her of two different methods.
In the fir6t method, ~he carbamate reaction mixture i8 added dropwi~e to the acid component. Strong acids are used. For example, mineral acids such as hydxochloric 25 acit, 6ulphuric acid, dilute nltric acid and phosphorir acid optionally in their aqueous form are suitable.
Strong organic acids such as o~alic acid, formic acid or acet~c acid or similarly strong organic acids which are at least a~ ~trong a~ acetic acid may also be used.
30 Hydrochloric acid and sulphuric acid are preferred, e~peci~lly 6ulphuric acid. The acid in the reaction ve88el i8 preferably at a temperature of 0 to 20C. The time taken for addition of ~he carbamate depends upon the vigorousne~s of gas e~Jolution (~hich set~ in 35 ~mmediately).

~g~3g ,' .
. ~ ,. . ~ .

1 32~276 The equivalent ratio of acid to base is approximately 1:1, i.e. 1 gram equivalent of protons is used per gram equivalent of OH~ ions or per gram equivalent of a compound containing tertiary amino groups capable o~ removing a H~ ion (approximately equivalent guantities). The reaction mixture is then neutral to basic and corresponds to the pH of a mixture of alkali metal salts or amine salts and an aromatic or aliphatic amion compound~ Stirring may then be continued for 5 to 30 minutes at 20C.
In a preferred variation of this process, the carbamate component and the acid component are introduced separately into a common reaction vessel. These are preferably added at a rate such that the same equivalent quantities of OH ions or of tertiary amino groups and of protons enter the reaction chamber within the same period of time to avoid disequilibrium between the two reactants.
Acid ion exchange resins of the type described above as useful in the first preferred embodiment may be used as strong acids in both variations of this process.
In another embodiment of the present invention, carbamate formation and recovery of the amine are accomplished by heat treatment of the reaction mixture or extraction with a solvent. Such processes are disclosed in U.S. Patent 4,540,720, issued September 10, 1985.
In this method, the isocyanate prepolymer component optionally dissolved in an isocyanate inert solvent, is mixed with a base and water to convert it 30` into a reaction mixture containing compounds carrying carbamate groups. The polyaminohydroxyl compound is recovered from the reaction mixture containing compounds with carbamate groups by either heat treating the reaction mixture with decomposition of the carbamate groups in the mixture and separating off the polyamino hydroxyl compound or extracting with a solvent.
LeA 24 534 -31-- . .

:, . : ,-" .
.~ , ~ 328276 If the i~ocyanate compounds are used in the form of solution~, the preferred temperature range i8 from 20 to 40C but ~ay be up to the boiling point of the particular ~olvent used. Solution~ of isocyanate 5 compounds may contain, for example, 10 to 1000 partQ of isocyanate prepo~ymer to lOD parts of solvent.
When the i~ocyanate compounds are mixed with the basic medium, ~he resulting reaction solution 6hould be at a low temperature in order to avoid side reactions 10 as much as po6sible~ The temperature of the reaction mixture of component~ should~ if possible be below lOO~Cp preferably below 70C and better still below The low vi cosity basic medium ~hould 15 preferably be at a very low temperature (e.g. at -25C
to 40~C, preferably 0C ~o 25nC) before ~he reaction.
In addition, the mixture may be cooled during ~he reaction ~o keep the reaction temperature within t~e optimwm range as far as pos~ible, although the 20 permixsible reaction temperatures also depend upon the method of mixing and the reaction procedure.
The ratio of liquid volume initially lntroduced into the reaction ves6el and liquid volume subsequently to be introduced i8 approximately in the range of 1:1 to 25 1:3 although the6e figure do not, of course, apply when a less preferred, ~ol~d isocyanate prepolymer i8 added in a finely dispersed form.
In a continuous process which i~ particularly suitable for large ~cale technical production, the 30 isocyanate compounds (optionally as solution~ and the aqueous base are introduced ~eparately in~o a common reaction chamber~ reacted together with the aid of vigorous mixing ~e.g. by means of a flow mixer) and rapidly di6charged from the mixlng chæmber. The 35 component~ may be dosed into the mixing hamber by means ~L539 .

,: . . . .
' ' : , 1 3~32.7~
of graduated dropping funnels or by means of a piston and/or membrane dosing pump or some other mechanical dosing device. When the components are dosed on a con-tinuous basis, very rapid reaction between the two com-5 ponents is preferred and may be achieved by mixing themtogether within a very short time (seconds or fractions of a second) by means of a suitable, optionally mechani-cally driven device. The mixture is then discharged from the reaction chamber. Suitable apparatus are described in detail in U.S. Patent 4,540,720, issued September 10, 1983.
The reaction components are generally introduced to the flow mixer at temperatures of about -25C to 40C. When a dynamic mixer is employed, as is preferred, the reaction temperatures rise to about 50-150C due to the shearing forces produced, depending upon the heat of reaction. In general, however, it is advisable to keep the temperature below 100C (if necessary, by cooling the mixing apparatus).
If cosolvents are used, the temperature should be kept below the boiling point of those cosolvents if that boiling point is lower than the boiling point of water.
Various additives may be used to facilitate the reaction of the isocyanate groups with the aqueous base.
For example, one or more commercial emulsifiers may be added (e.g. in ~uantities of 0.01 - 1 part by weight to 100 parts of reaction mixture) to facilitate homogenization. Catalytically active compounds may also be added to increase the reaction velocity. Suitable catalytically active compounds include compounds containing tertiary amino groups of the kind generally known in polyurethane chemistry and used in the production of polyurethane foams to accelerate the isocyanate-water reaction.
LeA 24 534 -33 ~!

, , ~ ` ' ~ , ' ', ~' ' , 1 328~.76 In accordance with the present invention, the compounds containing carbamate groups obtained by mixing the i60cyanate compound~ with the basic medium are directly converted into compounds containing a~ino 5 groups, either by hea~ treating the reaction mixture containing the carbamate^carrying compound~ to ~ecover ~he amine or by ex~racting the reaction mixture with a solvent (carried ou~ continuously or on a batch basi6).
The heat treatment for oarbamate decompositicn 10 is preferably carried out under conditions re~ulting in removal by distillation of water and o any other solvents. The reaction mi~ture containing carbamate groups is heated to temperatures above 40C, preferably above 60C and most preferably above 80~C for about 30 15 to 480 minutes by means of a 60urce of heat.

The ~olvent distil~ off during this heat treatment.
Thi8 simultaneous heat treatment and ditill~tion may be carried out under reduced pressure, e.g. at 200 to 950 mbar. The reduction in pressure may be carried out 20 gradually and continuously. Thus distillation may be begun a~ normal pressure and termi~ated at about 0.5 mbar.
Any of the above-described treatment methods and modifications thereof which are described in the art 25 may be used for a continuous processO Continuous rcco~ery of the polyaminohydroxyl compound is preferably carried ou~ by a hea~ ~rea~ment of the reaction mixture containing ~ompound~ with carbamate groups after continuous production of the said reaction mixture.
The compounds containing carbamate groups may al80 be converted into the corresponding compounds containing amino groups (polyhydroxylamines according to the invention) by ~reatment of the reaction mixture containing carbamate compounds with a suitable ~olvent.

Le A 24 534 1 32~.76 In this method, it i8 particularly ~uitable to use water immi~cible organic solvents which are non-solvents for the compounds con~aining carbamate groups and for the carbonic acit ~alts produced bu~
5 which are good solvents for the amines formed ~n the reaction. Examples of such solvents include dichloromethane, trichloromethane, tetrachloromethane, cyclohexane, methylcyclohex&ne, pentane, hexane, benzene and toluene. Dichloromethane i~ particularly suitableO
In principle~ it would also be po6sible to use ~ater-mi~cible solvent6 provided they are at least poorer solvents for the carbonic acid salts than water.
Examples of such olvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-amyl alcohol, 15 cyclic ethers such a~ dioxane or ~etrahydrofuran, water-soluble acyclic ethers such as diethylene glycol dimethylether and ketones ~uch as acetone and methyl ethyl ketone. Here again, a two phase system is obtained after conver~ion of the compound containing 20 carbamate groups into a polyamine. The aqueous phase contains the carbonic acid ~alt while ~he amlne i8 concentrated in the organic phase. Due to their mutual miscibility, however, a cer~ain quantity of organic solvent and am~ne is also pre~ent ~n the aqueous phase : 25 while the organic phase contains a certain quantity of 6alt and water. The organic ph~æe must thereore be filtered again after removal of the solvent by distillation.
Extraction may be carried out at normal, 30 reduced or excess pressure and i8 preferably e~rried out at normal pre~sureO
The extraction process may be modified in that the reaction mixture con~aining compound~ with carbamate group~ may be mixed with ~ubequivalent quantitieæ of 35 acids tbased on the quantity of base, i.e. about 0.01 to ~, ~ , .: . .. . .

1 3~.76 0.99 equivalents of acid per unit equivalent of base) before or during the extraction. Both thi~ modification and the introduction of carbon dioxide are particularly suitable whenever an OHe:NCO ratio greater ~han 1:1 has 5 been used.
Catalytie hydrolysiæ of isocyanate compound~ to NH2 compounds in the presence of 801vent~, optionally very 6mall quantities of cataly~t i~ the most preferred proce6s for producing the polyhydroxylamine6 of the 10 present invention. ~See, DE-A 3,223,395, DE-A 3,223,400, DE-A 3,223,398, DE-A 3~223,397, DE-A 3,223,396, DE A 3,244,912.) This preferred process may be carried out as a sing~e stage proc~ss in which the i~ocyanate groups of 15 compounds containlng NCO group~ and OH groups and optionally i~ocyanate inert groups are hydrolyzed with water at a temperAture of from 20 to 210C, preferably 40 to 150C, optionally in the presence of compounds which are ba6ic in reaction as cataly~ts and in the 20 presence of at least S parts ~based on 100 parts o isocyanate prepolymer) of at least partly water-miseible polar ~olvents. The water-miscible polar olvents preferably contain carboxylic acid dialkylamide, lactam, te~raalkylurea~ sulphone, sulphoxide, phosphoric acid 25 dialkylamide, nitrile, ether or ~etone group~, and boil in the range of from 56 to 250C and have a dielectric constant of at least 10. A substantially homogeneous reaction mixture i6 maintained during the reaction.
In a particularly preferred embod~ment of this 30 process~ the baRic compound6~ based on 100 parts by weight of isocyanate prepolymer component are selected from 0.0001 to 10 parts by weight of tertiary amine compounds, amidines and other strong basic amine compound~; 0.0001 to 10 part6 by weight of alkali metal 35 hydroxides, alkaline earth metal hydroxide~, Le ~ 24 53~

.

32~76 tetraalkylammonium hydroxides9 alkali metal silica~es, alkali metal aluminates~ phenolates, thiophenolate~, mercaptides, hydrogen sulphide~ of alkali metalR, ~oluble alkali metal and alkaline earth metal ~alt~ of 5 (iso) (thio)eyanic acid and ~-diketone enolates; 0.0001 to 10 parts by weigh~ of carbonate6 and bicarbonates of alkali metal&; 0.0001 to 10 parts by weigh~ of alkali metal and alkaline earth metal ~alt~ of organic carboxylic acids, hydroxycarboxylic acids and/or aminocarboxylic acids 10 and mixtures thereof. The solvent component is made up of carboxylic acid dialkylamide and lactam 601vents, acetone or acetonitrile in quantities of > lO part~ by weight (ba8ed on 100 parts by weight of isocyanate prepolymer component) and ~ 0.75 equivalents of water per 15 equivalent of isocyanate groups in ~he isocyanate prepolymer component.
For complete conversion of the NC0 groups into NH2 ~roups it is necessary to u~e a~ least 0.75 mol of water per equivalent of NC0. If less than 0.5 mol of 20 water i~ usedS then prelengthening with urea formation preferentially takes place. On the other hand, it has 6urprisingly been found that a ~ery large excess of water also results in a greater amount of pre-lengthening. This al80 occur6 when the reaction mixture 25 is a single phase. I~ has been found tha~ the op~imNm quantity of water depends upon both the quantity o~
801vent u8ed and upon the quantity of NC0 groups to be converted.
The amount of water used for each equivalent of 30 NC0 groups ~8 therefore preferably > 0.75 mol of water, in particular 0.75 to 50 mol of water, especially 1 to 35 mol of water and mo6t preferably 1.25 to 12 mol of water. Based on 1000 g of ~olvent (e.g. DMF) water is used in quantities > 1 g, preferably > 5 g, more 35 preferably 10 to 500 g 1 mo~t preferably 20 to 300 g, and .

~ ~2~276 ~t the same time the quantity of water uGed ehould be at least ~ 0175 mol, preferably > 1 mol of water per equivalen~ of ~C0 groups. If the ab~olute quantity of water necessary and the mo~t advantageou~ ~olvent/water 5 ratio are ob~erved, then the quanti~y of solvent used i8 ' 10 parts, preferably ~ 100 parts, mo~t preferably up to 1000 parts by weight of 601vent to 100 parts by weigh~ of NC0 prepolymer component. It has been found that the mini~um quantity of solvent required for 10 complete conver~ion of NC0 to NH2 depends upon the reaction temperature. The higher the reaction temperature, the lower the quant~ty of ~olvent may be.
The quantity of water required i6 to a large extent unaffected b~ reaction temperature.
Simple preliminary experiments may be necessary to determine the optimum ratio of NC0 equivalents to water and to ~olvent within the above-discussed range~.
Compounds are considered to be catalysts if they ara capable of raLsing ~he NH number of the 20 amine( B ) in the product to a level above that obtained without using them. A catalyst may be ~olid or liquid but must be sufficiently ~olublet preferably completely ~oluble in the react10n mixture. Ba~ed on 100 parts by weight of the isocyanate componen~, the ca~alyst, i 25 used, is used in a quantity of O.OOOOS to 10 parts, preferably 0.001 to 5 parts~ ~os~ pre~era~ly 0.005 to 1 part by weight of eatalyst. The quantity of catalyst employed depends upon the solven~/water ratio. The optimum amount of ~atalyst iB lea~t when the 30 solv~nt/water rat~o i8 at the calculated optimum level but a certain minimum amount of catalyst may still be required. If the wa~er/solvent rat~o i~ not optimized, result6 may be impro~ed by increasing the quantity of catalyst. The quantity ~f catalyst to be employed for 35 complete conversion of NC0 group~ into NH2 group~ al~
~.e~9.

;

~ 3~8~7 6 depends upo~ the reaction temperature. It has been found that a larger quantity of catalyst i~ required at lower reaction temperatures (e.g. at 45C~ than at higher temperatures (e~g. at 100C). If the amine yield 5 is incomplete with a given quantity of catalyst, the yield may be increased by increasing the reaction temperature.
The process of the present invention could theoretically be carried out wi~hout a catalyst but very 10 high temperatures of about 150C and higher are then required for complete conversion of NCO groups into NH~
groups. The NH2 yield progressively falls with decreasing temperature if no catalyst i8 used.
Basic inorganic and organic salt3 may be used 15 as catalysts. In par~cicular, the following may be used as cataly~ts in addition to those already mentioned abo~re: hydroxides of alkali metals and alkaline earth metals and tetraalkylammonium hydroxides, in particular NaOH and KOH; ~oluble alumina~es, e.g. sodium aluminate;
20 carbonate~ of alkali metals, in par~:~cular ~oda and potaæh~ bicarbonates of alkali metalst in particular sodium and potassium bicarbonate; alkali metal and alkaline earth metsl salts of mono- and polycarboxylic acids free from isocyanate reactive groups; alkali metal 25 salts of phenols and thiophenols optionally substituted with isocyanate ~nert groups; soluble alkali metal and alkaline earth metal 8alt8 of weak acids ~uch as cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, 8ilicic acid~ acids of tri~alent to pentavalent 30 phosphorus, hydrocyanic acid and hydrazoic acid; alkall metal mercaptides and sulphides and hydrogen (poly)sulphdies~ ~diketone compounds such as sodium, pota~ium, magnesium and zinc acetyl acetonates and acetoacetates~ also chemically incorporated catalyst~
35 which contain both an isocyanate reactive group such as le~D_2L~ 39_ .. .. ~

: :

1 328~7 6 a hydroxyl, mercapto, primary and/or secondary amino group or ~etene aminal group and a group such as alkoxide, mercaptide, (thio)-phenolate, carboxylate, dialkyl tin, dialkylamino or amidine group which catalyze the reaction of isocyanate groups with isocyanate reactive groups such as OH or NH2.
Basic catalysts containing nitrogen such as tertiary amines are also suitable. These nitrogen containing catalysts have an aliphatic or cycloaliphatic structure. Examples of such catalysts include in particular trialkylamines and dialkylaminoalkylethers as well as acyclic, cyclic or polycyclic compounds containing at least one unit having an amidine and/or guanidine structure. Tertiary amines of the pyridine series and tertiary amines containing at least one aromatic group attached to the nitrogen atom te.g.
dimethlaniline) are also effective. Tertiary amines which are not water-soluble should preferably boil at temperatures below 250C, in particular below 200C.
Polyvalent metal compounds known in the literature as catalysts for isocyanate chemistry may also be used in the process of the present invention. These include in particular compounds of tin, zinc or lead such as dibutyl tin dilaurate, tin octoate and lead octoate~
They are, however generally less preferred.
The limits (in particular upper limits) which should be observed with respect to the quantities of solvents used in this process are: for every 100 parts by weight o~ isocyanate prepolymer compound, the quantity of solvent used in the reaction mixture for LeA 24 534 -40-~'~ .
.

;

~ 328~76 hydrolysis ~hould be ~ 10~ preferably 20 to 1000, most preferably 25 to 300 parts by weight.
The quantity of water and optionally Rolvent used should be ~ufficient o form a substantially 5 homogeneous (at the most slightly cloudy) or preferably a homogeneous, clear solution with ~he i~ocyanate compound at the reaction temperature~ 8 ~ . The quantity of water used is preferably sufficient to form a single phase mixture at any proeess temperature but alway~
10 within the lim~ts of w~at has been stated above concerning the ratio of solvent (e.g. DME) to water and the ratio of water to i~ocyanate prepolymer component.
The catalytically active compounds are ~enerally added ~o the solvent~ and water. They could 15 ~n some cas~ be added to the compound containing i~ocyanate groups but this i~ not preferred.
If the i~ocyanate compound i8 to be hydrolyzed to polyamine with a suficiently high amine ~umber (high conversion rate) it i8 advantageou~ to maintai~ the 20 concentration of isocyanate compound in the reaction mixture at ~90 wt~ ~, preferably '80 wt. Z.
At the same time, the quantity of 601vent added ~hould be sufiicient to maintain a substantially homogeneou~, preferably a completely homogeneous 25 reaction mi~ture~ but al~ays within the above-defined quantltative ratios o water to 801vent to isocyanate.
Prelengthening may occur as 8 sid~ reaction of the process. That i8, the isocyanate may react ~ith the amine already formed to produce ureas by ehain linking.
30 Thi6 side reaction can to a large extent be ~uppressed by carrying out the process in a dilute solution, using a catalyst and maintaining relatively high reaction temperatures, ~e.g. 80C to 130C). Although it i8 desirable to keep ~he extent of these ~ide react~ons as 35 low as possible, a cer~ain amoun~ o~ prelengthening may ~2L~
-4~ -- :

~ 3~7~) be accepted for economic reasons. Keeping the isocyanate concentration at 90 wt. % and maintaining a substantially homogeneous reaction mixture, however, enables the isocyanate groups to be virtually completely converted into NH2 groups if the process parameters are carefully observed.
The reaction is pr~ferably carried out in a homogeneous phase. Slight overdosing with water or with the isocyanate compound may give rise to cloudiness in the reaction mixture because the starting materials are then incompletely dissolved.
The hydrolysis reaction may be carried out at temperatures of from 20 to 210C, as already mentioned abo~e, but it is preferably carried out at 40 to 150C, most preferably at 80 to 130C because these temperatur~s provide the best volume/time yields combined with high solubility and, surprisingly, the least amount of urea prelengthening. In some cases it may be necessary to operate under pressure in order to reach sufficiently high temperatures. On the other side it is also possible to reduce pressure in some cases. Then it is possible to reduce the amount of catalyst or it is even possible to work without a catalyst.
The onset of the reaction is recognized by the almost spontaneous evolution of CO2. This can sven be observed at low temperatures, e.g. at 10C, but it is much more advantageous to employ higher temperatures in order to suppress urea formation. Thorough and rapid mixing with formation of a homogeneous solution of the reactants is important. This may be achieved mainly by using solvents but also by lowering the viscosity by application of elevated reaction temperatures. The reaction may be carried out either continuously or batchwise.
Information with respect to both the continuous and the batchwise process of the present invention is disclosed in U.S. Patent 4,565,645, issued January 21t l9B6.
LeA 24 534 -42-,. ~

.. . ~ : ., - ~ . -Working up of the product may also be carrled out continuously or batchwise. The reaction mixture is normally worked up by distillation, extraction or phase ~eparation or by a c~mbination of these method~.
If the isocyanate-containing compound ~till con~ain~ free (i.e. monomeric) isocyanate from the process of lts preparaticn, any monomeric amine ~ormed from thi~ monomeric isoc,-anate i8 liable to accumulate in the water/~olvent phase lf the product i8 worked up 10 by phase separation. The polyaminopolyol obtained by this 8imple method of working up is then virtually free from monomerO In that casep however, it may be advisable to free ~che aqueou~ ~olution from monomeric ~mine before it i8 reU6ed.
In the preferred method of working up, the reaction mixture i6 worked up without phase separation by di~tilling off the solvent or solvent/water mixture after terminat:ion of the reaction (no further evolution f C2 observed), preferably with t~e aid of a vacuum, 20 e.g. at 1 to 700 Torr, optionally followed by application of an even hlgher vacuu3n, e.g. 0.001 to 1 Torr to remo~e volatile residues. I~ has been found to be ad~antageou~ to carry out thi~ me~hod at temperatures beginning at about 60 to 100C and later riRing to 80 to 25 100C. The 601vene removed by diætillation may be used again, optionally everal time~.
The polyamino alcohols obtained by the various me~hods of working up are generally colorless to slightly colored, low tv medium viscosity (possibly 30 higher melting) products having the required amino/hydroxyl group content. These polyaminopolyols in addition may contain urethane and/or urea and/or uretdlone and/or iRocyanurate and/or biuret group~, depenting upon t~eir starting material~. In ~ome cases, 35 ether and/or acetal and/or carbona~e and/or ester andtor Le A 24 534 j, ~
' ' . ~ '` ' '' ` ' ~
, - - j. ` : !

~ 328~76 thioether and/or dialkylsiloxane groups and/or the residues of polybutadianes may also be present in the product groups if these were already present in the isocyanate compounds. Additional linkages may form as a result of side reactions. For example, urea groups may form during hydrolysis from parts already saponified and any still remaining isocyanate groups. The quantity o~
primary aromatic amino groups present in the poly-aminopolyols is at the most equal to the quantity of isocyanate groups in isocyanate prepolymer starting material.
The polyaminohydroxyl compounds of the presentinvention, especially those containing aromatic primary amino groups are preferred reactants for (optionally masked) polyisocyanates in the production of polyurethane ureas, cellular or non-cellular polyurethane(urea) plastics and polyurethane(urea) foams due to their low pressure. These polyaminohydroxyl compounds may be used either alone or in combination with other low molecular weight (molecular weights 32 to 399) and/or relatively high molecular weight (molecular weight 400 to about 12,000) compounds containing isocyanate reactive groups (hydroxyl, amino, thiol, hydrazide and similar groups).
Suitable starting components for the production of polyurethane plastics in accordance with known processes are mentioned above in connection with the preparation of the isocyanate prepolymer starting material. The above-listed disclosures also indicate auxiliary agents and additives which may optionally be used for the production of polyurethanes.

LeA 24 534 -44-..
. . , . :
, The use of the polyaminohydroxyl compounds of the present invention for ~he production of polyurethane(ureas)s is also a sub~ect of the present invention. These polyaminohydroxyl compounds may be S used, for example, for the production of elastomer~, coat~nga, and threads spun from melt~, solutions, dispersions and reactive component mixtures. The main purpose for which ~he polyaminohydroxyl compounds of the present invention are u~ed, however, i8 the productivn 10 of ~olded part~ with compact surfaces by the RIM
keaction injection molting) process in elosed molds for u~e in the manufacture of motor vehicles as mudguard~, door panels, swellers, bumpers, all-round panellng and ~poilers, Those polyaminohydro~yl eompounds in which the sum of equivalents of primary amino groups (EqNH 3, of hydroxyl groups (EqOH) and of any inert end groupR
(EqIN) minus the sum of equivalents of hydroxyl group~
and any inert groups present is equal to 2 + 0.25, 20 preferably 2 ~ 0.1 as represented by the equation:

( qNH Eq~H ~ EqIN) - (EqoH ~ EqIN) = ~ ~ 025 (A) (preferably - 2 ~ 0.1) are particularly suitable for the RIM process.
In the case of polyether compounds corresponding to formula (I), for example, ~his means that Sr + p ~ 8) - (p ~ 8) ~ 2 ~ 0.25, preferably 30 2 + 0.1. The presence of approximately two primary amino groups in the preferably relatively high molecular weight polyaminohydroxyl compounds containing urethane and/or urea groups of the present invention ensures a particularly smooth and favorable production of a : 35 polymer by the RIM process and correspondingly advantageous mechanical propertles of the product.
~_a 2i_~3~ 4 : ~ .

Where no inert end groups are present in the polyaminohydroxyl compound (as is preferred), the following compounds are preferred for use in a RIM
process:
5 tri 1 i 0.25, more preferably func~ional 1 ~ 0.10 hydroxyl groups poly-tetra- amino 2 ~ 0.25, more preferably functional hydroxyl 2 1 0.10 hydroxyl groups compounds penta- contain- and 3 ~ 0.25, more preferably functional ing 3 + 0.10 hydroxyl groups 2 ~ 9.~5 hexa- amino 4 ~ 0.25, more preferably 15 fucntional group~ 4 ~ 0.10 hydroxyl groups especially ~hose based on ~riunctional compounds.
The methods for producing molded parts (from integral foams) and the technology of RIM have been 20 fully deseribed in the literature. Such disclosure is mad~, ~or eacample, in the handbook, BAYER-Polyurethane, Order No. PU 50025/BAYER AG, D-5090 Leverkusen, Issue 1. 79, D100-779/847990, page~ 139-179, and in Ku~ststoff-Handbuoh, Volume 7, Polyurethane (publishers 25 C. Hanser-Verlag~, Munich~ Vienna, ~983, pages 333-390.
The polyaminohydroxyl compound~ of the present in~ent$on, in part~cular tho~e which fulfill the condition~ of Equation A and especially those based on tri~unctional polyethers yield molded part~ whieh have 30 increased rlgidity, both at room temperature and in particular at elevated temperatures (e.g. 120C), a higher heat distortion value and a distinctly bet~er "sa~" value when compared with corresponding poly~mino compounds containing amino end group6~ corresponding 35 polycarbo~yl compounds ~containing only OH group~) and mixture6 of these components.
Other applications for the polyaminohydroxyl compounds of the present invention include, for example~
their use a~ coupling components for diazo dyes, as ~46-- , - - , - . ~ . . -~ 328276 hardeners for epoxide and phenol resin~ and their use in any other known reactions of amines such as amide formation or imide formation and as other modifylng agent~ or polyamides.
The invention i6 further illustrated bu~ is not intended to be limited by the following examples in which all parts and percentages are by weight unless o~herwise specified.
~XAMPLES :
10 Example 1 400 g of a linear hydroxypolyether wi~h OH
num~er 28 prepared by blockwise addition, first of 80 wt. Z of propylene oxide and then of 20 wt X of ethylene oxide, to propylene glycol, and 22.2 g of 15 l~ophorone diiEocyanate ~IPDI) were stirred, first at 40C or 3 hour~ and then at 120C for 3 hour3. The isocyanate value of ~he NCOtOH prepolymer obtained was 0.7 wt. Z (theoxetical 0.99~) NCO for a 1:1 adduct of thi3 polyether and IPDI containing one free NCO group 20 and one free hydroxyl group. Thl8 prepolymer containing 1socyanate and hydro~yl groups wa~ immedia~ely converted into the ~mine as follows:
A mixture of 400 g of water, l g of an emulsifier (alkylsulfate-potassiumsalt type) and 4 g (O.l mol) of 25 NaOH was ~ntroduced in~o the reaction vessel at 20C. The prepolymer described above was run into this mixture at 20~C within 30 minutes with ~tirringO After further stirring at this ~emperature for 5 minutes, the reaction mixture was : stirred at 80C for one hour and water was ~hen 30 distilled off at 100C/18 mbar subsequently at 100C/0.13 mbar and the sal~ was filteret off. The polyEminohydroxyl protuct had the following properties:

~ : ., , ~ ~ . . , NH number (HC104): 26.3mg KOH/g (from acid titration) NH/OH number (AC20/Py):36.38 mg KOH/g (P~H plus 0~ group~
mea~ured) Acid number (Ac20 /Py) û.6 mg KOH/g 10 IPDA content (HPLC): 0.997 Z
Vi~cosity at 23C: 4,400 mPas.
E~ample 2 In this example9 an NCOtOH prepolymer having an isvcyanate content o 1.83% prepared from lOOO g (0.500 mol) of a polypropylene glycol with OH number 56 and ¦ 87 g (0.500 mol) of toluylene dii~ocyanate ~as used.
The prepolymer was worked up a~ ~oon as it had been 20 prepared and the above-mentioned isocyanate content had ¦ been reached to prevent the prepolymer from continuing to react to form an i~ocyanate-free high polymer polyurethane.
A mixture of 500 g of water, 28.4 g of NaOH
25 (0.71 mol) and 0.2 g of an emulsifier (Mersolat H of Bayer AG) was introd~ced into the reaction ~es~el at 20C. The prepolymer described above was then added with stirring at this temperature in the course of 20 minutes and ~tirring wa~ continued for a further 15 30 minutes at this temperature. The product wh~ch was then worked up ~s in Example 1 had the following properties:
NH number (HC104): ~0.4 mg KOlH/g NH/OH number (Ac20/Py3: 48 . 7 mg KOH/g Acid m~mber (Ac20tPy): 0.14 mg KOH/g 35 TDA content (HPLC): 0.297 X
H20 O o lO X (Karl Fi~cher3 Vi~cosity at 23C: 8,500 mPas.

LQ ~ ~5 3 4 , . :
.

Example 3 A prepolymer with isocyanate content 1.3%
prepared from lOoo g of a polyether triol with OH number 27 ~prepared by blockwise addition, first of 78 wt. % o~
propylene oxide and then of 22 wt. % o~ ethylene oxide to ~rimethylolpropane) and 43.4 g of toluylene-2,4-diisocyanate by stirring the components for one hour at 80C was used in this example. The product was worked up immediately after it had been prepared.
A mixture of 1 liter of water, 22.3 g of NaOH
(0.56 mol) and 0.5 g of Mersolat~ H emulsifier was introduced into the reaction vessel at 20C. The NCO/OH
prepolymer described above was added with stirring at this temperature in 15 minutes and stirring was continued at this temperature for a further 15 minutes. The product which was worked up as in Example 1 had the following properties:
NH number tHC104): 19.5 mg KOH/g (theroretical:
17.2 Mg KOH/g) NH/OH number (Ac2O/Py): 36.5 mg KOH/g Acid number (AC2O/Py): 0.2 mg KOH/g TDA (HPLC) 0.062 %

Viscosity at 23C: 3800 mPas Example 4 An NCO/OH prepolymer with an NCO content of 1.3% prepared from 1000 g of the polyether from Example 3 and 55.9 g of toluylene-2,4-diisocyanate by heating at 80C for 90 minutes was used in this Example. The prepolymer was worked up as soon as it had reached the NCO content of 1.3%.
A cold mixture (20C) if 1000 g of water, 19 g of NaOH (0.475 mol) and 1 g of Mersolat* H emulsifier was LeA 24 534 49-*Trade-mark :~, . .

, , - : ;

~ 328276 introduced into ~he reaction ve~sel. 1 kg of ~he NCO/OH
prepolymer described above was added within 30 minutes and the mixture was then stirred for 10 minutes and kept at 80C with stirring for 1 hour. The reaction product 5 which was worked up as in Example 1 had the following propertie~:
NH number (HC104): 21.5 mg KOH/g NH/OH number (Ac20/Py): 32.2 mg KOH/g TDA (HPLC): 0.212 X
10 Acid number (Ac2O/Py) <0.1 mg KOH/g Vi6cosity at 23C: 6,500 mPaq Exam~le 5 The NCO/OH prepolymer u~ed in thi6 Example had j an NCO content of 0.61% and wa~ prepared from 9,500 g of 15 a polyether wi~h OH number 28 (prepared by blockwise addition, fir6t of propylene oxide and then of 17 wt. X
¦ of ethylene oxide to trimethylolpropane) and 276 g of toluylene-2, 4 -diisocyanate by stirrlng for 5 hours at 60C. This prepolymer contained on average about two OH
20 groups to every NCO group. It was worked up a~ follows immediately af~er it had been prepared:
A mixture heated to 90C of 1000 ml of dimethylformam~de (DMF), 50 ml of wa~er and 0.1 g of KOH
was introduced in~o the react~on ves8el. 1000 g of the 25 NCO/OH prepolymer described above was added at this temperature within 10 minute~. When all the prepolymer had been added ~and CO2 evolution had cea~ed) the 801vent and exce3~ water were diRtilled off by application of a vacuum (initially 19 mbar, 6ub~equently 30 0.13 mbar) and elevation of the bath ~emperature to 100C, The polyaminohydroxyl produc~ had the following propertie8:

Le~9 .

NH number (HCl04)o 10~4 mg KOH/g NH/OH number (Ac2O/Py): 30.4 mg KOH/g Acid number (AC2O/Py): '0.2 mg KOH/g TDA content (HPLC): 0.305 5 Viscosity at 23~C: 2,500 mPa~
Exa~le 6 The NCO/OH prepolymPr used ~n this exæmple had an NCO con~ent of l.SX and had been prepared from 500 g of the polyether from Example 5 and 29 g of toluylene-10 2,4-dlisocyanate by reacting the components for 3.5 hours at 60C. This NCO/OH prepolymer contained on average abou~ two NCO group8 to on~ OH group. It was used for further processing immediately after it had been prepared.
A mi~ture heated to 90~C of 1000 ml of DMF, 50 ml of water and 0.1 g of KOH was introduced into the reaction vessel, 1000 g of prepolymer described above were added within 12 minute~ with ~tirring and the product was then worked up as in Example 5. The 20 polyaminohydroxyl product had the following propertie~:
NH number ~HC104)~20.4 mg KOH/g NX/OH number ~Ac2O/Py):31.6 mg KOH/g TDA content (HPLC): 0.549 X
visc08ity at 23C: 3,200 mPa~
25 Example 7 A prepol~mer with NCO content of 2.1~ prepared rom 1000 g of a polyether with OH number 50 by 3 hours ~tirring with 144.5 g of 2,4-toluylene diisocyana~e at 60C was used in this example. The polyether used was a 30 mixture of two polyethers (A) and (B). Polyether (A) was obtained by blockwise addition~ first of 87 wt. X of proyylene oxite and then of 13 w~. X of ethylene oxide to glycerol and had an OH number of 35. Polyether (B) had an average functionality of 2.4 and was prepared by 35 the-addition of propylene oxide ~o a water/trimethylol-.

", : . -propane mixture having an OH equivalent ratio o 53~:47~. Its OH number wa~ 56. The OH number of the mi~ture was 50 and the functionality of the mixture was 2.5. The NCO/OH prepolymer was used for further 5 processing 12 hours after its preparation. During ~his time the NCO value fell from 2.3X to 2.1~. The prepolymer contained on average one hydroxyl group to every two NCO groups.
A mixture of 1,300 g of DMF, 40 ml of water and 10 û.02 g of KOH was introduced into the reaction vessel.
960 g of the prepolymer described above SNCO content 2.1X) were added within 20 minutes at an internal temperature of gnoc. The product which was then worked up as in Example 5 had the following propertie6:
15 NH number (HC104): 30.9 mg KOH/g NH/OH number (Ac20/Py): 50.8 mg KOH/g Acid number (Ac2O/Py) ' 0.1 mg KOH/g TDA content (~PLC): 1 . 364 a Viscosity at 25Co 3,740 mPas 20 Exam~?le 8 The NCO/OH prepolymer used in thiR example had an NCO cont~n~ of 1.06X and was prepared from 1100 g of ~he polyether mixture from Exzmple 7 by the reaction of this mixture with 57 g of toluylene-2,4-di~socyanate for 25 3 hours at 60C. The prepolymer obtained had an average of two OH groups to one NCO group.
A mixture of 700 g of DMF, 21 ml o water and 0.01 g of KOH was introduced into the reaction ve~sel.
1000 g of the prepolymer described above were added 30 within 20 minutes with s~irring at an internal temperature of 90C. The product which was worked up as in Example 5 had the following properties:

~e A 24_534 . . .~ . . -, : . . ~ - :

.. .
.

NH number (HC104): 13.5 mg KOH/g NH/OH number (Ac2O/Py):47 . O mg KOH/g Acid number (Ac2O/Py):~ O . l mg KOH/g TDA content (HPLC): 0.608 Z
5 Viscosity at 25C: 1,B70 mPa&
Example 9 The NCO/OH prepolymer used in thi6 example was obtainPd by reacting 1700 g of the polyether mixture from Example 7 with 238 g of toluylPne 2,4~diisocyanate 10 for 4 hours at 60C. It had an isocyanate content of 2.9~ and contained on average one hydroxyl group to nine NCO groups.
! A mixture of 600 g of DMF, 20 ml of water and 0.03 g of KOH was introduced into the reaction vessel.
lS 0.5 kg of the prepolymer described above ~ere added with Rtirring at an internal temperature of 90C. The reaction mixture was worked up as described in Example 5. The product had the following properties:
NH number (HC104): 38.6 mg KOH/g 20 NH/OH number (Ac~O/Py):51.4 mg KOH/g Acid number (AC2O/Py) :< 0.05 mg KOH/g TDA content (HPLC): 0.603 X
Viscosity at 25C: 8,300 mPas Example 10 The NCO prepolymer (1.3~ NCO) used in thiB
example wa~ prepared by reaction of 1,200 g of the polyether of Example 5 with 100.8 g of 4~4'-di-isocyanatodiphenylmethane for 3 hours at 50C. The NCO/OH prepolymer contained on average two NCO groups to 30 one hydroxyl group.
A mixture of 1000 g of DMF, 10 g of wat~r and 0.08 g of KOH was introduced into the reaction vessel.
0.5 kg of the prepolymer described above were added within 10 minutes at 90C. The product which was worked 35 up as in Example 5 had the following properties:

: Le A 24 s34 ', .' ~" -.: .' ' ~
.. :- : -1 32827h NH number ~HC104): 23.5 mg KOX/g NH/OH number (Ac20/Py): 36.8 mg KOH/g MDA content (HPLC): 2.12 Acid number (Ac2O/Py): ~ 0.2 mg KOH/g 5 Viscosity at 23C: 6,000 mPas Example 11 16.4 g (0.166 mol) of n-butylisocyanate were added to 500 g of a polyether polyol with OH number 56 obtained by the blockw~se addition of 95.3 wt. X of 10 propylene oxide followed by 4.7 wt. % o ethylene oxide to glycerol (s 0.5 mol OH). The reaction mixture was stirred for 3 hours at 90C and then for lb, hours at 80C. No NCO could be detec~ed by IR spectroscopy at the end of this time.
29 g (0.166 mol) of 2,4-diisocyanato~oluene were then added to this product and the mixture wa~
stirred at 60C or 9~ minute~. The isocyanate content fell to 1.26X (calculated 1.28Z).
450 g of this prepolymer were added within 20 20 minutes at 90C to a previously prepared mixture of 300 g of dimethylformamide, 4.8 ml of water and 0,02 g of KOH. Stirring was continued for S minutes at 90C
af~er all the prepolymer had been added. The volatile constituent~ were then dis~illed off. The product left 25 behind which contained terminal n-butylurethane, 4-methyl-3-aminophenylurethane and hydroxyl groups had the following properties:
NH number (HC10 ): 15 7 mg KOH/g (~heoretical ac~ording to NCO content: 16.9) NH/OH number (Ac20/Py): 36.3 mg KOHtg Viscosity at 25C 2COO mPas .
35 TDA conten~ tHPLC): 0~006 Z

Le A 24 534 1 3~827 6 use example In this example polyurethane urea elastomer moulded products were produced and their mechanical properties compared with each other. Recipes in which the NCO-reactive component contained a) a polyaminohydroxyl compound according to the invention (polyol C) or b) suitable comparative compounds (polyols A, B, and D) were used for the production of the moulded products. A
piston-type high-pressure metering device with an MQ-mixing head (made by Maschinenfabriken Hennecke, St. Augustin) and automatic control was used for the production of the moulded products. The operating pressure was 200 bars~
The polyol and isocyanate components mentioned below were intimately mixed using this apparatus and pro cessed into moulded parts with the mechanical properties described below. The temperatures of the raw materia~
were in each case 35-40C, the temperature of the mould was about 60C.
The mould used was made of polished steel, had internal dimensions of 200 x 300 x ~ mm and interior walls coated with an external release agent with a wax base (~Acmos Fluoricon 36/34 made by the Acmos company).
The filling time was about 1 sec., the demoulding time was 30 secs.
Recipes I-IV
NCO-reactive component:
75 parts of polyols A, B, C ord D
(for recipes I-IV) - 25 parts of a mixture of 65 parts of 1-methyl-3,5-diethyl-2,4 diaminobenzene and 35 parts of 1-methyl-3-5-diethyl-2,6-diaminobenzene ("Detda") 0.3 parts of Dabco* 33 LV (aminic catalyst made by Air Product~) 0.1 parts of UL 28 (tin catalyst made by Witco~
LeA 24 534 -55 *Trade-mark 1 3~276 Isocyanate component:
P~ 100, a commercial isocyanate, based on diphenyl methane diisocyanate; made by BAYER AG -NCO-content: 23 ~.
Indices: 100, 110 ~LY~. Polyethertriol with an OH number of 28, obtained by the bloc~-wise addition of 73 ~ by weight of propylene oxide and then 17 ~ by weight o ethylene oxide to trlmethylolpropane.
Polyol B: Polyether amine with an NH number of 24.5, obtained by the hydrolysls of an NCO prepolymer of polyol A and 2,4-toluylene-diisocyana~e with an NCO content of l . 9 9~ by weight ~process according to DE-A 3 613 249) .
~ taccordin~ to the invention):
Polyhydroxylamine compound with an ~NH~OH) number of 31.6 from example 6.
~IY~ Mixture of 66.6 parts of polyol B and 33 . 3 parts of polyol A.

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c ~ a ~ ~ f~ ~; UJ 5 ~
:~ ~ O 'I O i~ ~1 0 0 ,~ ~ U. ~ O q'~
~ o ~1 ~ ~ ~ E~ ~ ~ t) o a) ~ a~ ~7 0 . tv --I ~ h a~ h --I O n~
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Le A 24 534 -57-. .. ~- . .

J~ `

Although the invention has been described in detail in the foregoing for the purpose of lllustration, lt is to be understood that such detail is solely for that purpose and that variations can be made therein by S those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Le A 24 534 -58-,. . .

Claims (28)

1. A polyaminohydroxyl compound containing primary amino groups attached to the molecular skeleton by at least one of urethane and urea groups, and hydroxyl groups having a molecular weight of from 200 to 20,000 and a functionality of greater than 1 but less than or equal to 8 containing:
(a) 0.165-16.5 wt. % amino and hydroxyl groups in quantities such that the equivalent ratio of amino groups to hydroxyl groups is from 99:1 to 0.1:99.9:
(b) 0.295-29.5 wt. % at least one of urethane and urea groups; and (c) groups which do not react with amines and isocyanates in quantities such that the equivalent ratio of amine groups to inert groups is from 100:0 to 33.?:66.? and the equivalent ratio of hydroxyl groups to inert groups is from 100:0 to 33.? to 66.?.

2. The compound of Claim 1 having a molecular weight of from 400 to 12,000 and a functionality of from 1.5 to 6.

3. The compound of Claim 1 having a molecular weight of from 1000 to 7000 and a functionality of from 2 to 4.

4. The compound of Claim 1 containing 0.4-5 wt. % amino and hydroxyl groups.

5. The compound of Claim 1 in which the equivalent ratio of amino groups to hydroxyl groups is from 80:20 to 20:80.

6. The compound of Claim l which further contains polyether groups.

\

7. The compound of Claim 1 in which the number of equivalents of primary amino groups is 2 -0.25.

8. The polyaminohydroxyl compound of Claim 1 corresponding to the formula in which X represents an NH group or 0, Y represents hydrogen or a monovalent organic group, R represents the residue of a polyamine, polyalcohol or amino alcohol, R1 represents a C2-C4-alkylene group, an alkyl-substituted C2-C4-alkylene group or aryl-substituted C2-C4-alkylene group,.
R2 represents the residue of a polyisocyanate, q represents a number from 1 to 2, m, n, o represent numbers sufficient to bring the molecular weight of the polyaminohydroxyl compound in the range of from 200 to 20,000 and p, r and s each represent a number such that p + r + s is equal to a value of from 2 to 8 and the ratio of p to s is from 100:0 to 33.?:66.?, the ratio of r to p is from 99:1 to 0.1:99.9 and the ratio of r to s is from 100:0 to 33.?:66.?.

9. The compound of Claim 8 in which Y
represents an alkyl, aryl or alkoxyl group.

10. The compound of Claim 8 in which Y
represents OCONH-monovalent organic group or an NHCONH-monovalent organic group.

11 The compound of Claim 8 in which each represents an ethylene or 1,2-propylene group

12. A mixture containing (a) 75-100 wt. % of the polyaminohydroxyl compound of Claim 8, (b) 0-5 wt. % of a compound corresponding to the formula R2(NH2)q+1 in which R2 represents the residue of a polyisocyanate and q represents a number from 1 to 2 or secondary products thereof, and (c) 0-20 wt. % of a polyol or aminopolyol from which the polyaminohydroxyl compound (a) was prepared.

13. The mixture of Claim 12 in which compound (c) corresponds to at least one of the formulae in which X represents an NH group or 0, Y represents hydrogen or a monovalent organic group, R represents the residue of a polyamine, polyalcohol or amino alcohol, R' represents a C2-C4-alkylene group, an alkyl-substituted C2-C4 alkylene group or an aryl-substituted C2-C4 alkylene group, m, n and o represent numbers sufficient to bring the molecular weight of the compound within the range of from 200 to 20,000, and p, r and s represent numbers such that p + r + s is equal to a value of from 2 to 8 and p:s = 100:0 to 33.?:66.?, r,p = 99:1 to 0.1:99.9, r:s = 100:0 to 33.?:66.?.

14. A mixture containing (a) 75-100 wt. % of the polyaminohydroxyl compound of Claim 1, (b) 0-5 wt. % of a compound corresponding to the formula R2(NH2)q+1 in which R2 represents the residue of a polyisocyanate, and q represents a number from 1 to 2, and (c) 0-20 wt. % of a polyol or aminopolyol corresponding to that from which polyaminohydroxyl compound (a) was prepared.

15. A process for the production of the poly-aminohydroxyl compound of Claim 1 in which (a) an isocyanate containing hydroxyl groups and also at least one of urethane and urea groups and having a functionality of from greater than 1 to 8 in which (1) 0.3-25.9 wt. % free NCO groups and (2) 0.295-29.5 wt. % at least one of urethane and urea groups are present and the ratio of NCO groups to hydroxyl groups is in the range of from 90:100 to 0.1:99.9 is hydrolyzed with (b) at least 0.75 mol of water for each equivalent of NCO groups to form the polyaminohydroxyl compound,

16. The process of Claim 15 in which the isocyanate (a) also contains groups that are inert with respect to isocyanate groups in an amount such that the ratio of isocyanate groups to inert groups is from 100:0 to 80:20 and the ratio of hydroxyl groups to inert groups is from 100:0 to 33.3:66.6.

17. The process of Claim 15 in which at least 1 mol of water for each equivalent of NCO groups is used.

18. The process of Claim 15 in which the isocyanate (a) has a functionality of from 2 to 4.

19. The process of Claim 15 in which a hydrolysis catalyst selected from basic compounds, tertiary amines, metal catalysts and mixtures thereof is employed.

20. The process of Claim 15 in which the hydrolysis is carried out in the presence of a solvent.

21. A process for the production of the polyaminohydroxyl compound of Claim 1 in which (a) an isocyanate containing 0.3-25.9 wt. %
free NCO groups and 0.295 to 29.5 wt. % at least one of urethane and urea groups having a functionality of from greater than 1 to 8 in which the ratio of NCO
groups to hydroxyl groups is from 90:100 to 0.1:99.9 is mixed with (b) at least 0.75 mol of water for each equivalent of NCO groups and (c) a base to form a reaction mixture containing compounds with carbamate groups and converting the carbamate groups to amine groups.

22. The process of Claim 21 in which the conversion to amino groups is accomplished by at least one of heat treatment, acid treatment and extraction with an organic solvent.

23. A process for the production of the polyaminohydroxyl compound of Claim 1 in which (a) an isocyanate containing 0.3-25.9 wt. %
free NCO groups and 0.295 to 29.5 wt. % at least one of urethane and urea groups having a functionality of from greater than 1 to 8 in which the ratio of NCO
groups to hydroxyl groups is from 99.1 to 0.1:99.9 is hydrolyzed at 25 to 210°C in a substantially homogeneous phase with (b) at least 0.75 mol of water for each equivalent of NCO groups in the presence of (c) a basic catalyst and (d) a water-miscible, aprotic dipolar solvent.

24. The process of Claim 23 in which solvent (d) is dimethylformamide.

25. A process of the production of poly-urethanes(ureas) comprising reacting the poly-aminohydroxyl compound of Claim 1 with a polyisocyanate by a reaction injection molding process.

26. A process of the production of poly-urethanes(ureas) comprising reacting the poly-aminohydroxyl compound of Claim 7 with a polyisocyanate by a reaction injection molding process.

27. A process of the production of poly-urethanes(ureas) comprising reacting the poly-aminohydroxyl compound of Claim 8 with a polyisocyanate by a reaction injection molding process.

28. A process for the production of a poly-urethane(urea) comprising reacting the mixture of Claim 12 with a polyisocyanate by a reaction injection molding process.