PROCESS FOR THE PREPARATION OF WATER DISPERSIBLE POLYURETHANES

PROCEDE POUR LA PREPARATION DE POLYURETHANES POUVANT FORMER DES DISPERSIONS AQUEUSES

English Abstract

Abstract of the Disclosure
This invention relates to a process for the production
of water dispersible polyurethanes by reacting polyisocyanates
with sulphonate group containing diols. The sulphonate diol-
have the general formula:
<IMG>
wherein
A and B, which may be the same or different, each
represents a divalent aliphatic hydro-
carbon group containing from 1 to 6 carbon
atoms,
R represents hydrogen an aliphatic hydro-
carbon group containing 1 to 4 carbon
atoms or a phenyl group,
x(+) represents an alkali metal carbon or
ammonium group which may be substitured
n and m, which may be the same or different, each
represents an integer between 0 and 30
inclusive,
o and p, represent 0 or 1, and
q represents an integer of 0 or 2
sufficient amounts of this diol are used to provide
the final poymer with a suphonate group content of about 0.1
LeA 15,933

to 6 wt.%. In a preferred embodiment, a prepolymer is formed
in substance with the sulphonate bearing diol, the polyiso-
cyanate and optionally other reactive hydrogen bearing com-
pounds. The prepolymer is then chain extended with water and
water soluble polyamines. This second stage may take place in
water and the polyamines may carry sulphonate groups.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:-
1. A process for the preparation of polyurethanes
which contain sulphonate groups by reacting polyisocyanates
with diols which contain sulphonate groups and optionally other
compounds which are at least difunctional for the purpose
of the isocyanate polyaddition reaction and contain hydrogen
atoms which are reactive with isocyanate groups, characterized
in that the diols which contain sulphonate groups have a
melting point or softening point below 120°C and correspond
to the following general formula:
(1)
<IMG>
and are used in such quantities that the polyurethane has
as SO3(-) group content of from 0.1 to 6%, weight, in which
formula
A and B, which may be the same or different, each represents
a divalent aliphatic hydrocarbon group containing
from 1 to 6 carbon atoms;
R represents hydrogen, an aliphatic hydrocarbon group
containing from 1 to 4 carbon atoms or a phenyl group;
X(+) represents an alkali metal cation or an ammonium group
which may be substituted;
n and m, which may be the same or different, each represents
an integer between from 0 to 30;
o and p represent 0 or 1; and
q represents an integer of from 0 to 2.
2. Embodiment of the process according to Claim 1,
in which preparation of the polyurethane is accompanied by
dispersion of the polyurethane in water, characterized in that
LeA 15,933
27

a prepolymer which contains free isocyanate groups is prepared
in a first reaction step from the diol which contains sulphonate
groups and optionally other compounds which are at least di-
functional for the purpose of the isocyanate polyaddition
reaction and contain hydrogen atoms which are reactive with
isocyanate groups and excess quantities of organic polyisocyanate,
and the said prepolymer is then mixed in a second reaction step
with from 0.2 to 10 times its quantity, by weight, of water.
3. Embodiment according to Claim 2, characterized
in that water and a polyamine which contains exclusively primary
and/or secondary amino groups and has a molecular weight above
31 and optionally contains S03(-) X(+) substituent are used to
chain extend the prepolymer,wherein X(+) is as defined in Claim 1
and in cases where such polyamines containing sulphonate groups
are used, the total quantity of diol which contains sulphonate
groups and of polyamine which contains sulphonate groups is so
chosen that the resulting polyurethane contains from 0.1 to 6%,
by weight, of S03(-) groups, based on the solids content.
4. A process for preparing water dispersible poly-
urethanes comprising
a) preparing a prepolymer by reacting polyisocyanates
with diols containing sulphonate groups and having
a melting point or softening point below 120°C
of the formula
(1)
<IMG>
wherein
A and B, which may be the same or different, each represents a
divalent aliphatic hydrocarbon group containing from
1 to 6 carbon atoms,
LeA 15,933
28

R represents hydrogen, an aliphatic hydrocarbon group
containing 1 to 4 carbon atoms or a phenol group,
x(+) represents an alkali metal cation or ammonium group
which may be substituted
n and m, which may be the same or different, each represents
an integer between 0 and 30 inclusive
o and p represent 0 or 1, and
q represents an integer of from 0 to 2
and optionally other compounds containing at least two hydrogen
atoms per molecule which are reactive with isocyanate groups
such that the final polymer produced has an SO3(-) group content
of from 0.1 to 6% by weight and the prepolymer reactants have
an isocyanate to isocyanate reactive hydrogen ratio of about 1.05
to 6; and
b) chain lengthening the prepolymer with conventional
chain lengthening agents.
5. The process of Claim 4, wherein
a) the optionally present reactive hydrogen bearing
compounds carry the active hydrogen as hydroxyl
groups,
b) the NCO to OH ratio of the prepolymer reactants
is about 1.1 to 3,
c) the prepolymer formation is carried out in
substance at temperatures between about 30
and 170°C,
d) the prepolymer is mixed with about 0.2 to
10 times its weight of water at temperatures of
about 1 to 180°C, and
e) the prepolymer is chain lengthened with water
and water soluble chain lengthening agents that are
more reactive with isocyanate groups than water.
LeA 15,933
29

6. The process of Claim 5, wherein
a) the optionally present reactive hydrogen
bearing compounds are mainly diols with
molecular weights between about 1000 and
6000 selected from the group consisting of
hydroxypolyesters, hydroxypolyethers, hydroxy-
polythioethers, hydroxypolyacetals, hydroxy-
polycarbonates and hydroxypolyester amides,
b) the prepolymer is prepared at temperatures
between about 50 and 120°C.,
c) the sulphonate diol is selected from those of
the general formula
<IMG>
wherein
R is methyl or hydrogen, n and m are limited
to 0 to 3 and
i) A and B are methylene groups, o, p and
q are all 1, or
ii) A is a methylene group, B is an ethylene
group, o and p are both 1, and q is 0, or
iii) B is a methylene group, o is 0, p is 1
and q is 2;
d) the water soluble chain lengthening agent is a
diamine with a molecular weight above 31 in
which the amino groups are exclusively primary
or secondary and
e) the final polymer has a sulphonate group con-
tent of about 0-.6-to 3 wt. % based on the solid
polymer.

7. The process of Claim 6, wherein
a) X(+) in the formula of said sulphonate diol
is a lithium cation or a NH4(+) ion,
b) n and m in formula (1) of Claim 4 are 0, and
c) the chain lengthening agents include diamines
modified by chemically fixed sulphonate
groups.
8. In a process for preparing water dispersible
polyurethanes by reacting polyisocyanates with compounds
carrying at least two hydrogen atoms reactive with isocyanate
groups and ionic groups the improvement comprising reacting
polyisocyanates with sulphonate bearing diols having a melting
point or softening point below 120°C of the general formula
(1)
<IMG>
wherein
A and B which may be the same or different, each repre-
sents a divalent aliphatic hydrocarbon group
containing from 1 to 6 carbon atoms,
R represents hydrogen, an aliphatic hydrocarbon
group containing 1 to 4 carbon atoms or a phenol
group,
X(+) represents an alkali metal castioy or ammonium
group which may be substituted,
n and m which may be the same or different, each repre-
sents an integer between 0 and 30 inclusive,
o and p represent 0 or 1, and
q represents an integer of from 0 to 2.
31
LeA 15,933-Ca.

9. A process for preparing water soluble poly-
urethanes comprising
a) forming a prepolymer in substance at tempera-
tures between about 30 and 190°C. and an NCO
to OH ratio of about 1.05 to 6 by reacting
i) sulphonate containing diols having a
melting point or softening point below
120°C of the general formula
(1)
<IMG>
wherein
A and B which may be the same or different, each repre-
sents a divalent aliphatic hydrocarbon group
containing from l to 6 carbon atoms,
R represents hydrogen, an aliphatic hydrocarbon
group containing l to 4 carbon atoms or a
phenol group,
X(+) represents an alkali metal cation or ammonium
group which may be substituted,
n and m which may be the same or different, each repre-
sents an integer between 0 and 30 inclusive,
o and p represent 0 or l, and
q represents an integer of from 0 to 2.
ii) polyisocyanates of the formula
(2) Q(NCO)2
wherein
Q represents C4 to C12 alkyl, C6 to C15 cycloalkyl,
C6 to Cl5 aryl or C7 to Cl5 aralkyl, and
32

iii) dihydroxy compounds having molecular weights
of about 1000 to 6000 selected from the
group consisting of polyesters, polyethers,
polythioethers, polyacetals, polycarbonates
and polyester amides, and
b) chain extending the prepolymer with water and
water soluble diamines having molecular weights
of about 32 to 600 and exclusively primary or
secondary amino groups the proportion of reac-
tants being so selected that the final polymer
has a sulphonate group content of about 0.1 to
6 wt. %.
10. A solvent free process for the preparation of
aqueous polyurethane dispersions which comprises
a) the solvent free preparation of an NCO termin-
ated prepolymer by the reaction of
i) polyisocyanates,
ii) diols which contain sulphonate groups
and have melting or softening points
below 120°C of the general formula
<IMG>
wherein
A and B which may be the same or different, each represents
a divalent aliphatic hydrocarbon group containing
from 1 to 6 carbon atoms,
R represents hydrogen, an aliphatic hydrocarbon group
containing from 1 to 4 carbon atoms or a phenyl group,
33

X(+) represents an alkali metal cation
n and m, which may be the same or different, each represents
an integer between from 0 to 30;
o and p represent 0 or l; and
q represents an integer of from 0 to 2 and
iii) optionally other compounds which are at
least difunctional for the purpose of
the isocyanate polyaddition reaction and
contain hydrogen atoms which are reactive
with isocyanate groups, sufficient
amounts of ii) being used to provide the
final polymer with 0.1 to 6 wt. % of
SO3(-) groups and
b) the dispersion in water of said prepolymer by
either
i) reacting the terminal isocyanate groups
to form acylated amino end groups and
then combining the prepolymer with
water which may contain aqueous formalde-
hyde or formaldehyde donors, or
ii) combining said prepolymer directly with
water which may contain water soluble
chain lengthening agents or polyamines
under such conditions as to effect chain
extension of the prepolymer.
11. A process for the solvent free preparation
of aqueous polyurethane dispersions which comprises
a) the solvent free preparation of an NCO
34

terninated prepolymer by the reaction of
i) polyisocyanates,
ii) diols which contain sulphonate groups
and have melting points below 120°C or
the formula
<IMG>
wherein
A and B which may be the same or different, each represents
a divalent aliphatic hydrocarbon group containing
from 1 to 6 carbon atoms;
X(+) an ammonium group which may be substituted;
o and p represent 0 or 1; and
q represents an integer of from 0 to 2 and
iii) optionally other compounds which are
at least difunctional for the purpose
of the isocyanate polyaddition reaction
and contain hydrogen atoms which are
reactive with isocyanate groups,
sufficient amounts of ii being used to
provide the final polymer with 0.1 to
6 wt. % of SO3(-) groups and
b) the combination of said prepolymer with water
LeA 15.993-Ca.

containing polyamines having chemically fixed
ionic groups under such conditions as to
effect chain extention of the prepolymer.
12. A solvent free process for the preparation of
aqueous polyurethane dispersions which comprises
a) the solvent free preparation of an NCO
terminated prepolymer by the reaction of
i) polyisocyanates,
ii) diols which contain sulphonate groups and
have melting points below 120°C of the
formula
<IMG>
wherein
R represents hydrogen or a methyl group;
n and m which may be the same or different, each represents
an integer of from 0 to 3; and
X(+) represents an alkali metal cation
iii) optionally other compounds which are at
least difunctional for the purpose of the
isocyanate polyaddition reaction and con-
tain hydrogen atoms which are reactive with
isocyanate groups,
sufficient amounts of ii being used to provide
the final polymer with 0.1 to 6 wt. % of SO3(-)
groups, and
36

b) the dispersion in water of said prepolymer
by either
i) reacting the terminal isocyanate groups
to form acylated amino end groups and
then combining the prepolymer with water
which may contain
aqueous formaldehyde or formaldehyde donors, or
ii) combining said prepolymer directly with
water which may contain water soluble
chain lengthening agents or polyamines
such conditions as to effect chain
extension of the prepolymer.
13. A solvent free process for the preparation
of aqueous polyurethane dispersions which comprises
a) the solvent free preparation of an NCO
terminated prepolymer by the reaction of
i) polyisocyanates,
ii) diols which contain sulphonate groups
and have softening or melting points below
120°C of the formula
<IMG>
wherein
R represents hydrogen or a methyl group
37

n and m which may be the same of different, each represents
an integer of from 0 to 3; and
X(+) represents an alkali metal cation
iii) optionally other compounds which are at
least difunctional for the purpose of
isocyanate polyaddition reaction and
contain hydrogen atoms which are reactive
with isocyanate groups,
sufficient amounts of ii being used to provide the
final polymer with 0.1 to 6 wt. % of SO3(-) groups,
and
b) the dispersion in water of said prepolymer by
either
i) reacting the terminal isocyanate groups
to form acylated amino end groups and then
combining the prepolymer with water which
may contain aqueous formaldehyde or formal-
dehyde donors, or
ii) combining said prepolymer directly with
water which may contain water soluble
chain lengthening agents or polyamines
under such conditions as to effect the
chain extension of the prepolymer.
14. A solvent free process for the preparation of
aqueous polyurethane dispersions which comprises
a) the solvent free preparation of a NCO terminated
prepolymer by the reaction of:
38

i) polyisocyanates
ii) diols which contain sulphonate groups
and have melting points below 120°C of
the general formula
<IMG>
wherein
A and B which may be the same or different, each represents
a divalent aliphatic hydrocarbon group containing
from 1 to 6 carbon atoms;
R represents hydrogen, an aliphatic hydrocarbon group
containing from 1 to 4 carbon atoms or a phenyl
group,
X(+) an ammonium group which may be substituted;
n and m which may be the same or different, each represents
an integer of from 0 to 30 and their sum is greater
than 0,
o and p represent 0 or 1; and
q represents an integer of from 0 to 2, and
iii) optionally other compounds which are at
least difunctional for the purpose of the
isocyanate polyaddition reaction and
contain hydrogen atoms which are reactive
with isocyanate groups,
sufficient amounts of ii being used to provide the
39

final polymer with 0.1 to 6 wt. % of SO3(-) groups,
and
b) combining said prepolymer directly with water
and polyamines having chemically fixed ionic
groups under such conditions as to effect
chain extension of the prepolymer.
15. The process of Claim 10, wherein
a) the optionally present reactive hydrogen bear-
ing compounds carry the active hydrogen as
hydroxyl groups,
b) the NCO to OH ratio of the prepolymer reactants
is about 1.1 to 3,
c) the prepolymer formation is carried out in
substance at temperatures between about 50 and
120°C,
d) the prepolymer is mixed with about 0.2 to 10
times its weight of water at temperatures of
about 1 to 180°C, and
e) the prepolymer is chain lengthened with water
and water soluble chain lengthening agents that
are more reactive with isocyanate groups than
water.
16. The process of Claim 15, wherein
a) the optionally present reactive hydrogen bearing
compounds are mainly diols with molecular
weights between about 1000 and 6000 selected
from the group consisting of hydroxypolyesters,
hydroxypolyethers, hydroxypolythioethers,
hydroxypolyacetals, hydroxypolycarbonates and
hydroxypolyester amides,

b) the prepolymer is prepared at temperatures
between about 50 and 120°C.,
c) the sulphonate diol is selected from those of
the general formula (1) of Claim 10 wherein
R is methyl or hydrogen, n and m are limited
to 0 to 3 and
i) A and B are methylene groups, o, p and
q are all 1, or
ii) A is a methylene group, B is an ethylene
group, o and p are both 1, and q is 0, or
iii) B is a methylene group, o is 0, p is 1 and
q is 2;
d) the water soluble chain lengthening agent is a
diamine with a molecular weight above 31 in
which the amino groups are exclusively primary
or secondary and
e) the final polymer has a sulphonate group content
of about 0.6 to 3 wt. % based on the solid poly-
mer.
17. The process of Claim 16, wherein
a) X(+) is a lithium cation or a NH4(+) ion,
b) n and m are 0, and
c) the chain lengthening agents include diamines
modified by chemically fixed sulphonate groups.
18. A process for preparing water soluble poly-
urethanes comprising
41

a) forming a prepolymer in the absence of solvent
at temperatures between about 30 and 120°C and
an NCO to OH ratio of between about 1.05 and 6
by reacting
i) sulphonate containing diols having a melting
point or softening point below 120°C of the
general formula
<IMG>
wherein
A and B which may be the same or different, each repre-
sents a divalent aliphatic hydrocarbon group
containing from 1 to 6 carbon atoms,
R represents hydrogen, an aliphatic hydrocarbon
group containing 1 to 4 carbon atoms or a phenyl
group,
X(+) represents an alkali metal cation or when
n + m > O or when q = 1 an ammonium group which
may be substituted,
n and m which may be the same or different, each repre-
sents an integer between 0 and 30 inclusive,
o and p represent 0 or 1, and
q represents an integer of from 0 to 2 with,
ii) polyisocyanates of the formula
(2) Q(NCO)2
42

wherein
Q represents C4 to C12 alkyl, C6 to C15 cycloalkyl,
C6 to C15 aryl or C7 to C15 aralkyl, and
iii) dihydroxy compounds having molecular weights
of about 1000 to 6000 selected from the group
consisting of polyesters, polyethers, poly-
thioethers, polyacetals, polycarbonates and
polyester amides,and
b) chain extending the prepolymer with water and
water soluble diamines having molecular weights
of about 32 to 600 and exclusively primary or
secondary amino groups the proportion of reac-
tants being so selected that the final polymer
has a sulphonate group content of about 0.1 to
6 wt. %.
43

Description

Mo-1549-P
LeA 15,933
~o6~04;3
PROCESS FOR THE PREPARATION OF
WATER DISPERSIBLE POLYURETHANES
Background of the Invention
Processes for the preparation of stable, aqueous poly-
urethane polyurea dispersions are known (e.g. DBP No. 1,184,946
which is equivalent to U.S. Patent No. 3,388,087; DAS No. 1,237,
306 which is equivalent to U.S. Patent No. 3,461,103; DOS No.
1,495,745 which is equivalent to U.S. Patent No. 3,479,310 and
German DOS 1,770,068 which is equivalent to U.S. Patent
3,756,992 as well as Gérman DOS 2,019,324 which is equivalent
to U.S. Patent 3,686,108 and German Patent 1,178,586 which is
equivalent to British Patent 1,043,260 and also DOS No.
1,595,602; see also D. Dieterich et al, Angew. Chem. 82, 53
(1970)). The dispersions already described are based on the
principle of incorporating hydrophilic centers into a macro-
molecular chain of a polyurethane polyurea molecule. In the
known dispersions, these hydrophilic centers or so-called
"internal emulsifiers" are ionic groups or ether functions.
The ionic groups are either incorporated in the prepolymer in
the form cf certain diols or used as modified amines for chain
- lengthening the prepolymers, each of which has at least two NCO
end-groups.
High quality polyurethane films which are suitable, e.g.
for coating textiles, have hitherto been obtained from dis-
persions produced by processes in which organic solvents were
used in the polyaddition reaction. By this method it is
possible to operate in homogeneous solutions for obtaining
products up to relatively high molecular weights and thus
achieve problem-free dispersion. In particular, high ~uality,
finely-divided and stable dispersions may be obtained in this
way even with a low ionic group content.
LeA 15,933 ~1

1(~6104~
This highly developed process which includes both
anionic, cationic and non-ionic emulsifier segments has the
disadvantage of requiring extensiye operations for distilling
off and rectifying the organic solvent. This is connected with
a poor volume/time yield in the production process. The
organic solvent used as reaction medium increases the risk of
explosion and fire during the process. If attempts are made
to produce such products without organic solvents one obtains,
at best, relatively coarse dispersions the film forming
capacity and mechanical properties of which are inadequate for
numerous purposes.
A process for solvent-free preparation of polyurethane
dispersions is also known, the so-called "melt dispersion
process" (DOS No. 1,770,068 which is equivalent to U.S. Patent
3,75S,992, D. Dieterich and H. Reiff, Angew. makromol. Chem.
76, 85 (1972)). In this process, an oligourethane which has
been modified with ionic groups and contains acylated amino
end-groups is reacted with formaldehyde to convert it into the
corresponding oligourethane which contains methylol end-groups
attached to acylated amino groups and this oligourethane is then
chain lengthened by a heat treatment which gives rise to con-
densation of the reactive methylol end-groups. This chain
lengthening reaction may be carried out in the presence of water
80 that an aqueous dispercion of polyurethane is obtained
directly. This process is particularly suitable for producing
cationically modified polyurethanes or anionic polyurethanes
which contain carboxylate groups. The necessary combination of
the isocyanate polyaddition reaction with the above-mentioned
chain lengthening reaction by means of polycondensable methylol
groups which are attached to acylamino end-groups is so~ewhat
more complicated than the known isocyanate polyaddition
carried out by the prepolymer process in which prepolymers which
LeA 15,933 -2-

~10~104;~
contain isocyanate groups are reacted with conventional chain
lengthening agents, such as water or diamines. This extra
expenditure could be justified in the process according to
DOS No. l,770,068 on the grounds that this process made it
possible for the first time to produce polyurethane dispersions
without the aid of special stirrers and without emulsifiers
or solvents.
The problem of producing aqueous dispersions of poly-
urethanes which contain sulphonate groups and are therefore
substantially unaffected by electrolytes by a simple process
which does not make use of the above aids and is confined
to the methods of the isocyanate polyaddition reaction remained
unsolved. Qualitatively high grade dispersions of polyurethanes
which contain sulphonate groups have hitherto been obtained from
prepolymers which contain NCO end-groups by chain lengthening
solutions of these prepolymers in organic solvents with diamino-
sulphonate solutions. Attempts to carry out this process
without solvents have hitherto failed; it was impossible to
obtain dispersions from which films with acceptable physical
properties could be obtained.
It has now surprisingly been found that high quality
dispersions of sulphonate group-containing polyurethanes which
are substantially free from the influence of electrolytes may
be obtained by a simple isocyanate polyaddition reaction without
the aid of stirrers with high shearing forces and without the
aid of emulsifiers or solvents if ~uite specific sulphonate
group containing diols which wi~l be described below are used
in the production of the polyurethanes.
Summary of the Invention
This invention therefore relates to a process for the
preparation of polyurethanes which contain sulphonate groups
LeA 15,933 -3-

10~10~;~
by reacting polyisocyanates with diols which contain sulphonate
groups and optionally in addition other compounds which contain
hydrogen atoms that are reactive with isocyanate groups and which
are at least difunctional in the isocyanate polyaddition reaction,
characterized in that the diols containing sulphonate groups
have a melting or softening point below 120C and correspond to
the following general formula:
. H2)n (A)o-cH-(B)p-O-(cH2-cH-o) -H
R (IH2)q R
So (~) ~+)
are used in such quantities that the polyurethane contains from
0.1 to 6% by weight, of SO3( ) groups. In the above formula,
A and B which may be the same or different, each represents
a divalent aliphatic hydrocarbon group containing
from 1 to 6 carbon atoms;
R represents hydrogen, an aliphatic hydrocarbon group
containing from 1 to 4 carbon atoms or a phenyl group,
X(+) represents an alkali metal cation or an ammonium
group which may be substituted;
n and m which may be the same or different, and represent~
an integer of from 0 to 30,
o and p represent 0 or 1; and
q represents an integer of from 0 to 2.
Detailed Descri~tion of the Invention
The diols with sulphonate groups used in the
process according to the invention are preferably the following:
1) those of Formula (I):
LeA 15,933 -4-

1()61043
H-(ocH-cH2)n-o-cH2-cH-cH2o(cH2-cH-o)m-H
R CH2 R
SO (~)X(+) (I)
wherein
R represents hydrogen or a methyl group;
n and m which may be the same or different, each represents
an integer of from O to 3; and
X(+) is as defined above;
2) those of Formula (II):
H-(O-CH-CH2) -0-CH2-CH-CH -CH -O(CH -CH-O) -H
R 1~ (~) (+) R (II)
wherein
R represents hydrogen or a methyl group;
n and m which may be the same or different, each represents
an integer of from O to 3; and
X( ) is as defined above; and
3) those of Formula (III):
lS H-(-o-cH-cH2)n-o-cH-cH2o(cH2-cH-o-)m-H
R 7H2 R
CH2
S03( )X(+) (III)
wherein
R represents hydrogen or a methyl group;
LeA 15,933 -5-

~0~1~)4;~
n and m which may be the same or different, each represents
an integer of from 0 to 3; and
X( ) is as defined above.
It is particularly preferred to use those diols
with sulphonate groups for the process according to the invention
which have a melting or softening point below 120C. This
condition is fulfilled in the case where n = m = 0 (compounds
(I), (II) and (III) in particular if X(+) is a lithium cation
or a NH4(+) ion. If sodium or potassium salts of the diols
with sulphonate groups are to be used, it is particularly
advisable to use compounds of the formulae (I), (II) and (III)
wherein n and m (in the statistical average) represent from
0.8 to 2. Those representatives of the last-mentioned com-
pounds wherein R represents a methyl group are quite particularly
preferred.
The preparation of compounds (I) is carried out
quite simply by reacting the optionally alkoxylated 2-methylene-
propane-1,3-diol with a bisulphite X HSO3 in an aqueous medium.
The unsaturated diol is dissolved in water and reacted with an
aqueous solution of the bisulphite which has previously been
adjusted to pH 7.1 with dilute X OH solution. The reaction
mixture is stirred at room temperature and at the same time the
pH is maintained at from 7.0 to 7.1 by the addition of dilute
sulphuric acid. The reaction is completed when the pH remains
constant. The reaction mix~:ure is acidified to a pH of from
2 to 3 and exaess SO2 i8 driven off by stirring. The mixture
is then neutralized with dilute X OH solution and evaporated to
dryness. The sulphonate-containing diol is then extracted with
methanol. Bisulphites X HSO3 and alkaline solutions X OH
wherein X represents potassium, sodium, lithium, or ammonium are
preferably used for this process. Conversion of the resulting
LeA 15,933 -6-

10610~3
sulphonate diols into those wherein X represents some other
component, for example a substituted ammonium group, may easily
be achieved by replacing the cation X(+) by a hydrogen ion by
means of an ion exchanger and then neutralizing the resulting
free acid with the desired base. The cation X(+) in the
sulphonate diols used in the process according to the invention
may be not only alkali metal cations, but any ammonium cations
of the formuls:
R'
H~ R~
R"'
wherein
R', R" and R"' which may be the same or different, each
preferably represents hydrogen or an alkyl
group with from 1 to 4 carbon atoms, R' and
R" when taken together with the central nitrogen
atom may form a heterocyclic ring, for example
a morpholine or hexahydropyridine ring.
Compounds (II) may be prepared in analogous manner
by the chemical addition of bisulphite to optionally alkoxylated
2-butene-1,4-diol.
The preparation of compounds (III) may be carried
out in analogous manner by chemical addition of bisulphite to
optionally alkoxylated l-butene-3,4-diol.
The bisulphite addition to such unsaturated diols
has been described in B~4p2n Patent Specificatlon 827, ??4.
Whether sulphonate diols which contain ether groups
or those which are free from ether groups are used for the
process according to the invention depends primarily on the melt-
ing or softening point of the diols which, as mentioned above,
LeA 15,933 -7-

106~04;~
should preferably be below 120C. The melting point of the
sulphonated diols falls with increasing degree of alkoxylation.
Compounds of formula (III) generally have a honey-like consist-
ency even when free from ether groups, regardless of the nature of
the cation X(+). It is therefore not necessary, although
possible, to use diols with ether groups instead of the~correR-
ponding compounds (III) which are free from ether groups. The
compatibility of the sulphonate diols which are an essential con-
stituent of the invention with the other compounds optionally
used in the process according to the invention, which are at
least difunctional in ~he isocyanate polyaddition reaction and
contain hydrogen atoms capable of reacting with isocyanate groups,
increases with increasing degree of alkoxylation.
Any organic polyisocyanates may be used in the
process according to the invention. It is preferred to use
isocyanates of the formula Q(NCO)2 wherein Q represents an
aliphatic hydrocarbon group containing from 4 to 12 carbon
atoms, a cycloaliphatic hydrocarbon group containing from 6 to
15 carbon atoms, an aromatic hydrocarbon group containing from 6
to 15 carbon atoms or an araliphatic hydrocarbon group con-
taining from 7 to 15 carbon atoms. The following are examples
of such preferred diisocyanates: tetramethylene-diisocyanate,
hexamethylene diisocyanate, dodecamethylene-diisocyanate, 1,4-
diisocyanato -cyclohexane, l-isocyanato-3,3,5-trimethyl-5-
isocyanatomethyl cyclohexane, 4,4'-diisocyanatodicyclohexyl-
methane, 4,4'-diisocyanato-dicyclohexyl-propane-(2,2); 1,4-
diisocyanato-benzene, 2,4-diisocyanatotoluene, 2,6-diisocyanato-
toluene, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-
diphenyl-propane-(2,2), p-xylylene-diisocyanate, ,,','-tetra-
methyl-_- or ~-xylylene-diisocyanate and mixtures of these
compounds.
LeA 15,933 -B-

106104~
The higher functional polyisocyanates known in
polyurethane chemistry, as well as the modified polyisocyanates
which are also known, such as polyisocyanates with carbodi-
imide groups, allophanate groups, isocyanurate groups, ure-
thane groups and/or biuret groups may, of course, also beused as part of all of the polyisocyanate component.
The average molecular weight range of these poly-
isocyanates is from about 140 to abou~ 1000.
The compounds optionally used in the process
tO according to the invention, which are at least difunctional
in the isocyanate polyaddition reaction and which contain
hydrogen atoms which are reactive with isocyanate groups
include, in particular, organic compounds within a molecular
weight range of from about 6~ to lO,000, preferably from
about lO00 to 6000, which contain a total of two amino
groups, thio groups, carboxyl groups and/or hydroxyl groups.
The dihydroxy compounds are preferred. Compounds which
have a functionality of 3 or more in the isocyanate polyaddi-
tion reaction may also be added in small quantities to achieve
a certain degree of branching and, as mentioned above, tri-
functional or higher functional polyisocyanates may be used
for the same purpose.
The hydroxyl compounds preferably used are the
hydroxy polyesters, hydroxypolyethers, hydroxypolythioethers,
hydroxypolyacetals, hydroxypolycarbonates and/or hydroxypoly-
ester amides known in polyurethane chemistry. Suitable
polyesters with hydroxyl groups include, e.g. reaction pro-
ducts of polyhydric, preferably dihydric alcohols with the
optional inclusion of trihydric alcohols, with polyba~ic,
3 preferably dibasic, carboxylic acids, Instead of free
polycarboxylic acid~, the corresponding polycarboxylic acid
anhydrides or esters of lower alcohols or mixtures thereof
LeA 15,933 -9-

~10~
may be used for producing the polyesters. The polycarboxylic
acids may be aliphatic, cycloaliphatic, aromatic and/or
heterocyclic and may be substituted, e.g. with halogen atoms,
and/or unsaturated. The following are examples:
succinic acid, adipic acid, suberic acid, azelaic acid,
sebacic acid, phthalic acid, isophthalic acid, trimellitic
acid, phthalic acid anhydride, tetrahydrophthalic acid
anhydride, hexahydrophthalic acid anhydride, tetrachloro-
phthalic acid anhydride, endomethylene tetrahydrophthalic
acid anhydride, glutaric acid anhydride, maleic acid, maleic
acid anhydride, fumaric acid, dimeric and trimeric fatty
acids, such as oleic acid, optionally mixed with monomeric
fatty acids, dimethylterephthalate and bis-glycol terephtha-
late. Suitable polyhydric alcohols include, e.g. ethylene
glycol, propylene-1,2- and -1,3-glycol, butylene-1,4- and
-2l3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentyl-
glycol-cyclohexanedimethanol (1,4-bis-hydroxymethyl-cyclohexane),
2-methyl-propane-1,3-diol, glycerol, trimethylolpropane,
hexane-1,2,6-triol, butane-1,2,4-triol, trimethylolethane,
pentaery~hritol, quinitol, mannitol and sorbitol, methyl
glycoside, diethylene glycol, triethyleneglycol, tetraethylene-
glycol, polyethyleneglycols, dipropylene glycol, polypropyl-
eneglycols, dibutyleneglycol and polybutylene glycols. The
polyesters may contain a proportion of carboxyl end-groups.
Polyesters of lactones, such as ~-caprolac~one, or hydroxy-
carboxylic acids, such as ~-hydroxy-caproic acid, may also
be used.
The polyethers with preferably 2 hydroxyl groups
which may also be used according to the invention are known
and may be obtained, e.g. by the polymerization of epoxides,
such as ethylene oxide, propylene oxide, butylene oxide,
LeA 15,933 -10-

10~i104;~
tetrahydrofuran, styrene oxide or epichlorohydrin, either
each on its own, e.g. in the presence of BF3, or by an addi-
tion of these epoxides, optionally as mixtures of successively,
to starting components which contain reactive hydrogen atoms,
such as alcohols or amines, e.g. water, ethylene glycol,
propylene-1,3- or -1,2-glycol, 4,4'-dihydroxy-diphenylpropa~e
or aniline.
Polyethers which are modified with vinyl polymers,
e.g. the polyethers which may be obtained by polymerizing
styrene or acrylonitrile in the presence of polyethers (U.S.
Patent Nos. 3,383,351; 3,304,273; 3,523,093 and 3,110J695 and
German Patent No. 1,152,536) are also suitable. The higher
functional polyethers of which a certain proportion may be
included are obtained in analogous manner by known methods
of alkoxylation of higher functional starter molecules, e.g.
ammonia, ethanolamine, ethylenediamine or sucrose.
Suitable polythioethers include, in parti~ular, the
condensation products obtained by condensing thiodiglycol
either on its own and/or with other glycols, dicarboxylic
acids, formaldehyde, aminocarboxylic acids or aminoalcohols.
The products obtained are polythio mixed ethers, polythio
ether esters or polythioether ester amides, depending on the
co-components.
Suitable polyacetals include, e.g. the compounds
which may be prepared from glycols, such as diethyleneglycol,
triethyleneglycol/ 4,4'-dioxethoxy-diphenyldimethylmethane and
hexane diol with formaldehyde. Polyacetals suitable for the
process according to the invention may also be prepared by
polymerizing cyclic acetals.
LeA 15,933 -11-

106104;~
Suitable hydroxyl polycarbonates are known and may
be prepared, e.g. by reacting diols, such as propane-1,3-diol,
butane-1,4-diol and/or hexane-1,6-diol, diethylene glycol,
triethyleneglycol or tetraethyleneglycol, with diarylcarbo-
nates, such as diphenylcarbonate or phosgene.
Suitable polyesteramides and polyamides include, e.g.
the predominantly linear condensates obtained from polybasic
saturated and unsaturated carboxylic acids or their anhydrides
and polyvalent saturated and unsaturated amino alcohols,
diamines, polyamines and mixtures thereof. Polyhydroxyl com-
pounds which already contain urethane or urea groups may
also be used. E~amples are linear polyamides from adipic acid
and 1.6-dl~mino-hexane, polyester amides from adipic acid,
hexanediol-1.6 and ethylene diamine.
Simple glycols, such as ethylene glycol, propylene
glycol, or hexamethylene glycol may, of course, also be used
in the preparation of the NC0 prepolymers, e.g. by the pre-
polymer method described below.
Representatives of these compounds which may be used
according to the invention have been described, e.g. in High
Polymers, ~701. XVI, "Polyurethanes, Chemistry and Technology"
by Saunders-Frisch, Interscience Publishers, New York, London,
Volume I, 1962, pages 32-42 and pages 44-54 and Volume II,
1964, pages 5-6 and 198-l99, and in Kunststoff-Handbuch,
Volume VII, Vieweg-~ochtlen, Carl-Hanser-Verlag, Munich, 1966,
e.g. on pages 45 to 71.
The process according to the invention for preparing
ionically modified polyurethanes, in particular with simul-
taneous conversion of these polyurethanes into an aqueous
dispersion, is preferably carried out by first preparing a
prepolymer with isocyanate end-groups from the sulphonate
diols which are essential to the invention, the polyisocyanate
LeA 15,933 -12-

lO~ilV4;~
components and the other compounds optionally used which are
preferably difunctional and contain hydrogen atoms which are
reactive with isocyanate groups. The reactants for producing
these prepolymers are preferably used in such proportions
that the ratio of isocyanate groups to the hydrogen atoms
which are reactive with isocyanate groups, which hydrogen
atoms are preferably in the form of hydroxyl groups, is from
about 1.05 to 6, preferably from about 1.1 to 3.
The sequence in which the individual reactants are
put into the process is unimpor~ant. A mixture of the sulpho-
nate diols and the optional polyhydroxyl compounds may be
reacted with the polyisocyanate component or an NC0 prepolymer
may first be prepared from the sulphonate diol and polyisocya-
nate component, and this prepolymer may then be further modi-
fied with a subequivalent quantity of the optional polyol,
which is preferably a diol. This process may also be reversed,
i.e. an NC0 prepolymer may firs~ be prepared from a polyol or
diol which i3 free from sulphonate groups and the polyisocya-
nate, and this prepolymer may then be converted,into an ioni-
cally modified prepolymer.
Preparation of the NC0 prepolymers is preferably
carried out in substance at from about 30 to 190C, preferably
from about 50 to 120C. Although the prepolymers may, of
course, be prepared in the presence of organic solvents, it
is regarded as one of the major advantages of the process
according to the invention tha'tsame solvents may be dispensed
with. Suitable solvents would be, for example, acetone,
methyl ethyl ketone, ethyl acetate, dimethylformamide or
cyclo-hexanone.
LeA 15,933 -13-

1(~6~04;~
In a second stage of the process, the NC0 prepolymer
obtained is now converted into the product of the process
according to the invention, the ionically modified polyure-
thane, by a known chain lengthening reaction. In the pre-
ferred embodiment of the process according to the invention,
this chain lengthening reaction is combined with conversion
of the product into an aqueous dispersion. The simplest
method of achieving this consists of using only water as
chain lengthening agent. This means that the prepolymer, which
is either liquid or of a honey-like consistency, is stirred up
with from about 0.2 to 10 times its weight of water. Simple
laboratory stirrers are sufficient for this operation although
dispersing machines with high shearing forces or non-mechanical
dispersing means, such as ultra-sonic waves of extremely high
frequency may, of course, be used if desired. The temperature
employed for the mixing process is from about 1 to 180C,
preferably from about 20 to 100C. This process may be carried
out under pressure.
The chain lengthening reaction may also be carried
out with mixtures of water and water-soluble chain lengthening
agents, preferably those which are more highly reactive with
isocyanate groups than is water. The NC0 prepolymer may also
b~ dispersed in water and the chain lengthening agent may be
added when the prepolymer has been dispersed. Suitable chain
lengthening agents for this purpo~e are, in particular, poly-
amines in which the amino groups are exclusively primary or
secondary amino groups, preferably diamines with molecular
weights above 31 and preferably from about 32 to 600. Examples
of such polyamines which may be used as chain lengthening
agents include: hydrazine, ethylene diamine, diethylene tri-
amine, 1,2-diaminopropane, 1,3-diaminopropane, 3,3,5-trimethyl-
LeA 15,933 -14-

~061043
5-aminomethyl-cyclohexylamine and 1,4-diaminobutane. Other
suitable bifunctional chain lengthening agents have been
described in German Offenlegungsschrift No. 1,495,847 and
in Genman Auslegeschrift No. 1,237,306. In this embodiment
of the process according to the invention, the quantity of
water used is also from 0.2 to 10 times the weight of the
NCO prepolymer.
In a particularly preferred embodiment of the pro-
cess according to the invention, the chain lengthening reac-
tion is carried out using a mixture of water and polyamines of
the type mentioned above which in addition are modified by
chemically fixed ionic groups, preferably chemically fixed
sulphonate groups. One such ionically modified chain
lengthening agent, for example, is the sodium salt of
ethylenediamino-2-ethanesulphonic acid.
The quantity of sulphonate diols which are essential
to the invention and their degree of alkoxylation, as well as
the quantity of the optional chain lengthening agent with 8ul-
phonate groups used for carrying out the process according
to the invention are chosen so that the products of the pro-
cess contain from about 0.1 to 6 and preferably from about
0.6 to 3% by weight of of S03( ) groups, based on the solids
content. The chain lengthening reaction in the second reac-
tion stage may also be carried out in the presence of sol-
vents in which the prepolymer is dissolved although it is one
of the major advantages of the process according to the inven-
tion that it is possible, in principle, to dispense with
such solvents. The solvents which may be used for the chain
lengthening reaction are the same as those used for preparing
the prepolymers.
LeA 15,933 -15-

4;~
The process according to the invention for preparing
ionically modified polyurethanes may, of course, also be
carried out by the method according to U.S. Patent No.
3,756,992, in which a prepolymer which contains acylated
amino end-groups is first prepared from the NCO prepolymer,
for example, by reacting it with urea, and this prepolymer
with acylated amino groups is then chain lengthened with
formaldehyde by way of the intermediate stage of prepolymers
which contain methylol end-groups.
Preparation of the aqueous dispersions of the pro-
ducts of the process may, of course, also be carried out
with the aid of external emulsifiers although it is one of
the major advantages of the process according to the inven-
tion that the use of such emulsifiers may be omitted.
~ultable e~ui6i~ie~s are e.g. s~lt3 of long chatn ~atty
acids,salts of alkyl aryl sulfonic acids, o~ethylated
alkyl phenols, block copolymers of ethylene oxide and
propylene oxide.
The process according to the invention may, of course,
also be carried out in the presence of conventional catalysts
which accelerate the NCO/OH reaction. A number of ~uch cata-
lysts are discu3sed in "Polyurethanes, Chemistry and Technol-
ogy", supra. and include lead benzoate, stannic chloride,
ferric chloride and triethylene diamine.
The process according to the invention enables high
quality polyurethane-(polyurea) dispersions to be produced
by a simple method using exclusively the principles of the
isocyanate polyaddition reaction. Since the products of the
process contain sulphonate groups as ionic centers, their
aqueous dispersions differ from dispersions of cationic or
Le A 15,933 - 16 -

106104;~
anionic polyurethanes which contain exclusively carboxylate
groups by their substantially higher stability to electro-
lytes and compatibility with pigments. Owing to the need for
protection of the environment, a substitute for the process
for producing PU latices using organic solvents is undoubtedly
desirable if not essential. While maintaining the high quality
of the dispersions normally obtained by a process in which
organic solvents are used, the process according to the
invention may dispense with the readily combustible organic
solvents and thus substantially reduce the risk of explosion
and fire. The process according to the invention ha~ the
further advantage of considerably increasing the volume/time
yields compared with those obtained in the known solvent
process since there are no volumes of solvent to be dealt
with and no energy and time consuming distillation processes
required.
The polyurethane(urea) dispersions prepared by the
process according to the invention are suitable for various
fields of application. For example, they may be used for
dressing leather or for coating various materials and parti-
cularly also for coating textiles. For this purpose, they
may be used ac bonding or top coats. ~hey may also be used
for textile foam coating. Their use as adhesives or lacquers
also constitute important fields of application.
~5 The invention is further illustrated, but is not
intended to be limited by the following examples in which
all parts and percentages are by weight unless otherwise
specified.
LeA 15,933 -17-

XAMPLE 1 iO6~0~3
Reaction mixture:
335.5 g of a polyester of adipic acid, hexanediol and neo-
pentylglycol (molecular weight 1678) (PE),
12.8 g of the sodium salt of propoxylated 3-hydroxy-2-
hydroxymethyl-propane-sulphonic acid-l
(molecular weight: 428~ (AD),
69.6 g of hexamethylene-1,6-diisocyanate,
700 g of deionized and
33.8 g of the sodium salt of ethylene diamino-2-ethane-
sulphonic acid (45% in water) (AAS solution)
Method:
A mixture of the sodium salt (AD) and hexamethylene-
1,6-diisocayante which has previously been stirred for about
5 minutes is added at 70C to the ester (PE) which has been
dehydrated in a vacuum at 120C. The reaction mixture is
stirred at 90C until the NCO value is 2.1~ and the water
and AAS solution are then added one after another with stirring.
A dispersion which has a solids content of 35% and a
viscosity measured in a Ford cup (4 mm nozzle) of 12 seconds
is obtained. The dispersion shows the Tyndall effect in
transmitted light.
The dispersion is suitable for textile coating. It
dries to clear, transparent, elastic films which are
distinguished by exceptionally high resistance to W irradiation.
The reduction in tensile strength at the end of a 400 hour test
is only 60%.
LeA 15,933 -18-

i1043
EXAMPLE 2
Reaction mixture:
335.4 g of a polyester of adipic acid, hexanediol and neo-
` pentylglycol (molecular weight: 1678) (PE),
71.9 g of hexamethylene-1,6-diisocyanate,
16 g of the sodium salt of propoxylated 3-hydroxy-2-
hydroxymethyl-propane-sulphonic acid-l (molecular
weight 428) (AD).
700 g of deionized water and
56.6 g of the sodium salt of ethylenediamino-2-ethanesulphonic
acid (45% in water) (AAS solution)
Method:
Hexamethylene-1,6-diisocyanate is added at 70C to
the ester (PE) which has been dehydrated in a vacuum at 120C,
and-the sulphonate diol (AD) is added about 5 minutes later
at 80C. The reaction mixture is stirred at 90C until the
NCO value is 3.5%. The mixture of deionized water and AAS
- solution is then added with stirring.
~ A dispersion with a solids content of 38% and a Ford
cup viscosity (4mm nozzle) of 12.4 seconds is obtained. The
disperslon shows a Tyndall effect in transmitted light.
The dispersion is suitable for textile coating. It
dries to a clear, translucent elastic film which has excellent
resistance to UV irradiation (4% loss of tensile strength in
r 25 the 400 hour test) and it loses only 10% of its initial tensile
strength after a 14 day hydrolysis test.
Tensile strength: 115 kp/cm2
Elongation at break: 1190%
LeA 15,933 -19-

COMPARISON EX~MPLE ~ ~104
Reaction mixture: ~
212 g of a polyester of adipic acid, hexanediol and
neopentylglycol (molecular weight: 1696) (PE),
37.8 g of hexamethylene-1,6-diisocyanate,
40.1 g of the sodium salt of ethylenediamino-2-ethanesulphonic
acid (45% in water) (AAS solution), and
600 g of deionized water.
Method:
:
Hexamethylene-1,6-diisocyanate is added at 80C to
the ester (PE) which has been dehydrated in a vacuum a~ 120C.
The reaction mixture is stirred at 110C until the NCO value
is 3.3%. The mixture of water and AAS solution is then stirred
in. A coarse dispèrsion with a solids content of 39.4~ is
obtained which sediments within a few minutes to form a mass
which cannot be redispersed.
EXAMPLE 3
Reaction mixture:
;-
428.6 g of a polyester of adipic acid and butane-1,4-diol
(molecular weight: 2143) (AB),
15.2 g of a propoxylated adduct of 2-buter,e-1,4-diol and
NaHSO3 (molecular weight 304) (AD),
87.5 g of 4,4'-diphenylmethanediisocyanate (44),
800 g of deionized water and
42.2 g of the sodium salt of ethylenediamino-2-ethanesulphonic
acid (45% in water) (AAS solution).
LeA 15,933 -20-

iO~;104~
Method:
The adduct (AD) is added at 80C to the ester (AB)
which has been dehydrated in a vacuum at 120C, and the
diisocyanate (44) is then added also at 80C. The reaction
mixture is stirred at 80C until the NCO value is 1.6. The
deionized water is then added, followed by the AAS solution.
Stirring is then continued for about 2 hours. The dispersion
obtained has a solids content of 38%. Its viscosity is about
8000 cP. It may be used as adhesive. It has a peel strength
of 2.2 kp/cm measured on soft PVC. It dries to a transIucent,
clear elastic film.
.
EXAMPLE 4
Reaction mixture:
428.6 g of a polyester of adipic acid and butanediol
(molecular weight 2143) (AB),
18 g of the sodium salt of propoxylated 3-hydroxy-2-
hydroxymethyl-propane-sulphonic acid-l ~molecular
weight 428) (AD),
- 73.2 g of hexamethylene-1,6~diisocyanate,'
800- g of deionized water and
67.6 g of the sodium salt of ethylenediamino-2-ethanesulphonic
acid (45% in water) (AAS solution).
Method: see Example 3
The resulting dispersion has a solids content of
- 25 36.4~. Its Ford cup viscosity (4mm nozzle) is 15 seconds.
It is suitable for use adhesive. It has a peel strength of
3.5 kp/cm determined on soft PVC. It dries to a translucent,
clear eiastic film.
LeA 15,933 -21-
~ . . . . . ... . _ . .

o~;~
EXAMPLE 5
Reaction mixture:
204.3 g of a polyester of adipic acid, hexanediol and neopen-
tylglycol (molecular weight 1634) (PE),
83.2 f of hexamethylene-1,6-diisocyanate,
61.8 g of a propoxylated adduct of 2-butene-1,4-diol and
Na~SO3 (molecular weight 412) (AD),
650 g of deionized water,
11.55 g of ethylene diamine (ADA) and
g of deionized water
Method-
. . .
The hexamethylene-(1,6) diisocyanate is added at
- 70C to the ester (PE) which has been dehydrated in a vacuum at
120C. The mixture is left to react for 10 minutes and then
slowly heated at 80C. It is found to have an NCO value of
about 11~. The adduct (AD) is then added and the mixture
is stirred until the NCO value is about 5.1%. Water at a -
temperature of 80C is stirred in. A mixture of ADA and 30 g
of water is added after about 5 minutes. ~tirring is then
continued for about one hour.
A dispersion with a solids content of 33.3~ and a
viscosity of 2600 cP is obtained. It dries at about 140C
to transparent, clear elastic films. It is suitable for
textile coating.
EXAMPLE 6
Reaction mixture:
978 g of a polyester of phthalic acid, adipic acid and
LeA 15,933 -22-
. . . _ _ _ _

106~043
ethylene glycol (molecular weight 1686) (PAA),
94.3 g of propoxylated adduct of 2-butene-1,4-diol and
NaHSO3 (molecular weight 400) (AD),
197 g of hexamethylene-1,6-diisocyanate,
66.2 g of urea and
2650 g of deionized water.
Method:
The ester ~PAA) is dehydrated in a vacuum at 120C
for 30 minutes and thèn cooled to 90C. The adduct (AD) is
added. Hexamethylene-1,6-diisocyanate is then added at 60C.
The reaction mixture is stirred at a maximum temperature of
100C for 95 minutes and then heated to 120C. Urea is added
and the mixture is left to react for one hour at 125C. It is
then cooled to 100C and water heated to 80C is stirred in.
The mixture is then stirred for about 1 - 2 hours without-heat-
ing. -
The dispersion has a solids content of 32.8% and aFord cup viscosity (4 mm nozzle) of 12 seconds.
~ The dispersion is suitable for use as emulsifier
and as polymerization starter for emulsion polymers ac~ording to
DOS No. 1,953,349. It may subsequently be chain lengthened
with formaldehyde (donors) according to U.S. PS No. 3,756,992
and may be used as primer for dressing leather, for example.
EXAMPLE 7
... .
Reaction mixture:
369.2 g of a polyester of phthalic acid, adipic acid and
ethylene glycol (molecular weight 1686) (PAA),
80.14 g of hexamethylene-1,6-diisocyanate,
- LeA 15,933 -23-

2106143
19.4 g of an adduct of butene-1,4-diol and Li-HSo3
(molecular weight 176) (AD),
18.7 of urea,
1000 g of deionized water and
70 g of formaldehyde (30% in water).
Method:
The ester (PAA) is dehydrated in a vacuum at 120C
for 30 minutes and then cooled to 60C. The diisocyanate is
reacted with the ester for 10 minutes, during which time the
temperature is slowly raised to 80C. The adduct (AD) is
stirred in at 80C and the mixture is heated to 115C. When
the NCO value reaches 2.65%, the temperature is raised to
130C and urea is added. No more free NCO is left after about
one hour. The deionized water (80C) is added at 100C.
Finally, the formaldehyde is added. The mixture is then
stirred for about 1 hour, during which time the temperature
slowly drops to room temperature.
The dispersion has a solids content of 31.2~ and a
Ford cup viscosity (4 mm nozzle) of 18 seconds.
.
~ It is suitable for use as primer for dressing leather.
It dries to transparent, clear elastic films.
EXAMPLE 8
Reaction mixture:
369.2 g of a polyester of p~thalic acid, adipic acid and
etl~ylene glycol (molecular weight 1686) (PAA),
82.1 g of hexamethylene-1,6-diisocyanate,
22.88 g of the lithium salt of 3,4-dihydroxy-butane-sulphonic
acid (AD) (molecular weight 176),
LeA 15,933 -24-

1061~
17.6 g of urea,
1000 g of deionized water and
g of formaldehyde (30% in water)
Method: see Example 7
The dispersion has a solids content of 31.3% and a
Ford cup viscosity (4 mm nozzle) of 17 seconds.
Instead of 22.8 g of the adduct (AD), 24.3 g of the
analogous ammonium salt which has a molecular weight of 187
may be used. A dispersion with a solids content of 31.5% and
a Ford cup viscosity (4 mm nozzle) of 17 seconds is obtained.
Both dispersions are suitable for use as primers
for dressing leather. Both show a Tyndall effect in transmitted
light. They dry to clear, elastic films.
EXAMPLE 9
Reaction mixture:
326.8 g of a polyester of adipic acid, hexanediol and
neopentyl glycol (molecular weight: 1634) (PE),
71.8~g of hexamethylene-1,6-dii~ocyanate,
6.99 g of an adduc~ of 2-butene-1,4-diol and NH4-HSO3
(molecular weight: 187) (AD),
650 g of deionized water and
54.9 g of the sodium salt of ethylenediamino-2-ethanesulphonic
acid (45% in water) (AAS solution).
~- Method: see Example 2
A finely-divided, non-sedimenting dispersion with a
solids content of 32.55% and a Ford cup viscosity (4 mm nozzle)
of 13.3 seconds is obtained.
LeA 15,933 -25-
~ . . _ _ . . .... . . .. . . . _ _ _ . _

10610~;~
Tlle dispersion dries to cl~ar, tran~slucent elastic
r i lms . 1 t iS suita~ or tex~ile ~oatinq.
:
EX~I'LI 10
React_on mixtu~-e.
326.8 g of a poLyester of adipic ~cid, hexanediol an~l
neopetltyl glycol (molecular weight: 1634) (PE),
71.8 g of hexamethylene-1,6-diisocyanate,
11.52 g of a propoxylated adduct of 1-butene-3,4-diol and
Nal~S03 (molecular weight: 308) (AD),
650 g of deionized water and
g of the sodium salt of ethylenediamino-2-ethanesulphonic
acid (45% in water) (ASS solution).
~ethod: see Example 2
A finely-divided dispersion with a solids content of
35.8% and a Ford cup viscosity (4 mm nozzle) of 14 seconds is
obtained.
The dispersion dries to clear, translucent elastic
films. It is suitable for textile coating.
Tensile strength: 35 kp/cm3
Elongation at break: 810%
Although the invention has been described in detail
in the foregoing for the purpose of illustration, it is to be
understood that such detail is solely for that purpose and
that variations can be made therein by those skilled in the
art without departing from the spirit and scope of the invention
except as it may be limited by the claims.
LeA 15,933 -26-
.~ .