Note: Descriptions are shown in the official language in which they were submitted.
21~8550
HYDROPHILIC POLYURETHANE-POLYUREAS AND THEIR USE AS
DISPERSANTS FOR SY~.~nh-~lC RESINS
Background of the Invention
Field of the Invention
The present invention relates to hydrophilic
polyurethane-polyureas and to their use, for example, as
emulsifiers in aqueous dispersions of hydrophobic
synthetic resins.
Description of Related Art
The range of water-dilutable binder systems is at
present still incomplete, so that at present the
replacement of all conventional coating compositions with
water-based systems is still not possible. In
particular, the air-drying alkyd resins, which are
generally employed in the form of solutions in aliphatic
or aromatic hydrocarbons, still cannot be replaced by
fully equivalent water-based compositions. Films of
aqueous dispersions of polymers, based, for example, on
polyvinyl acetate, polyolefins, or polyacrylates, fall
well short of the quality standard of conventional alkyd
resins both in their visual impression (evenness, gloss)
and in their protective effect (water resistance, weather
resistance).
Water-soluble alkyd resins for air-drying coating
materials have also so far failed to become established.
Part of the reason for this is that the average molecular
mass of the resins has to be lowered to achieve water-
solubility, which unavoidably retards the drying.
Moreover, despite their low molecular mass, these resins
require relatively large quantities of auxiliary solvents
(for example, glycol ethers, which are also toxic
solvents) and organic amines.
~ ~14~$~0
In contrast to these water-soluble resins, aqueous
dispersions of synthetic resins, especially alkyd resins
should enable an ideal solution to the problem, since in
this case it is generally possible to do away with
s organic solvents. Also the drying properties would be
expected to match those of the conventionally dissolved
resins, since it is unnecessary to limit the molecular
mass as for the water-soluble resins. Despite this,
synthetic resin dispersions of this kind have likewise
not hitherto acquired any great significance. The reason
is that to date there has not been a successful solution
to the problem of stabilizing the dispersions without
adversely affecting the other properties.
Synthetic resins, especially alkyd resins, are
predominantly hydrophobic substances which do not per se
form stable dispersions in water. It is therefore
necessary to add emulsifiers. Emulsifiers are generally
substances having an amphipathic molecular structure,
i.e., they are composed of a hydrophobic and a hydro-
philic moiety. As a result of this structure the
emulsifier molecules accumulate at the water/resin
interface, reduce the interfacial tension, and thus
enable the formation of very fine resin droplets in the
aqueous phase.
The synthesis of high molecular weight polyurethane-
polyureas by chain extension in the aqueous phase is
known and is described generally, for example, in
DE-A 26 24 442 and in EP-A 0 089 497. The suitability of
specific polyurethane-polyureas as emulsifiers, however,
was not known.
For synthetic resin dispersions, the best results
achieved up to now have been with nonionic emulsifiers
formed by condensation of ethylene oxide with octyl- or
nonylphenol, i.e., in which the hydrophobic moiety is
composed of the alkylphenol radical and the hydrophilic
moiety is composed of the polyethylene glycol chain.
Systems of this kind are described in U.S. Patents
3,223,658, 3,269,967, and 3,440,193 and in DD Patent
88 883 and DE-A 27 54 091. Emulsifiers of this kind,
~148550
_ -3-
added in quantities of from 5 to 10%, give synthetic-
resin dispersions of serviceable stability. The
disadvantage is that these emulsifiers remain unchanged
in the film and thus bring about a significant reduction
in the water resistance. The scope for application of
such dispersions is therefore very restricted.
DE-A 39 00 257 describes nonionically hydrophilic
polyurethanes which have (meth)acryloyl groups and their
use as reactive emulsifiers for urethane (meth)acrylates
which are not dispersible in water. With these
emulsifiers, however, only a limited number of synthetic
resins can be emulsified. For instance, owing apparently
to their deficient compatibility, they are unable to
emulsify styrene-free unsaturated polyester resins or
alkyd resins.
DE-A 40 04 641 describes air-drying polyurethane
resins which contain both polyols and monoalcohols having
polyunsaturated groups. Up to 40% of conventional alkyd
resins can be incorporated into these resins by
emulsification. German Patents DE 27 54 141, DE
27 54 092 and DE 24 40 946 describe alkyd resin
dispersions which are stabilized in the aqueous phase
using emulsifiers which comprise polyethylene glycols,
fatty acids, andtor allyl ethers.
Olefinically unsaturated polyurethanes comprising a
~,~-ethylenically unsaturated ether alcohol component are
described in EP-A 0 501 247, as is their use as reactive
emulsifiers. They are predominantly employed as
emulsifiers for unsaturated polyester resins, and are
unsuitable for alkyd resins. Owing to their double
bonds, these emulsifiers can be incorporated into the
film during oxidative drying, thereby improving the water
resistance. The low molecular mass of these emulsifiers,
however, permits limited migration of the emulsifiers in
the film, as a result of which the properties of the
resulting film suffer.
A further problem of these alkyd resin emulsions, in
addition to slow drying, is their poor pigmentability,
since it is generally not impossible with the above-
`~ _4_ 21~85~
described emulsions to obtain glossy, highly pigmented
films.
SummarY of the Invention
An object of the invention was therefore to develop
emulsifiers which are able to stabilize hydrophobic
synthetic resins in the form of dispersions in water and
which do not adversely affect the properties of the films
formed after drying, especially with respect to gloss,
drying, weather resistance and water resistance.
Another object of the present invention was to
provide aqueous synthetic-resin dispersions having
storage stability, pigmentability and drying properties
which are improved in relation to the known prior art.
These objects have been achieved by the provision of
the hydrophilic polyurethane-polyureas of the invention
and by their use according to the invention.
In particular, in accordance with the present
invention, there are provided hydrophilic polyurethane-
polyureas which are obtained by reacting:
(A) a polyisocyanate component comprising at least one
organic polyisocyanate,
(B) at least one isocyanate-reactive fatty acid
derivative,
(C) optionally, a compound other than (B), (D) and (E),
containing more than two functional groups selected
from hydroxyl and carboxyl groups,
(D) a polyalkylene glycol component having a molecular
mass in the range from 500 to 10,000 g/mol, and
(E) a compound having at least one active hydrogen atom
which reacts faster than water with NCO groups,
while maintaining a molar ratio of isocyanate groups to
the sum of hydrogen atoms of the isocyanate-reactive
groups, (such as hydroxyl and amino) based on all of the
starting components (A) to (E), of from 0.5:1 to 2:1,
preferably from 0.7:1 to 1.5:1.
In accordance with another aspect of the invention,
there has been provided an aqueous dispersion comprising
214855~
_ -5-
a hydrophobic synthetic resin and a hydrophilic
polyurethane-polyurea as described above as an
emulsifier.
In accordance with the invention, there has also
been provided a coating composition comprising the poly-
urethane-polyurea and a substrate coated therewith.
Further objects, features, and advantages of the
invention will become apparent from the detailed
description of preferred embodiments that follows.
Detailed Description of Preferred Embodiments
The present invention provides aqueous dispersions
of polyurethane-polyureas that are useful as reactive
emulsifiers for synthetic resins which are otherwise not
dispersible in water, and aqueous dispersions that
contain synthetic resins that are otherwise not
dispersible in water.
The synthetic resins employed include any desired
resins or mixtures thereof, and are preferably any
commercial alkyd resin grades. The alkyd resins may be
modified slightly in order to increase stability on
storage.
The resin dispersion may be prepared in any desired
manner. In general, for the preparation of the
dispersions, the resins are generally employed in the
solvent-free state, although relatively small quantities
of solvent may also be added. The amount of solvent must
not exceed 10 % of the mass of the resin, preferably less
than 5 % is used, most preferred less than 2 %.
To increase its storage stability, the alkyd resin
can be modified such that its acid number is as low as
possible. This modification can either be carried out
during the preparation of the alkyd resin, by esterifi-
cation with further alcohols, or else the acid groups can
be esterified subsequently using an epoxide. Suitable
epoxides include all monoepoxides, which are described,
for example, in the handbook "Epoxidverbindungen und
Epoxidharze" [Epoxide compounds and epoxy resins] by
21485S~
--6--
A.M. Paquin, Springer Verlag, Berlin 1958, chapter IV,
and in Lee Neville "Handbook of Epoxy Resins", 1967,
chapter 2. Particularly suitable are epoxidized fatty
acids and Cardura~ E10 (Versatic acid glycidyl ester from
Shell Chemie). However, it is possible to use any type
of alkyd resin, either alone or in combination with other
resins which are to be dispersed. Also, resins other
than alkyd resin can also be dispersed in water by use of
the emulsifier of the present invention.
The polyurethane-polyureas according to the
invention can be prepared by reacting the starting
components (A) to (E) mentioned above in proportions
suitable to give a polyurethane-polymer resin.
Preferably from 0.1 to 1 mol of component (B), from 0 to
0.8 mol of component (C), from 0.1 to 0.8 mol of
component (D) and from 0.01 to 0.3 mol of component (E)
are employed per mole of component (A). It is
particularly preferred to employ from 0.2 to 0.6 mol of
component (B), from 0 to 0.6 mol of component (C), from
0.2 to 0.6 mol of component (D), and from 0.02 to
0.25 mol of component (E) per mole of component (A).
Component (A) comprises at least one organic
polyisocyanate. Any desired polyisocyanates, include
resins including isocyanate groups, or mixtures of
polyisocyanate can be used. Suitable polyisocyanates for
the invention include aliphatic, cycloaliphatic, and/or
aromatic polyisocyanates containing at least two
isocyanate groups per molecule and having a molecular
mass of from 168 to 1,000 g/mol, preferably from 168 to
300 g/mol. Preference is given to compounds having from
two to four isocyanate groups per molecule, and
particular preference to those having two or three
isocyanate groups per molecule. Mixtures of different
polyisocyanates can also be used, in which case it is
also possible to mix polyisocyanates of different
functionalities. It is preferred to use diisocyanates
which may contain up to 20 mol % of higher-functional
isocyanates as a further constituent of the mixture.
21485~0
_ 7
Suitable aromatic polyisocyanates include the
isomers or isomer mixtures of phenylene diisocyanate,
tolylene diisocyanate, xylylene diisocyanate, biphenylene
diisocyanate, naphthylene diisocyanate and diphenyl-
methane diisocyanate, and biphenyl tetraisocyanate,preferably naphthyl tetraisocyanate, tolylene diiso-
cyanate, and xylylene diisocyanate.
Examples of useful cycloaliphatic polyisocyanates
include isophorone diisocyanate (l-isocyanato-3,3,5-
trimethyl-5-isocyanatomethylcyclohexane, "IPDI"), cyclo-
pentylene diisocyanate, and the hydrogenation products of
aromatic diisocyanates, such as cyclohexylene diiso-
cyanate, methylcyclohexylene diisocyanate, and dicyclo-
hexylmethane diisocyanate.
Examples of aliphatic polyisocyanates are
diisocyanates of the formula
O = C = N - (CR2)r - N = C = O
in which r is an integer from 2 to 20, in particular from
6 to 8, and R is hydrogen or a lower alkyl radical having
from 1 to 8 carbon atoms, preferably 1 or 2 carbon atoms.
Examples of these include trimethylene diisocyanate,
tetramethylene diisocyanate, pentamethylene
diisocyanate, hexamethylene diisocyanate, propylene
diisocyanate, ethylethylene diisocyanate,
dimethylethylene diisocyanate, methyltrimethylene
diisocyanate, and trimethylhexane diisocyanate.
Particular preference is given to diphenylmethane
diisocyanate and tolylene diisocyanate and to the isomer
mixtures thereof, and to isophorone diisocyanate,
dicyclohexylmethane diisocyanate, trimethylene
diisocyanate, tetramethylene diisocyanate, and
hexamethylene diisocyanate. Vinyl polymers which contain
isocyanate groups and are formed by copolymerization of,
for example, cyanatoethyl (meth)acrylate or dimethyl-
isopropylbenzyl isocyanate with alkyl (meth)acrylatesand/or (alkyl)vinylbenzenes can also be used. Mixed
aliphatic/aromatic isocyanate compounds are similarly
~14~5~0
_ 8
suitable. One example of a particularly preferred
compound is tetramethylxylylene diisocyanate.
Diisocyanates of the type specified later by way of
example are preferred as component (A), although
polyisocyanates of higher functionality, for example,
biuret-, isocyanurate- or urethane-modified
polyisocyanates based on the above-mentioned simple
diisocyanates are also suitable. These derivatives
generally have a molecular mass of up to 1000 g/mol. The
preparation of such derivatives is described in, for
example, U.S. Patents No. 3,124,605, No. 3,183,112, No.
3,919,218, and No. 4,324,879, each of which is
incorporated by reference.
The isocyanate-reactive fatty acid derivative (B)
may be any such compound. By "derivative" it is meant
that the fatty acid has been modified to contain groups
which are reactive with isocyanate groups. Any type of
compound so modified can be used. Preferred compounds
contain from 10 to 40 carbon atoms, at least one hydroxyl
or amino group and, if desired, at least one C=C double
bond. The number of isocyanate-reactive functional
groups is generally from one to four, preferably one or
two. Examples of these fatty acid derivatives include
fatty alcohols such as lauryl alcohol, stearyl alcohol,
oleyl alcohol, linoleyl alcohol, or linolenyl alcohol.
Ethoxylated fatty alcohols containing from 1 to 30,
preferably 1 to 20, and more preferably from 1 to 10,
ethylene oxide units can also be employed, for example,
GenapolX 0-020 (Hoechst AG).
Further useful compounds are the alcohols which are
obtained by reacting an unsaturated acid with an epoxide,
such as a monoepoxide, for example, a fatty acid such as
linseed oil fatty acid or soy oil fatty acid with an
epoxide such as Cardura0 E10 or other epoxides. Partial
esters of polyhydroxy compounds, for example, glycerol,
trimethylolpropane or pentaerythritol, and partially
hydrolyzed fats can also be employed, examples being
Ligalub0 40/1 (fatty acid glycerol monoester from
214855~
g
P. Graeven Fettchemie). Also suitable are fatty amines
such as, for example, Genamin~ (Hoechst AG).
Component (C) is an optional component and is any
compound which is of relatively high functionality and
contains more than 2, generally from 3 to 8, particularly
preferably from 3 to 6, hydroxyl and/or carboxyl groups.
In this context it is possible to use those compounds
which contain only hydroxyl groups. Useful examples
include trimethylolpropane, trimethylolethane, glycerol,
ditrimethylolpropane, pentaerythritol, and dipenta-
erythritol. Other suitable compounds contain at least
one, preferably from one to three and particularly
preferably one or two hydroxyl groups and at least one,
preferably from one to three and particularly preferably
one or two carboxyl groups. Suitable hydroxycarboxylic
acids are, for example, bishydroxyalkane carboxylic
acids, dimethylolpropionic acid, glycolic acid, malic
acid, tartaric acid, tartronic acid, citric acid, and
2,6-dihydroxybenzoic acid. Compounds containing only
hydroxyl groups are also useful. Similarly, mixtures of
two or more of these compounds may also be used.
Component (D) comprises one or more polyalkylene
glycols, which are preferably linear, having a number-
average molecular mass of from 500 to 10,000 g/mol,
preferably from 1,000 to 6,000 g/mol. Any such glycols
are useful. Preference is given to polyalkylene ether
glycols which have a content of ethylene oxide units of
at least 80 mol %, preferably up to 100 mol %, of the
alkylene oxide units. "Mixed" polyalkylene glycols of
this kind are formed, for example, by using mixtures of
different alkylene oxides, for example, ethylene oxide
and propylene oxide in a molar ratio of from about 8 to
2, for the preparation of the polyether glycols by
alkoxylation of appropriate divalent initiator molecules
&uch as, for example, water, ethylene glycol, or
propylene glycol.
The compounds employed as component (E) are those
which are also called "chain extenders" in the art. Any
compounds having at least one active hydrogen atom which
~1~855~
--10--
reacts faster than water with NC0 is useful. The
functional groups of these compounds may be hydroxyl
groups, primary and secondary amino groups, and/or
mercapto groups. The number of functional groups is at
least one, preferably from two to four and particularly
preferably two or three. The suitable compounds may
carry only one kind of functional group or may carry
different functional groups in the same molecule.
Examples include primary and secondary amines, hydrazine,
and substituted hydrazines having at least two
isocyanate-reactive hydrogen atoms. Particular
preference is given to diamines and polyamines, examples
being ethylenediamine, butylenediamine, tolylenediamine,
isophoronediamine, 3,3'-dichlorobenzidine, triethylene-
tetramine, diethylenetriamine, hydrazine, and substituted
hydrazines such as dimethylhydrazine. Examples of
further suitable chain extenders which carry different
functional groups are alkanolamines such as N-aminoethyl-
ethanolamine, ethanolamine, and diethanolamine.
Carboxyl-containing amines or hydrazine derivatives, for
example, lysine, glutamic acid, and adipic acid mono-
hydrazide, may also be used. Similarly, mixtures of such
compounds can also be employed.
The hydrophilic polyurethane-polyureas of the
invention may be prepared in any desired manner, but are
preferably prepared in two steps. First, a hydrophilic
isocyanate-functional prepolymer is synthesized which
then, after dispersion in water, is reacted with the
chain extenders described under (E).
The preparation of the prepolymer by reacting the
above-mentioned starting components (A) to (D) may be
carried out in bulk or in solvents which are inert toward
isocyanate groups, such as ketones, tertiary alcohols,
ethers or esters, specific examples being acetone, methyl
ethyl ketone, ethyl acetate, butyl acetate, or toluene,
or mixtures of such solvents, while maintaining preferred
reaction temperatures of from 20 to 200C, in particular
from 50 to 150C. In this context, components (B) to (D)
can be reacted with component (A) simultaneously or in
2148~5~
steps. In practice, for example, one possible procedure
is to introduce components (B) to (D) as initial charge
and to react them within the above-mentioned temperature
ranges with the isocyanate (A) until the NC0 content has
fallen to a specific value, which requires calculation.
This prepolymer is then dispersed in water and
reacted with component (E) at temperatures of, for
example, from 40 to 100C. After a reaction period of,
for example, from 1 to 5 hours and, if desired, after
adding ammonia or amines, the aqueous dispersion of the
polyurethane-polyurea is obtained.
In this context, in principle, the nature and
proportions of the starting components are chosen within
the above-mentioned ranges such that the ratio of the
number of isocyanate groups to the number of hydrogen
atoms in hydroxyl groups and amino groups in components
(A) to (D) is from 0.5:1 to 2:1, preferably from 0.7:1 to
1.5:1.
The urethane formation reactions can be catalyzed in
a manner known per se, for example, by tin octoate,
dibutyltin dilaurate, or tertiary amines. Likewise, the
polyurethane can be protected against premature and
unwanted polymerization and/or oxidation by addition of
appropriate inhibitors and antioxidants, respectively, in
quantities of in each case from of, for example, 0.001 to
0.3% based on the mass of the overall mixture.
The hydrophilic polyurethane-polyureas, possibly
containing unsaturated groups, which are obtained in this
way have a number-average molecular mass Mn (which can be
determined by the method of gel permeation chromatography
using polystyrene as standard) which can be varied
depending on intended use of the polymer, and which is
generally from 2,000 to 20,000 g/mol, preferably from
2,000 to 15,000 g/mol. A content by mass of olefinic
double bonds (calculated as -C=C-, molecular mass =
24 g/mol) is generally from 0 to 6%, preferably from 1 to
4%, and a content by mass of ethylene oxide units
-CH2-CH2-0-, incorporated by way of polyethylene glycol,
21485~0
_ -12-
is generally from 20 to 90%, preferably from 30 to 85~,
and with particular preference from 40 to 80%.
These hydrophilic polyurethane-polyureas can be used
/ in any desired number, and are valuable emulsifiers for
hydrophobic synthetic resins which are not dispersible by
themselves in water. Such synthetic resins have, for
example, a number-average molecular mass Mn (determined
as above) of from 500 to 10,000 g/mol, preferably from
500 to 5,000 g/mol.
The synthetic resin dispersions may be prepared in
any desired manner. For example, to prepare such
synthetic-resin dispersions, the synthetic resins are
first of all mixed with the above-described polyurethane-
polyurea dispersions, if desired in the presence of the
inert solvents described above. The mixtures generally
contain from 20 to 97 parts by weight, preferably from 40
to 95 parts by weight, of the above-identified
hydrophobic synthetic resins as a mixture with from 3 to
80 parts by weight, preferably from 5 to 60 parts by
weight, of the above-mentioned, emulsifying, hydrophilic
polyurethane-polyureas. It is, however, important to
select the nature and proportions of the individual
components, within the framework of the statements which
have been made, in such a way that the content by mass of
ethylene oxide units originating from component (D) in
the water-dispersible mixtures is not more than 20%,
preferably not more than 15%. The mixtures can be
prepared simply by mixing the individual components, if
desired in the presence of further solvents such as, for
example, hydrocarbons, alcohols, ketones, glycol ethers,
or N-methylpyrrolidone.
To prepare the aqueous synthetic-resin dispersions
of the invention, the mixtures according to the invention
are dispersed in water, either by simply stirring water
into the mixture of the synthetic resins with the
polyurethane-polyurea dispersions, using conventional
dissolvers, or by pouring the mixture into water with
vigorous stirring. If desired, it is possible first to
add some of the water to the above-described mixture and
~14855~
-13-
then to pour this mixture, with stirring, into the
remaining quantity of water. In this way it is possible
to obtain stable oil-in-water emulsions.
The aqueous dispersions which are obtained in this
way are valuable aqueous binders for coating
compositions. They can be used as such or in combination
with auxiliaries and additives which are known from paint
technology, for example, fillers, pigments, solvents,
and/or leveling aids, to produce coatings on any desired
substrates.
Through the use of the emulsions according to the
invention, aqueous dispersions of alkyd resins with an
alkyd content of up to 60% by mass can be prepared. A
typical alkyd content is 25 through 55~ .
Examples of suitable substrates include, for
example, paper, cardboard packaging, leather, wood,
plastics, nonwovens, films, textiles, ceramic materials,
mineral materials, glass, metal, coated metal, synthetic
leather, and photographic materials such as, for example,
paper bearing a photographic layer.
These coating compositions can be applied in any
known manner, for example, by spraying, knife coating,
rolling, brushing, dipping, or flow coating. After
evaporation of the water and of any inert solvents which
may have been used in addition, the crosslinking of the
coatings can take place, for example, by curing with
metal salts of siccative acids and (hydro)peroxides or
other siccatives at temperatures between room temperature
and 250C.
The present invention is illustrated by the
following, non-limiting examples. In the examples below,
all quantities should be read as masses and all
percentages as contents by mass.
Examples: Preparation of the polyurethane-polyurea
disper~ions
a I ~f855~
- -14-
Example E 1
56 g of linseed oil fatty acid and 52 g of Cardura~
E10 (glycidyl esters of neodecanoic acid) (catalyst:
chromium octoate) are reacted at 120C until an acid
number of c 1 mg KOH/g is reached (raw material III).
54 g of dimethylolpropionic acid are dissolved at about
80C in 200 g of polyethylene glycol 1000. 100 g of
Solvesso0 100 mixture of branched aliphatic hydrocarbons
with medium boiling range and the raw material III are
added to the solution. Then, after heating to 80C, 98 g
of tetramethylxylylene diisocyanate (TMXDI) and 70 g of
tolylene diisocyanate are added dropwise at a rate such
that the temperature does not exceed 85C (about 30 min).
Once all the isocyanate has been added, the mixture is
subsequently stirred at temperature for one hour and then
the reaction temperature is raised to 90C. The
temperature is maintained until the isocyanate content
has fallen to 1.59%. 1400 g of heated, deionized water
are then added over the course of 10 minutes with
vigorous stirring. This is followed immediately by the
rapid dropwise addition (over about 5 min) of 7.5 g of
triethylenetetramine dissolved in 75 g of water. After
a reaction period of 3 hours at 80C, 5 ml of 25%
strength ammonia solution are added, and then the mixture
is cooled. A pasty dispersion is obtained.
Example E 2
14 g of dimethylolpropionic acid are suspended at
about 80C in 100 g of polyethylene glycol with a molar
mass of 1000 g/mol. 100 g of Solvesso0 100 and 59 g of
Genapol0 O-100 (ethoxylated fatty alcohol) are added to
the suspension. Then, after heating to 70C, 27 g of
tetramethylxylylene diisocyanate (TMXDI) and 35 g of
tolylene diisocyanate (TDI) are added dropwise at a rate
such that the temperature does not exceed 70C (about
30 min). Once all the isocyanate has been added,
stirring is continued at temperature for one hour and
then the reaction temperature is raised to 90C. The
temperature is maintained until the isocyanate content
214855~
_ -15-
has fallen to 1.7%. 500 g of heated, deionized water are
then added over the course of 10 minutes with vigorous
stirring. This is followed immediately by the rapid
dropwise addition (over about 5 min) of 3.75 g of
triethylenetetramine dissolved in 37.5 g of water. After
a reaction period of 3 hours at 80C, 5 ml of 25%
strength ammonia solution are added and the mixture is
cooled. A pasty dispersion is obtained.
Example E 3
59 g of Genapol~ O-100 are mixed with 200 g of
polyethylene glycol with a molar mass of 2000 g/mol, and
the mixture is heated to 70C. 100 g of SolvessoX 100
are added to the solution. After the mixture has been
heated to 70C, 54 g of tetramethylxylylene diisocyanate
(TMXDI) are then added dropwise at a rate such that the
temperature does not exceed 70C (about 30 min). Once
all the TMXDI has been added, stirring is continued at
temperature for one hour and then the reaction
temperature is raised to 90C. The temperature is
maintained until the isocyanate content has fallen to
1.4%. 500 g of heated, deionized water are then added
over the course of 10 minutes with vigorous stirring.
This is followed directly by the rapid dropwise addition
(over about 5 min) of 3.75 g of triethylenetetramine
dissolved in 37~5 g of water. After a reaction time of
3 hours at 80C the mixture is cooled. A pasty
dispersion is obtained.
Example E 4
14 g of dimethylolpropionic acid are suspended at
about 80C in 100 g of polyethylene glycol with a molar
mass of 1000 g/mol. 100 g of Solvesso~ 100 and 59 g of
GenapolX O-100 (ethoxylated fatty alcohol) are added to
the suspension. The mixture is heated to 70C and then
27 g of tetramethylxylylene diisocyanate (TMXDI) and 35 g
of tolylene diisocyanate (TDI) are added dropwise at a
rate such that the temperature does not exceed 70C
(about 30 min). Once all the isocyanate has been added,
- 21~85~ ~
-16-
stirring is continued at temperature for one hour and
then the reaction temperature is raised to 90C. The
temperature is maintained until the isocyanate content
has fallen to 1.7%, and 100 g of Solvesso~ 100 are added.
Then 500 g of heated, deionized water are added over the
course of 10 minutes with vigorous stirring. This is
followed immediately by the rapid dropwise addition (over
about 5 min) of 3.75 g of triethylenetetramine dissolved
in 37.5 g of water. After a reaction period of 3 hours
at 80C, 5 ml of 25% strength ammonia solution are added
and the mixture is cooled. A pasty dispersion is
obtained.
Example E 5
27 g of dimethylolpropionic acid are suspended at
about 80C in 100 g of polyethylene glycol 1000. 50 g of
Solvesso0 100 and 27 g of Genamin~ OL 100 (ethoxylated
fatty amine) are added to the suspension. The mixture is
heated to 70C and then 51.2 g of tetramethylxylylene
diisocyanate (TMXDI) and 37 g of tolylene diisocyanate
(TDI) are added dropwise at a rate such that the
temperature does not exceed 70C (about 30 min). Once
all the isocyanate has been added, stirring is continued
at temperature for one hour and then the reaction
temperature is raised to 90C. The temperature is
maintained until the isocyanate content has fallen to
1.1%. Then 400 g of heated, deionized water are added
over the course of 10 minutes with vigorous stirring.
This is followed immediately by the rapid dropwise
addition (over about 5 min) of 3.75 g of
triethylenetetramine dissolved in 37.5 g of water. After
a reaction period of 3 hours at 80C, 5 ml of 25%
strength ammonia solution are added and the mixture is
cooled. A pasty dispersion is obtained.
Example D 1
140 g of the emulsifier E 1 are added to 200 g of a
commercial alkyd resin having an oil content of 68%
(e.g., AlftalatX AR 680 100% alkyd resin based on
~148553
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.
ricinene oil, oil length = 68) and the mixture is stirred
at 70C for about 30 minutes until it is homogeneous.
Following the addition of 1 ml of 25% strength aqueous
ammonia, 200 g of deionized water heated to 70C are
added dropwise very slowly (about 3 hours) with vigorous
stirring. A milky, structurally viscous dispersion is
obtained.
Example D 2
140 g of the emulsifier E 4 are added to 200 g of a
commercial alkyd resin having an oil content of 56%
(Alftalat~ SAS 560 100% alkyd resin based on soy bean
oil, oil length = 56) which has been reacted with
CarduraX E10 to an acid number of below 1 mg of KOH per
g of resin and the mixture is stirred at 70C for about
30 minutes until it is homogeneous. Following the
addition of 1 ml of 25% strength aqueous ammonia, 200 g
of deionized water heated to 70C are added dropwise very
slowly (about 3 hours) with vigorous stirring. A milky,
structurally viscous dispersion is obtained.
Example D 3
140 g of the emulsifier E 4 are added to 200 g of a
commercial alkyd resin having an oil content of 63%
(Alftalat~ AS 632 100% alkyd resin based on soy bean oil,
oil length = 63) which has been reacted with Cardura2 E10
to an acid number of below 1 and the mixture is stirred
at 70C for about 30 minutes until it is homogeneous.
Following the addition of 1 ml of 25% strength
aqueous ammonia the mixture is poured with vigorous
stirring into water heated at 70C.
Example D 4
140 g of the emulsifier E 4 are added to 200 g of a
commercial oil-free polyester having an OH number of 115
and an acid number of 5 (Alftalat~ AN 950, oil length =
95) and the mixture is stirred at 70C for about
30 minutes until it is homogeneous.
214855 0
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Following the addition of 1 ml of 25% strength
aqueous ammonia, 200 g of deionized water heated to 70C
are added dropwise very slowly (about 3 hours) with
vigorous stirring. A milky, structurally viscous
dispersion is obtained.
All of the other emulsifiers listed are processed in
accordance with the above-described examples to give
dispersions.
While the invention has been described with
reference to certain preferred embodiments, numerous
modifications, alterations, and changes to the preferred
embodiments are possible without departing from the
spirit and scope of the invention.
